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ASPHALTS 

AND 

ALLIED SUBSTANCES 

Their Occurrence, Modes of Production, 
Uses in the dirts and Methods of Testing 

BY 
HERBERT ABRAHAM 

President^ The Rnberoid Co.; President ', Asphalt Shingle and 

Roofing Industry 



FOURTH EDITION 




NEW YORK 

D. VAN NOSTRAND COMPANY, INC. 

250 FOURTH AVENUE 



Copyright, 1918 and 1920, 

BY 
D. VAN NOSTRAND COMPANY 



Copyright, 1929, 1938 by 
D. VAN NOSTRAND COMPANY, INC. 



All rights reserved. No part of this book may 
be reproduced in any form without permission 
in writing from the publisher, except by a 
reviewer who may quote brief passages in a 
review to be printed in a magazine or newspaper. 



First Published, August 1918 



Second Edition, August 1920 



Third Edition, November 1929 

Reprinted, April 1932 



Fourth Edition, January 1938 



PRINTED IN U. 3. A. 



PRESS OF 

BRAUNWORTH & CO.. INC. 
BUILDERS OF BOOKS 
BRIDGEPORT. CONN. 



PREFACE TO FOURTH EDITION 

The present edition of "Asphalts and Allied Substances" has 
been revised in several material respects. Although in the main, 
the textual sequence of the earlier editions has been followed, the 
subject matter has been amplified so as to cover the ground more 
intensively from the earliest dawn of civilization, down to the very 
last word in this rapidly growing branch of technology. 

Several new chapters have been added. The section relating to 
"Methods of Testing" has been completely rewritten to conform 
with the most recent practices. References to patents and to the gen- 
eral literature have been brought up to date, and more than 12,000 
such citations have been segregated in an appendix at the end of the 
volume, where they would not interfere with the continuity of the 
text and yet be readily accessible to the interested reader. The "Bib- 
liography" has likewise been expanded to embrace more than 900 
treatises. 

No effort has been spared to make this new edition as compre- 
hensive as the limitations of space and the author's available time 
have permitted. 

HERBERT ABRAHAM. 

NEW YORK CITY, 

September 15, 1937. 



PREFACE TO THIRD EDITION 

During the decade which has elapsed since the publication of the 
Second Edition of <4 Asphalts and Allied Substances/' the technology 
of bituminous substances has made great strides under the pressure 
of rapidly increasing production. The output of crude petroleum 
has not only increased- by leaps and bounds, but has gravitated to- 
wards oil-fields yielding a greater percentage output of asphalt. Sim- 
ilarly, coal tar and coal-tar pitch have been produced in larger 
amounts, because of the widespread introduction of equipment for 
recovering these valuable by-products. 

Accordingly, the supply of petroleum asphalt and coal-tar resid- 
uals has more than kept pace with their utilization in the arts, and 
this has been reflected by a substantial reduction in their market 
price. Not only has this condition rendered these substances avail- 
able to a larger consuming field, but it has also served to stimulate 
inventors to adapt them to new uses. 

The increasing commercial importance of bituminous substances 
has been evidenced by greater efforts to perfect and standardize 
their methods of test, through such agencies as The Federal Speci- 
fication Board (organized by the United States Government), and 
many scientific societies, including especially the American Society 
for Testing Materials, through w r hose courtesy the author has been 
given permission to reprint their specifications and tests in this book. 

To keep pace with this rapidly developing art, it has accordingly 
been necessary to rewrite the book completely, and thereby bring it 
up-to-date. 

HERBERT ABRAHAM 

NEW YORK Cn% 
November i, 1929* 



vii 



PREFACE TO FIRST EDITION 

This treatise has been written for those interested in the fabrica- 
tion, merchandising and application of bituminous products. It 
embraces: (i) methods serving as a guide for the works chemist 
engaged in testing and analyzing raw and manufactured products; 
(2 ) data for assisting the refinery or factory superintendent in blend- 
ing and compounding mixtures; (3) information enabling the am- 
bitious salesman to enlarge his knowledge concerning the scope and 
limitations of the articles he vends; and (4) the principles underly- 
ing the practical application of bituminous products for structural 
purposes, of interest to the engineer, contractor and architect. Sub- 
ject-matter of sole value to the technical man has been segregated in 
Part V, u Methods of Testing," excepting the outline of the "Chem- 
istry of Bituminous Substances" appearing in Chapter III. These 
sections, however, may be passed over by the non-technical man, 
without interfering materially with the continuity of the work. 

In view of the vast amount of ground covered in this volume, and 
fully realizing the limitations of his proficiency in some of its 
branches and ramifications, the author has taken it upon himself to 
draw freely from contemporary text-books and journal articles. In 
such instances, his endeavor has been to place due credit where it 
belongs, by referring to the source of such extraneous information. 
Nevertheless, there has been included a substantial amount of orig- 
inal data accumulated by the author during the past nineteen years, 
most of which appears in print herein for the first time. 

Topics which have been ably presented in other reference books, 
as for example the technology of pavements, etc., have purposely 
been subordinated to those concerning which little data have hitherto 
been available. To the latter belong such subjects as petroleum 
asphalts ; fatty-acid pitches ; bituminized roofings, floorings and other 
fabrics; bituminous paints, cements, varnishes and japans. 

Certain branches of the industry have developed along different 
lines in Europe than has been the case in this country, especially 



IX 



X PREFACE TO FIRST EDITION 

the treatment of peat and lignite (Chapter XV), also pyrobitumin- 
ous shales (Chapter XVI) . In such instances, the methods in vogue 
abroad before the great war are described with more or less detail. 
It must be borne in mind in this connection, that the war has mate- 
rially interfered with the prosecution of these industries abroad, and 
the data presented should be so construed, even though not specific- 
ally stated in the text. 

Whereas the greatest pains have been taken to establish the ac- 
curacy of every assertion, as well as the authenticity of every alleged 
fact, the author does not flatter himself that he has escaped the 
pitfalls which must perforce beset the path of a writer who under- 
takes to delve into a subject as complicated as the one under consid- 
eration, concerning which there are so many divergent views. 

Appreciation is expressed for the valuable suggestions and assist- 
ance rendered by W. A. Hamor, D. R. Steuart, Prevost Hubbard, 
S. R. Church, E. B. Cobb, David Wesson, Clifford Richardson, S. C. 
Ells, and the author's immediate associates. 

HERBERT ABRAHAM. 

NEW YORK CITY, 
July i, 1918. 



TABLE OF CONTENTS 



PART I GENERAL CONSIDERATIONS 
CHAPTER I 

PAGE 

HISTORICAL REVIEW x 

Origin of the Words "Asphalt," "Bitumen" and "Pitch" Fossils Preserved 
by Means of Asphalt Use of Asphalt by the Sumerians (about 3800 to 2500 
B.C.) King Sargon of Accad (about 3800 B.C.) Manishtusu King of Kish 
(about 3600 B.C.) Ornaments (about 3500 B.C.) At Tell-Asmar in Eshunna 
(3200 to 2900 B.C.) Lugal-daudu King of A dab (about 3000 B.C.) Ente- 
mena of Shirpula (about 2850 B.C.) Ur-Nind King of Lagash (about 2800 
B.C.) Ornaments and Sculptured Objects (2800 to 2500 B.C.) Gudea of 
Lagash (about 2700 B.C.) Tablets of Gilgamish (about 2500 B.C.) Bur- 
Sin King of Ur (about 2500 B.C.) Use of Asphalt by Pre-historic Races 
in India (about 3000 B.C.) Use of Asphalt by the Early Egyptians (2500 
to 1500 B.C.) Use of Asphalt in Biblical Times (2500 to 1500 B.C.) Use 
of Asphalt by the Babylonians (2500 to 538 B.C.) King Khammurabi (about 
2200 B.C.) Queen S emir amis (about 700 B.C.) King Nabopolassar (625 to 
604 B.C.) King Nebuchadnezzar (604 to 561 B.C.) Use of Asphalt by the 
Assyrians (1400 to 607 B.C.) King Adad-Nirari 1 (about 1300 B.C.) King 
Tukulti-Ninurta II (890 to 884 B.C.) King Sargon (722 to 705 B.C.) 
King Sennacherib (704 to 682 B.C.) Use of Asphalt in Constructing Lake- 
Dwellings (about 1000 B.C.) References to Bituminous Substances by Greek 
and Roman Writers (500 B.C. to 817 A.D.) Herodotus (484-425 B.C.) 
Thucydides (471-401 B.C.) Hippocrates (460-377 B.C.) Xenophon (430- 
357 B.C.) Aristotle (384-322 B.C.) Theophrastus (372-288 B.C.) Antigonus 
(about 311 B.C.) Hannibal (247-183 B.C.) Vergil (70-19 B.C.) Strabo 
63 B.C. 24 A.D.) Diodorus Siculus (about 50 A.D.) Virtuvius (about 50 
A.D.) Pliny the Elder (23-79 A.D.) Josephus Flavius (37-95 A.D.) Plutarch 
(about 46 A.D.) Tacitus (55-117 A.D.) Aelian (Aelianus Claudius) (about 
loo A.D.) Dioscorides (about 150 A.D.) Dion Cassius (155-230 A.D.) 
Philostratus (The Elder) (about 200 A.D.) Geoponica (200-300 A.D.) Afri- 
canus (about 300 A.D.) Ammianus Marcellinus (330-395 A.D.) Theophanes 
(758-817 A.D.) About 950 A.D., Abu-L-Hasan Masudi About 985 A.D., Abd 
Al Mukaddasi About 1248 AJX, Pierre de Joinville About 1300 A.D. Marco 
Polo About 1350 A.D., Sir John- Mandeville 1494-1555, Georg Agricola 
1498, Christopher Columbus About 1500, Use of Asphalt in Peru 1535, 
Discovery of Asphalt in Cuba 1563, Cesar Fredericke 1595, Sir Walter 
Raleigh- 1599, First Classification of Bituminous Substance* 1608, William 
Shakespearei 6 5 6, Early Dictionary Definition of "Bitumen" 1660, John 
Milton 1661, Commercial Production of Wood Tar 1672, First Accurate 
Description of Persian Asphalt Deposits 1673, Discovery of Elaterite 1681, 

xi 



xii TABLE OF CONTENTS 

PAGE 

Discovery of Coal Tar and Coal-Tar Pitch 1691, Discovery of Illuminating 
Gas from Coal 1694, Discovery of Shale Tar and Shale-tar Pitch 1712- 
1730, Discovery of Val de Travers, Limmer and Seyssel Asphalt Deposits 
1722, First Use of Tar for Flat Roofs 1746, Invention of the Process of 
Refining Coal Tar 1752, Samuel Foote 1777, First Exposition of Modern 
Theory of the Origin of Asphalt 1788, Discovery of Lignite Tar 1780- 
1790, Discovery of "Composition" or "Prepared" Roofing 1792-1802, Manu- 
facture of Coal Gas and Coal Tar on a Large Scale 1797-1802, Exploitation 
of Seyssel Asphalt in France 1815, Commercial Exploitation of Coal-tar 
Solvents 1820, Manufacture of Asphalt-saturated Packing Papers in Switzer- 
land 1822, Discovery of Scheereite and Hatchettite 1830, Discovery of 
Paraffin Wax 1832, Coal-tar First Used for Paving 1833, Discovery of 
Ozokerite 1835, First Asphalt Mastic Foot Pavements Laid in Paris 1836, 
Asphalt First Used in London for Foot Pavements 1837, Publication of First 
Exhaustive Treatise on the Chemistry of Asphalt 1837, Discovery of Bitu- 
minous Matter in the United States 1838, Discovery of Process for Preserv- 
ing Wood with Coal-tar Creosote 1838, Asphalt First Used in the United 
States for Foot Pavements 1841, First Use of Wood Block Pavement 1843, 
Bituminous Matters Discovered in New York State 1844-1847, First Compo- 
sition Roofing in the United States 1850, Discovery of "Asphaltic Coal" in 
New Brunswick, Nova Scotia 1852, First Modern Asphaltic Road 1854, 
First Compressed Asphalt Roadway Laid in Paris 1858, First Modern As- 
phalt Pavement Laid in Paris 1863, Discovery of Grahamite in West Vir- 
ginia 1869, The First Compressed Asphalt Pavement in London 1870-1873, 
First Asphalt Roadways in the United States 1876, First Trinidad Asphalt 
Pavement Laid in the United States 1880, Use of Asphalt "Chewing-gum" 
in Mexico 1881, Use of Chemicals for Oxidizing Coal Tars and Petroleum 
Asphalts 1885, Discovery of Uintaite (Gilsonite) in Utah 1889, Discovery 
of Wurtzilite in Utah 1891, Exploitation of the Bermudez Asphalt Deposit, 
Venezuela 1892, Use of Bermudez Asphalt on a Large Scale 1894, Use f 
Air for Oxidizing Petroleum Asphalt 

CHAPTER II 

TERMINOLOGY AND CLASSIFICATION OF BITUMINOUS SUBSTANCES 51 

Bituminous Substances Bitumen Pyrobitumen Petroleum Mineral Wax 
Asphalt Asphaltite Asphaltic Pyrobitumen Non-asphaltic Pyrobitumen 
Tar Pitch Classification of Bituminous Substances. 



CHAPTER III 

CHEMISTRY OF BITUMINOUS SUBSTANCES 65 

Composition of Non-mineral Matrix Composition of Associated Min- 
eral Constituents Composition of Associated Non-mineral Constitu- 
ents Behavior with Solvents Behavior on Subjecting to Heat Re- 
actions with Gases Oxygenation Hydrogenation Reactions with 
Acids Liquid Sulfur Dioxide Sulfuric Acid and Sulfur Trioxide Nitric 
Acid Sulfuric Acid and Formaldehyde Reactions with Alkalies Reac- 
tions with Metalloids Sulfur and Sulfur Dichloride Selenium Phos- 
phorusHalogens Reactions with Metallic Salts. 



TABLE OF CONTENTS xiii 

CHAPTER IV 

PAGE 

GEOLOGY AND ORIGIN OF BITUMENS AND PYROBITUMENS 82 

Geology Age of the Geological Formations Character of the Associated 
Minerals Modes of Occurrence Springs Lakes Seepages Subterranean 
Pools or Reservoirs Impregnated Rock in Strata Filling Veins Movement 
of Bitumen in the Earth's Strata Hydrostatic Pressure Gas Pressure 
Capillarity Gravitation Effect of Heat Origin and Metamorphosis of 
Bitumens and Asphaltic Pyrobitumens Probable Origin of Bitumens 
and Asphaltic Pyrobitumens Inorganic Theories Vegetable Theories Ani- 
mal Theories Metamorphosis of Mineral Waxes, Asphalts, Asphaltites and 
Asphallic-Pyrobitumens from Petroleum Origin and Metamorphosis of 
Non-Asphaltic Pyrobitumens. 

CHAPTER V 

ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES AND THEIR 

MANUFACTURED PRODUCTS 98 

Production of Asphalts, Asphaltites and Asphaltic Pyrobitumens 
World Production Production in the United States Production of Tars 
and Pitches Tars Derived from Coal Tars and Pitches Derived from 
Wood Other Tars and Pitches Manufactured Products Bituminous 
Paving Materials Bituminous Roofing Products Asphalted Felt-base Floor 
Coverings. 



PART II SEMI-SOLID AND SOLID BITUMENS AND 

PYROBITUMENS 

CHAPTER VI 

METHODS OF MINING, TRANSPORTING AND REFINING 112 

Mining Methods Open-cut Quarrying Tunnelling Special Methods 
Methods of Shipment and Transportation Methods of Refining De- 
hydration Distillation Comminution Sedimentation Extraction 
Extraction by Means of Water Extraction or Precipitation with Solvents 
Methods of Storage. 

CHAPTER VII 

MINERAL WAXES 129 

Ozokerite Europe Galicia Rumania Russia Terek Province Kuban 
Province Kutais Province Tiflis Province Baku Province Kars Province 
Asia State of Turkestan Siberia Philippine Islands North America 
United States UtafiTexasHatchettite or Hatchettine Scheereite 
Kabaite Montan Wax. 



Xiv TABLE OF CONTENTS 

CHAPTER VIII 

PAGE 

NATIVE ASPHALTS OCCURRING IN A FAIRLY PURE STATE 139 

North America United States Kentucky Oklahoma Utah California 
Oregon Mexico State of Tamaulipas State of Vera Cruz Cuba Prov- 
ince of Matanzas Province of Santa Clara Province of Camaguey Province 
of Santiago de Cuba South America Venezuela State of Bermudez State 
of Zulia Europe France Department of Puy de Dome Albania Se*le- 
nitza Greece Zante Russia Kutais Province Tiflis Province Uralsk 
Province Asia Syria Villayet of Beirut Mesopotamia (Iraq) Hit Ain 
el Maraj Ain Ma* Moura Quijarah, Ramadi and Abu Gir Asiatic Russia 
Sakhalin Philippine Islands Island of Leyte. 

CHAPTER IX 

NATIVE ASPHALTS ASSOCIATED WITH MINERAL MATTER 155 

North America United States Kentucky Missouri Indiana Oklahoma 
Arkansas Alabama Louisiana Texas Utah Wyoming Cali- 
fornia Canada Alberta Province Manitoba Province Mexico States of 
Vera Cruz and Tamaulipas Cuba Province of Matanzas Province of Pinar 
del Rio Province of Havana Province of Camaguey Province of Santiago 
de Cuba South America Trinidad Brazil State of Parand State of 
Sao Paulo Argentina Province of Jujuy Province of Chubut Province 
of Mendoza Colombia Department of Bolivar Department of Antioquia 
Department of Santander Department of Boyacd Equador Province of 
Guayas Europe France Department of Landes Department of Gard 
Department of Haute-Savoie Department of Ain Department of Basses- 
Alpes Department of Puy~de-D6me Department of Haute Vienne Switzer- 
land Alsace-Lorraine Spain Burgos Province Germany Province of 
Hanover Province of Westphalia Province of Hessen Province of Baden 
Province of Silesia Jugoslavia Province of Dalmatia Province of Herze- 
govina Province of Styria Austria Province of Tyrol Hungary Prov- 
ince of Bihar Czecho-Slo<vakia Province of Trencsen Provinces of Moravia 
and Silesia Rumania Albania S61enitza Italy Compartment of Marches 
Compartment of Abruzzi e Molise Compartment of Calabria Compart- 
ment of Campania Compartment of Sicily Greece Department of Triphylia 
Department of Achaia lolian Islands Department of Phocis Depart- 
ment of Phthiotis Departments of Eurytania and Arta Northern Depart- 
ments Portugal Province of Estremadura Spain Province of Santander 
Province of Alava Province of Navarre Province of Gerona Province of 
Tarragona Province of Soria Province of Burgos Province of Almeria 
Province of Valencia Russia (in Europe) Simbirsk Province Kazan Prov- 
ince Samara Province Terek Province Kutais Province Tiflis Province 
Baku Province Asia Syria (Levant States) Vilayet of AleppoVilayet of 
Beirut Vilayet of Sham Palestine- Mesopotamia (Iraq) Valiyet of Bagdad 
Asiatic Russia Uralsk Province State of Turkestan Kamchatka Penin- 
sulaSakhalin Island Tur key-in- Asia (Asia Minor) Anatolia Arabi a 
Vilayet of El Hasa Sinai Peninsula -Egypt India Kashmir District Ha- 
zara District Bel uchistan District Bombay Island China Chinese Turkes- 
tan Japan -Akita Prefecture Prefectures of Yamagata, Aomori and Dis- 
trict of Hokkaido Australia New South Wales Western Australia North- 



TABLE OF CONTENTS XV 

PAGE 

ern Territory Tasmania New Zealand Dutch East Indies Buton (Boe- 
ten) IslandAfrica Algeria Province of Oran Nigeria Rhodesia -Mad- 
agascar. 

CHAPTER X 

ASPHALTITES 2Z7 

GILSONITE or UINTAITE North America United States Utah Oregon- 
Asia Russia Archangel Province GLANCE PITCH North America West 
Indies Barbados Santo Domingo (Haiti) Cuba Province of Pinar del 
Rio Province of Santa Clara Province of Camaguey Mexico State of 
Vera Cruz United States Utah Central America Nicaragua District 
of Chontales Salvador Department of San Miguel South America 
Colombia Province of Tolima Province of Bolivar Europe Germany 
Bentheim Syria (Levant States) Vilayet of Sham Palestine Mesopotamia 
(Iraq) GRAHAMITE North America United States West Virginia 
Texas Oklahoma Colorado Mexico State of Vera Cruz State of San 
Luis Potosi State of Tamaulipas Cuba Province of Pinar del Rio Prov- 
ince of Havana Province of Santa Clara South America Trinidad 
Argentina Province of Mendoza Province of Neuquen Peru Province of 
Tarma. 

CHAPTER XI 
ASPHALTIC PYROBITUMENS 202 

ELATERITE England Derbyshire County Australia State of South Australia 
Asiatic Russia State of Turkestan WURTZILITE United States Utah 
Albertite Canada Province of New Brunswick Province of Nova Scotia 
United States Utah South America Falkland Islands Germany Prov- 
ince of Hanover Australia Tasmania Portuguese West Africa Province 
of Angola IMPSONITE North America United States Oklahoma Ar- 
kansas Nevada Michigan South America Peru Provinces of Canta 
and Yauli Province of Huarochiri Brazil State of Sao Paulo Australia 
West Australia. 

CHAPTER XII 
PYROBITUMINOUS SHALES 275 



PART 1 1 ITARS AND PITCHES 

CHAPTER XIII 
GENERAL METHODS OF PRODUCING TARS 278 

Destructive Distillation Composition of the Substance The Temperature 
The Time of Heating The Pressure The Efficiency of the Condensing 
System Partial Combustion with Air and Steam Partial Combustion 
with a Limited Access of Air Cracking of Oil Vapors. 



xvi TABLE OF CONTENTS 

CHAPTER XIV 

PAGE 

WOOD TAR, WOOD-TAR PITCH AND ROSIN PITCH ................... 288 

Wood Tar and Wood-tar Pitch Varieties of Wood Used Yields of 
Distillation Hardwood Distillation Method of Distilling Refining Proc- 
esses Soft (Resinous) Wood Distillation Method of Distilling Refining 
Processes Hardwood Tar and Pine Tar Hardwood-tar Pitch and Pine-tar 
PitchRosin Pitchr-Raw Materials Used Methods of Distilling Products 
Obtained Properties of Rosin Pitch "Burgundy Pitch." 

CHAPTER XV 

PEAT AND LIGNITE TARS AND PITCHES .............................. 305 

Peat Tar and Peat-tar Pitch Formation of Peat Varieties of Peat 
Methods of Collecting Dehydrating Processes Methods of Distilling Refin- 
ing Processes Properties of Peat Tar Properties of Peat-tar Pitch Lignite 
Tar and Lignite-tar Pitch Varieties of Lignite Mining Methods 
Methods of Distilling Products Obtained Treating Impure Lignite Proper- 
ties of Lignite Tar Refining Processes Products Obtained Properties of 
Lignite-tar Pitch. 

CHAPTER XVI 
SHALE TAR AND SHALE-TAR PITCH .................................... 2 



Shale Mining Retorts Used for Distillation Pumpherston Retort Hender- 
son or Broxburn Retort Methods of Recovering Shale Tar Products Ob- 
tained Properties of Shale Tar Refining of Shale Tar Properties of Shale- 
tar Pitch. 

CHAPTER XVII 

COAL TAR AND COAL-TAR PITCH ...................................... 336 

Bituminous Coals Used Temperature of Treatment Production of Gas- 
Works Coal Tar Retorts Used Methods of Recovery Products Obtained _ 
Production of Coke-oven Coal Tar Retorts Used Methods of Recovery _ 
Products Obtained Production of Blast-furnace Coal Tar Methods of Re- 
covery Production of Producer-gas Coal Tar Products Obtained Produc- 
tion of Low-temperature Tars Products Obtained Properties of Coal 
Tars Methods of Dehydrating Coal Tar Settling Use of Cen- 
trifugesHorizontal Stills Tube Heaters Cascade System Methods of 
Distilling Coal Tar Simple Batch Stills Vacuum Distillation Steam Dis- 
tillation Gas Recirculation Continuous Stills Tube Stills Collector- 
Main Condensers Recovery and Treatment of Coal-tar Distillates Recovery 
and Treatment of Coal-tar Residuals Commercial Varieties of Coal-tar Pitch 
Pitch Coke Properties of Coal-tar Pitches Gas-works Coal-tar Pitches- 
Coke-oven Coal-tar Pitch Blast-furnace Coal-tar Pitch Gas-producer Coal- 
tar Pitch Low-temperature Coal-tar Bitch Anthracene Pitch Naphthol 
Pitch Cresol Pitch. 



TABLE OF CONTENTS XVii 

CHAPTER XVIII 

PAGE 

WATER-GAS AND OIL-GAS TARS AND PITCHES 378 

Carburetted Water-gas Tar Method of Production Properties of Water- 
gas Tar Oil-gas Tars Methods of Production Pintsch Gas Oil-water 
Gas Blau Gas Properties of Oil-gas Tars Refining of Water-gas and Oil- 
gas Tars Properties of Water-gas-tar Pitch and Oil-gas-tar Pitch. 

CHAPTER XIX 

FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH 386 

Fatty-acid Pitch Sources from which Obtained Production of Candle and 
Soap Stocks Hydrolysis by Means of Water Hydrolysis by Means of Con- 
centrated Sulfuric Acid Hydrolysis by the "Mixed Process" Hydrolysis by 
Means of the Sulfo-compounds Hydrolysis by Means of Ferments Refining 
Vegetable Oils by Means of Alkali Refining of Cotton-seed Oil Refining 
of Corn-Oil Refining Refuse Greases Refining Packing-house and Carcass- 
rendering Greases Refining Bone Grease Refining Garbage and Sewage 
Greases Refining Woolen-mill Waste Treatment of Wool Grease Physical 
and Chemical Properties of Fatty-acid PitchesBone Tar and Bone-tar 
Pitch Methods of Production Physical and Chemical Characteristics 
Glycerine Pitch. 

PART IFPYROGENOUS ASPHALTS AND WAXES 

CHAPTER XX 

PETROLEUM ASPHALTS 409 

Varieties of Petroleum Asphaltic Petroleums Semi-asphaltic Petroleums 
Non-asphaltic Petroleums Dehydration of Petroleum Settling Cen- 
trifuging Tube-stills Distillation of Petroleum Batch Stills Steam 
Distillation Dry Distillation Continuous Stills Tube or Pipe Stills 
Cracking Processes Liquid Phase Cracking Tube-and-tank Process 
Cross Process Holmes-Manly Process Mixed Phase Cracking Burton 
Process Dubb's Process Liquid Products Semi-solid to Solid Distillates 
Semi-solid to Solid Residues Residual Oils Varieties Obtained Physical 
and Chemical Characteristics Blown Petroleum Asphalts Processes Used 
Advantages of "Blowing" Over the Steam-distillation Process Physical and 
Chemical Characteristics Sulfurized Asphalts Residual Asphalts Proc- 
esses Used Physical and Chemical Characteristics Methods of Distinguish- 
ing between Petroleum Asphalts and Native Asphalts Sludge Asphalts 
Methods of Production Physical and Chemical Characteristics. 

CHAPTER XXI 

PARAFFIN WAX, WAX TAILINGS AND RESINS 466 

Paraffin Wax Sources from which Obtained Physical and Chemical Char- 
acteristics Wax Tailings Methods of Production Physical and Chemical 
Characteristics Petroleum Resinsr Asphaltic Resins. 



XViii TABLE OF CONTENTS 

CHAPTER XXII 

PAGE 

WURTZILITE ASPHALT 472 

Method of Production Still Used Depolymerization Process Grades of 
Wurtzilite Asphalt Produced Chemical and Physical Characteristics. 



PART V MANUFACTURED PRODUCTS AND 

THEIR USES 

CHAPTER XXIII 

COMPOUNDING OF BITUMINOUS SUBSTANCES 476 

General Considerations Hardness, Fusibility, Penetration, Approximate 
Comparative Volatility, Weatherproof Properties and Efficiency of Fluxing 
of Various Bituminous Substances Principles Involved in Preparing Mixtures 
Binary Mixtures Softening of the Substance and Lowering its Fusing- 
point Augmenting the Adhesive Properties of the Substance Increasing the 
Fluidity of the Substance when Melted Effecting a More Perfect Union or 
Blending of the Constituents Hardening the Substance, Raising its Fusing- 
point and Increasing its Stability Rendering the Mixture Less Susceptible to 
Temperature Changes Increasing the Tensile Strength of the Mixture 
Making the Mixture More Weatherproof Rendering Wax-like, Unctuous 
to the Feel, or Lessening the Tendency Towards Stickiness Tertiary and 
Complex Mixtures Classes of Bituminous Mixtures Soft (Liquid) Bitumi- 
nous Products Medium (Semi-liquid to Semi-solid) Bituminous Products 
Hard (Solid) Bituminous Products Processes of Compounding Bituminous 
Substances. 

CHAPTER XXIV 

BITUMINOUS SUBSTANCES ADMIXED WITH DISCRETE AGGRE- 
GATES 494 

Methods of Incorporating Discrete Aggregates Colloidal Particles Ad- 
mixed Mechanically Inorganic Organic Liberated "In Situ" Inorganic 
Organic Fillers (Powders) Including Pigments Inorganic Oxides 
Silicates Carbonates Sulfates Phosphates Miscellaneous Rock Products 
Pyrogenous Products Black Pigments Colored Pigments Organic Vege- 
table Products Black Pigments Fibers Inorganic Organic Granular 
Matter Inorganic Organic Coarse Mineral Aggregates Crushed 
Rock, Stone, Gravel or Slag Graded Aggregates Combinations of the 
Foregoing. 

CHAPTER XXV 

BITUMINOUS SUBSTANCES DISPERSED IN WATER 503 

Types of Bituminous Dispersions Forms of Apparatus Used Charac- 
ter of the Bituminous Substance Character of the Dispersing Agent 
Inorganic Substances Hydroxides Oxides Silicates Sulfates Phosphates 
Sulfides or Polysulfides Alkalies Miscellaneous Organic Substances Fats 



TABLE OF CONTENTS xix 

PAGE 

and Oils Resins Soaps Sulfonated Vegetable Oils Sulfite Liquor Min- 
eral-Oil Derivatives Carbonaceous Matter Alkaline Bases Proteins or Pro- 
teids Albumenoids Pectins Gums and Algae Polysaccharides and Herai- 
celluloses Tannins Miscellaneous Parlous Combinations Clay in Com- 
bination Sodium Silicate in Combination Soaps in Combination Sulfonated 
Vegetable Oils in Combination Alkaline Caseinates in Combination Glue or 
Gelatine in Combination Tannic Acid in Combination Uses of Bitumin- 
ous Dispersions. 

CHAPTER XXVI 
BITUMINOUS SUBSTANCES DISSOLVED IN SOLVENTS 514 

Classes of Solvents Function of Solvents Behavior of Solvents Solubility 
of Bituminous Substances Adsorption of Bituminous Substances. 



CHAPTER XXVII 

SOLID, SEMI-SOLID AND SEMI-LIQUID BITUMINOUS COMPOSITIONS. 526 

Adhesive Compounds for Built-up Roofing and Waterproofing Work Ad- 
hesive Compounds for Waterproofing Below Ground Above Ground Ad- 
hesive Compounds for Built-up Roofing Work Plastic-slate Cement 
Calking Compounds Bituminous Grout Bituminous Enamel for the Inside 
of Steel Ships Bituminous Enamel Bituminous Primer Bituminous Enamel 
for Acid-proofing Concrete Surfaces Pipe Dips and Pipe-sealing Compounds 
Pipe Dips Pipe Wrappings Pipe-sealing Compounds Electrical Insulat- 
ing Compounds Vacuum Impregnating Compounds Cable-splicing and Pot- 
head Compounds Battery-box Compounds "Carbons" for Batteries, Electric 
Lights and Armature Brushes Bituminous Rubber Substitutes Molded Com- 
positions Mixtures for Small Molded Articles Preformed Joints and Wash- 
ers Molded Brake-linings, Clutch-facings and Friction Elements Bitumin- 
ated Cork Mixtures Battery Boxes Fibrated Bituminous Compositions 
Roof Tiles Floor Tiles Floor and Step Treads Artificial Lumber and Rail- 
road Ties Pipes and Conduits Burial Vaults Phonograph Records Bi- 
tuminated Leather Mixtures Briquette Binders Core Compounds Miscel- 
laneous Bituminous Products Bituminous Fuels Tars and Oils for the 
Flotation of Ores Waterproofing Compounds for Portland-cement Mortar 
and Concrete Pure Bituminous Substances Bituminous Substances in Emul- 
sified Form Methods of Use Sponge Asphalt Asphalt Dust and Filaments 
Asphalt Jelly. 

CHAPTER XXVIII 

BITUMINOUS PAVING MATERIALS 567 

Bituminous Binders Liquid Asphaltic Binders Semi-solid to Solid As- 
phaltic Binders Coal-tar Binders Cut-back Products Bituminous Emulsions 
Mineral Aggregates Bituminous Compositions for Dust-laying 
(Cold Application) Bituminous Emulsions Non-emulsified Products 
General Considerations Bituminous Surfacings Surface Treatment Silt 
Roads Clay Roads Sandy Roads Seal-Coats To Loose Surfaces To 
Bonded Surfaces To Old Bituminous Surfaces To Non-bituminous Sur- 
faces Road-Mix Wearing Course Open Aggregate ("Macadam Type") 



XX TABLE OF CONTENTS 

PAGE 

Dense Aggregate ("Graded Type") Plant-Mix Wearing Course Open Ag- 
gregate ("Macadam Type")- Dense Aggregate ("Graded Type") Bitumi- 
nous Macadam Pavements Foundation Base Course Surface Course 
Bituminous Emulsions Penetration Method Road-Mix Method Bitumi- 
nous Concrete Pavements Foundation Base Course ("Black-base") 
Surface Course, Coarsely-graded Type Surface Course, Finely-graded Type 
Asphalt Emulsions Sheet-asphalt Pavements Foundation Binder and 
Surface Courses General Considerations Bituminous Joint-Fillers Fill- 
ing the Joints Asphalt-block Pavements Foundation Laying the Blocks 
Bituminized Wood-block Pavements Methods of Impregnation Creo- 
sote Preservatives Foundation Cushion Layer Filling the Joints General 
Considerations Asphalt Mastic Foot-Pavements and Floors Asphalts 
Used Methods of Preparation Methods of Application Asphalt Mastic 
Roofs Bituminous Expansion Joints Promolded Strips Bituminized 
Fabric Strips Laminated Strips Armored Strips Bituminous Rail-fillers 
Asphalt Bridge-planking Bituminous Revetment. 

CHAPTER XXIX 

BITUMINIZED FABRICS, FELTS AND PAPERS FOR ROOFING, FLOOR- 
ING, WATERPROOFING, BUILDING AND INSULATING PURPOSES 617 

Prepared Sheet Roofings Felted Fabrics Rag-felt Methods of Fire- 
proofing Rag-felt String-felt or Threaded-felt Asbestos Felt Woven Fa- 
brics Bituminous Saturating Compositions Asphaltic Products Tar Prod- 
ucts Bituminous Coating and Adhesive Compositions Fillers Black Pig- 
ments Colored Pigments Inorganic Surfacings Fine Mineral Particles 
Moderately Coarse Mineral Granules Coarse Mineral Granules Organic 
Surfacings Saturated Felt Saturating the Fabric Tarpaulins Brattice 
Cloth Tents and Awnings Waterproof Membranes Wrapping Cloth 
Teredo-proof Coverings Roof Coverings for Railway Cars Prepared Roll- 
roofings Single-layered Prepared Roofings Laminated Roofings Decora- 
tive Roll-roofings Scalloped and Serrated Roll-roofings Asphalt Shingles 
General Features Features Pertaining to Thickness Shingles Surfaced 
with Mineral Granules Rear Surface Coating Shingles Surfaced with Min- 
eral Granules and Coated with Hydraulic Cement Shingles Surfaced with 
Slate-veneer or Tile or Asbestos-cement Shingles Surfaced with Metals 
Shingles Reinforced with a Core of Sheet-metal or Wire Laminated Shingles 
Combinations with Asbestos Felt Combinations Involving the Use of 
Wooden Shingles Miscellaneous Forms Individual Shingles Forming 
Rectangular Patterns when Laid Forming Diamond-shaped Patterns when 
Laid Forming Hexagonal Patterns when Laid Forming Octagonal Patterns 
when Laid Forming Circular Patterns when Laid Forming Thatched Ef- 
fects when Laid Reversible Forms Strip Shingles Forming Rectangular 
Patterns when Laid Forming Diamond-shaped Patterns when Laid Form- 
ing Hexagonal Patterns when Laid Forming Octagonal Patterns when Laid 
Forming Circular or Curved Effects when Laid Forming Thatched Effects 
when Laid Forming Miscellaneous Patterns when Laid Reversible Forms 
Asphalt Sidings Fastening Devices Lap-cement Nails Metal Cleats for 
Roll-roofings Concealed Nailing for Roll-roofings Forming Standing Seams 
Methods of Packaging Methods of Laying Roofings and Shingles Laying 
the Fabric in a Single Course Built-up Roofs Laying Asphalt-shingle 
Roof a Fire-resisting Properties of Prepared Roofings and Shingles Bi-, 



TABLE OF CONTENTS xxi 

PAGE 

tuminized Floor Coverings Saturated Felt Base Method of Printing 
Waterproofing Membranes Materials Used Preparing the Underly- 
ing Surface Selecting and Installing the Waterproofing Membrane Pro- 
tecting the Waterproofing Membrane Insulating and Building Papers 
Raw Paper Stock Bituminous Saturation Bituminous Coating Compositions 
Method of Manufacture Bituminized Papers for Electrical Insulation 
Bituminized Papers for Wrapping and Packing Purposes Bitumin- 
ized Papers for Mulching Plants and Crops Blasting Fuses Bi- 
tuminized Cords and Ropes Insulation for Electrical Transmission 
Wires Bituminized Fiber Conduits Asphalt Pipes Brake Linings 
and Clutch-facings for Automobiles Insulating and Acoustical Felts 
for Automobiles Electrical Insulating Tape Bituminized Wall- 
Board Bituminous Insulating Board Acoustical Blocks Bitum- 
inous Stucco-base and Plaster-board* 

CHAPTER XXX 

BITUMINOUS LACQUERS, CEMENTS, VARNISHES, ENAMELS AND 

JAPANS 720 

Bituminous Lacquers and Paints Nature of the Base Nature of the Fill- 
ers and Pigments Nature of the Solvents Methods of Manufacture Types , 
of Bituminous Paints Masonry Coatings Clear Damp-proofing Paints 
Black Damp-proofing Paints Stone Backing Paints for Resurfacing Prepared 
Roofings Asphalt Fibrous-Roof-Coating Acid-resisting Coatings Bitumi- 
nous Coatings for Metal or Wood Anti-fouling Paints Bituminous Emulsion 
Paints Flooring Compositions for Cold Application Bituminous Cements 
Method of Manufacture Method of Use Bituminous Varnishes 
Method of Manufacture Bituminous Enamels Method of Manufacture 
Cellulose-Ester Lacquers Bituminous Japans Method of Manufacture 
Uses. 

PART VI METHODS OF TESTING 
CHAPTER XXXI * 

SAMPLING 757 

General Methods Definitions Sampling Crude, Refined and Blended Bi- 
tuminous Substances Sampling at Place of Manufacture When Material 
is Pumped under Pressure When Materials Flow by Gravity Sampling at 
Point of Delivery Semi-solid or Solid Materials Liquid Materials Solid 
Bituminous Materials in Crushed Fragments or Powder Sampling Bitumi- 
nous Paving Materials Sampling Bituminized Fabrics Sampling 
Bituminous Lacquers, Cements, Varnishes and Japans, also Bitumi- 
nous Emulsions. 

CHAPTER XXXII 

EXAMINATION OF CRUDE, REFINED AND BLENDED BITUMINOUS 

SUBSTANCES 776 

Synoptical Table of Bituminous Substances Physical Characteristics 
Color Color in Mass Color in Solution Homogeneity To the Eye Under 
Microscope When Melted In Solution Appearance Surface when Aged 



xxii TABLE OF CONTENTS 

PAGE 

Fracture Lustre Streak Water Absorption Diffusibility Specific Gravity 
Hydrometer Method Westphal Balance Method Bottle Method Pyk- 
nometer Method Analytical Balance Method Voids (Entrapped Air) Col- 
loidal Capacity-^Clzy Dispersions Ultramicroscopic Count of Colloidal Par- 
ticlesMechanical Tests Viscosity Engler Method Saybolt ( Furol) 
Method Absolute Viscosity Hutchinson's Method Float Test Schutte 
Method Falling Ball Method Alternating Stress Method Falling Coaxial 
Cylinder Method Hardness or Plasticity Moh's Scale Penetrometer Con- 
sistometer Susceptibility Index Ductility Dow' s Method Author's Method 
Tensile Strength ( Cohesiveness) Author's Method Adhesiveness 
Riehm's Method Wedmore's Method Brown's Method Surface Tension 
Nellensteyn's Method Interfacial Tension Thermal Tests Thermal Con- 
ductivity A.S.T.M. Method Specific Heat Heat Content Thermal Ex- 
pansion A.S.T.M. Method Breaking Point Knife Test Reeve and Yea- 
ger's Method Fraas Method Solidifying-PointMetzgeT's Method Soften- 
ing-Point or Fusing-Point Kramer-Sarnow Method Ring-and-Ball Method 
Cube Method Compression Method A.S.T.M. Method for Petrolatum 
A.S.T.M. Method for Paraffin Wax Flow-Point Richardson's Method 
Liquefying-Point Ubbelohde's Method Twisting-Point Taylor's Method 
Volatile Matter A.S.T.M. Method Evaporation Test A.S.T.M. Method 
Distillation Test A.S.T.M. Method FW/-/>o*w/ Pensky-Martens Tester- 
Cleveland Tester Tag Closed Tester Tag Open Tester Burning-Point- 
Fixed Carbon Solubility Tests Solubility in Carbon Bisulfide Where 
the Constituents are Not to be Examined Further Where the Constituents are 
to be Examined Further Carbenes Richardson's Method Solubility in 
Petroleum Naphtha Insoluble in Benzol ("Free Carbon") Solubility in 
Other Solvents Chemical Tests Water Substances Distilling at Low Tem- 
peraturesSubstances Distilling at High Temperatures Elemental Composi- 
tion Carbon Hydrogen Sulfur Nitrogen Oxygen (in Non-mineral Mat- 
ter) Molecular Weight Freezing-point Method Tar Adds Contraction 
Method Liberation Method Naphthalene Solid Paraffins Holders Method 
Sulfonation Residue Residue Insoluble in Concentrated Sulfuric Acid- 
Residue Insoluble in Water Dimethyl Sulfate Method Formolite Reaction 
Nastjukoff Method Degree of MercurationSaponifiable Constituents Free 
Acids (Acid Value) Lactones and Anhydrides (Lactone Value) Neutral 
Fats (Ester Value) Saponification Value Separation of Saponifiable Con- 
stituentsExamination of Unsaponifiable Constituents Examination of Sa- 
ponifiable Constituents Glycerol ^/>^//*V Constituents Free Asphaltous 
Acids Asphaltous Acid Anhydrides Asphaltenes Asphaltic Resins Oily 
Constituents Diazo Reaction Graefe's Method Anthraquinone Reaction 
Liebermann-Storch Reaction Colorimetric Method. 

CHAPTER XXXIII 

EXAMINATION OF BITUMINOUS SUBSTANCES COMBINED WITH 

DISCRETE AGGREGATES IOI 7 

Physical Tests of Finished Product Pawing Compositions, Asphalt Mas- 
tic Bituminous Grouts, Pipe-sealing Compounds, etc. Specific Gravity- 
Voids Resistance to Moisture Effect of Water on Adhesion Hardness Re- 
sistance to Displacement Extrusion of Binder Under Pressure Resistance to 
Impact Brittleness or Shatter Test Coefficient of Wear Molded Materials 
Thickness Resistance to Moisture Tensile Strength Compressive Strength 



TABLE OF CONTENTS xxiii 

PAGE 

Flexural Strength Distortion Under Heat Softening-Point Resistance to Im- 
pact Electrical Tests Separation of Finished Product into Its Compo- 
nent Parts Separation of the Bituminous Matter and Discrete Aggre- 
gate Methods Suitable for Aggregates Associated with an Asphaltic Binder 
Hot Extraction Method Cold Extraction Method Centrifugal Extraction 
Method Method Suitable for Aggregates Associated with Coal-tar Pitch 
Binder Recovery and Examination of Extracted Bituminous Matter 
Separation of Bituminous Constituents Examination of the Separated 
Aggregate Inorganic Aggregates Granularmetric Analysis Elutriation 
Test Air-separation Test Adsorptive Capacity of Fine Fillers Specific 
Gravity Organic Particles^ Fibers t Fillers t etc. 



CHAPTER XXXIV 

EXAMINATION OF BITUMINIZED FABRICS 1072 

Physical Tests of the Finished Product Weight per Unit Area For 
Saturated Felted and Woven Fabrics For Smooth-roll and Mineral-surfaced 
Roll-roofing For Mineral-surfaced Shingles Thickness Strength Tensile 
Strength Bursting Strength Tearing Strength Pliability Mandrel Test 
Reeve and Y eager Test Resistance to Dampness Water Absorption Resis- 
tance to Heat For Asphalt-saturated Fabrics For Coal-tar Saturated Fabrics 
Only For Asphalt Roll-roofings and Shingles Electrical Tests Special 
Tests Applicable to Insulating Tape Tensile Strength Adhesion Oven 
Test Tackiness Separation of Finished Product into Its Component 
Parts Separation of Bituminous Matter, Mineral Matter and Fibrous 
Constituents Moisture Analysis of Saturated Fabrics (Single-layered) 
Analysis of Saturated and Coated Fabrics (Single-layered) Recovery 
and Examination of Extracted Coatings and Saturation Ex- 
amination of the Separated Mineral Surfacing and Admixed Min- 
eral Constituents Examination of the Separated Fabric Weight per 
Unit Area ("Number") Uncorrected Number Moisture Corrected Number 
Thickness Tensile Strength Porosity Speed with which the Felt Will 
Saturate Vertical Method Horizontal Method Saturating Capacity Fiber 
Composition. 

CHAPTER XXXV 

EXAMINATION OF BITUMINOUS SOLVENT COMPOSITIONS 1117 

Physical Tests of the Finished Product RSsumt of Physical Tests Spe- 
cific Gravity Viscosity Plasticity and Mobility Flash-point Spreading 
Capacity and Workability Draining Test Time of Drying Hiding Power 
Color Gloss Hardness, Abrasion and Adhesion Water Absorption Re- 
sistance to Heat Resistance to 'Oil Resistance to Acids and Alkalies Dielec- 
tric Strength Estimation, Recovery and Examination of the Solvent 
Estimation and Recovery of Solvent Evaporation Method Steam Distillation 
Method Examination of the Solvent Estimation, Recovery and Exam- 
ination of Pigment and Filler Estimation and Recovery of Pigment and 
Filler Examination of the Pigment or Filler Estimation, Recovery and 
Examination of the Base Estimation and Recovery of the Base Examina- 
tion of the Base. 



xxiv TABLE OF CONTENTS 

CHAPTER XXXVI 

PAGE 

EXAMINATION OF BITUMINOUS DISPERSIONS 1 132 

Physical Tests of the Finished Product Method of Identification 
Homogeneity Appearance Under Microscope Sieve Test Settlement Test 
Stability on Aging Viscosity Demulsibility Calcium-chloride Test Fer- 
rous-sulfate Test Behavior with Aggregate ("Coating Test")Miscibility 
with Water Effects on Freezing Resistance to Water After Setting With- 
out Aggregate When Mixed with Aggregate Separation of the Disper- 
sion into its Component Parts Distillation ResidueWater and Volatile 
Oils Dispersing Agents. 

CHAPTER XXXVII 

WEATHERING TESTS "47 

Effects of WeatheringEvaporationOxidationCarbonizationPoly- 
merizationEffects of Moisture Actual Weathering Test Testing Bitu- 
minized Fabrics Testing Bituminous-solvent Compositions Testing Crude, 
Refined or Blended Bituminous Substances Accelerated Weathering Test 

Testing Bituminized Fabrics Testing Bituminous-solvent Compositions 

Testing Bituminous Compositions Modified Accelerated Weathering 
Test. 

TEMPERATURE CONVERSION TABLE 1182 

BIBLIOGRAPHY "*3 

REFERENCES I2 3 1 

INDEX '435 



ASPHALTS AND ALLIED SUBSTANCES 



PART I 
GENERAL CONSIDERATIONS 



CHAPTER I 
HISTORICAL REVIEW 

Origin of the Words "Asphalt," "Bitumen" and "Pitch." 

The word "asphalt" is claimed to have been derived from the 
Accadian term "asphaltu" or "sphallo," meaning "to split." It was 
later adopted by the Homeric Greeks in the form of the adjective 
dcr^aX^, c's, signifying "firm," "stable," "secure," and the correspond- 
ing verb dcr<aAia>, tiro), meaning "to make firm or stable," "to se- 
cure." It is a significant fact that the first use of asphalt by the 
ancients was in the nature of a cement for securing or joining 
together various objects, and it thus seems likely that the name itself 
was expressive of this application. From the Greek, the word 
passed into late Latin, and thence into French ("asphalte") and 
English ("asphalt"). 

The expression "bitumen" originated in the Sanskrit, where we 
find the words "jatu," meaning "pitch," and "jatu-krit," meaning 
"pitch creating," "pitch producing" (referring to coniferous or res- 
inous trees). The Latin equivalent is claimed by some to be origi- 
nally "gwitu-men" (pertaining to pitch), and by others, "pixtumens" 
(exuding or bubbling pitch), which was subsequently shortened to 
"bitumen," thence passing via French into English. From the same 
root is derived the Anglo Saxon word "cwidu" (Mastix), the 
German word "Kitt" (cement or mastic) and the old Norse word 
"kvada." 



2 HISTORICAL REVIEW I 

The following terms have been traced throughout the various 
ancient languages: 

Sumerian: 

Esir (petroleum and native asphalt) ; esir-lah (hard, glossy 
asphalt) i ; esir-harsag (rock asphalt) ; esir-e-a (mastic asphalt) ; se- 
li-ud (pine tar) ; kunin or esir-ud-du-a (pitch). 

Sanskrit: 

Jatu (native asphalt also pitch) ; sila-jatu or asmajatam-jatu 
(rock asphalt). 

Assyrian and Accadian: 

Iddu, ittu, it-tu-u, or amaru (native asphalt) ; kukru or kir-kir- 
anu (pine tar) ; sippatu or kupru or ku-pur (pitch). In Babylonia, 
pitch is still termed "kupru." 

Hebrew : 

Zephet or hemar (native asphalt) ; zephet or kopher or kofer 
(pitch). In Exodus (II, 3) we find the words "hemar" and 
"zephet" denoting pitch. 

Arabic and Turkish: 

Seyali or zift or zipht (native asphalt) ; chemal or humar (hou- 
mar) or gasat (qasat) (rock asphalt) ; ghir or gir or kir or kafr 
(mastic asphalt) ; zipht or kir or kafr (pitch) ; neftgil (mineral 
wax). 

Greek: 

Maltha (soft asphalt) ; asphaltos (native asphalt) ; pissasphal- 
tos or pittasphaltos or pittolium (rock asphalt) ; pissa-hygra or 
pisselaion (pine tar) ; pissa or pitta (pitch) ; ampelitis (mineral 
wax and asphaltites) ; spinos (bituminous coal) ; anthrax (anthra- 
cite coal). 

La tin : 

Maltha or bitumen liquidum (soft asphalt); bitumen (native 
asphalt) ; pixliquida or serum picis (pine tar) ; pix (pitch) ; gagates 
(asphaltite and jet and lignite) ; lapis thracius (bituminous coal) ; 
carbo (anthracite coal). 

Fossils Preserved by Means of Asphalt. One of the most in- 
teresting cases on record is in connection with the fossilized remains 
of plants and animals recovered from the Rancho-la-Brea asphalt 
pits in Los Angeles County, California, about eight miles from the 
City of Los Angeles. 1 These consist of a series of crater-like pits, 



I FOSSILS PRESERVED BY MEANS OF ASPHALT 3 

generally disconnected, now filled with asphalt, from which a variety 
of prehistoric flora and fauna have been excavated, including the 
trunks of trees, pine cones, acorns, mastodons, woolly mammoths, 
elephants, the ancient ox, giant sloth, camel, saber-toothed tiger, 
lion, horse, wolf, cave bear, and numerous species of vultures and 



w . '.i 




Courtesy i-/os /\ngcies museum. 



FIG. 2. Cypress Tree Preserved by Asphalt for 25,000 Years, Rancho-Ia-Brea Asphalt 

Pits, California. 

carnivorous birds, all now extinct. The theory has been advanced 
that the pits were originally formed by "blow-outs'* of gas from an 
underlying oil deposit, forming surface craters of funnel-like shape, 
filled by an inflow of soft, sticky asphalt, which in time became 
quiescent, possibly crusting over, but deadly to any form of beast 



HISTORICAL REVIEW 



that stepped into them. Once mired in the asphalt, the victim's 
struggles would only sink it deeper and attract a host of carnivores 
to the feast. These in turn would only contribute so many more 
victims to the insatiable greed of the trap. Then came carrion 
eaters, vultures, eagles and many others, which contributed avian 




Courtesy Los Angeles Museum. 

FIG. 3. Bones of Pre-historic Animals Excavated from Rancho-la-Brea Asphalt Pits. 

remains to the mass. An artist's conception of the "Death Trap" 
of Rancho-la-Brea is illustrated in Fig. i. The skeletons have been 
preserved perfectly by the asphalt. They have been identified by 
archeologists as belonging to the pleistocene or glacial period, which 
according to authorities terminated about 25,000 years ago, or 
long before the advent of man. 



I USE OF ASPHALT BY THE SUMER1ANS 5 

Figure 2 shows the trunk of a pleistocene cypress found in one 
of the pits in an upright position, packed solidly about with bones 
of the aforementioned animals, and preserved in almost its original 
state by the asphalt which surrounded it. This represents one of 
the oldest specimens of wood in existence and bears mute evidence 
of the remarkable preservation properties of asphalt. 

Figure 3 shows a mass of prehistoric elephant bones, as they were 
being excavated from the asphalt in an adjacent pit. In no other 
known mineral deposits are the bones of these huge beasts preserved 
as well as in the asphalt beds of Rancho-la-Brea. A smaller deposit 
of a similar character has been found near McKittrick, Cal. 2 

Use of Asphalt by the Sumerians (about 3800 to 2500 B.C.)- 3 
The earliest recorded use of asphalt by the human race was by the 
pre-Babylonian inhabitants of the Euphrates Valley in southeastern 
Mesopotamia, the present Iraq, formerly called Sumer and Accad 
(Akkad), and later Babylonia. In this region, between the river 
Nile in Egypt and the Indus river in India, there occur various de- 
posits of asphalt as illustrated in Fig. 4. The following historical 
data have been recorded: 

King Sargon of Accad (about 3800 B.C.}. A legend has come 
down through the ages that King Sargon, while an infant, was 
placed in a reed basket coated with asphalt, by his mother Itti-Bel, a 
Priestess, and set adrift on the waters of the Euphrates river during 
one of its frequent overflows. 4 This corresponds closely with the 
tale of Moses, later appearing in the Bible. 

Manishtusu, King of Kish (about 3600 B.C.}. The bust of 
this early Sumerian ruler was found in the course of excavations 
at Susa, in Persia, whence it is supposed to have been carried by an 
Elamite conqueror in the twelfth century B.C. 5 In describing this 
statue, M. J. de Morgan states ; "the eyes, composed of white lime- 
stone, once ornamented with black pupils now fallen off, are held in 
their orbits with the aid of bitumen 9 , the face appears rough; the 
beard and hair are of conventional design; as regards the inscrip- 
tion, it is engraved in lineal cuneiform characters of the most ancient 
style." The original is at the Louvre and is illustrated in Fig. 5. 

Ornaments (about 3500 B.C.}. Fragments of a ring com- 
posed of asphalt have been unearthed above the flood layer of the 
Euphrates at the site of the prehistoric city of Ur in southern Baby- 



HISTORICAL REVIEW 




FIG. 4. Asphalt Deposits between Nile and Indus Rivers. 



I USE OF ASPHALT BY THE SUM BRIANS 7 

Ionia, ascribed to the Sumerians of about 3500 B.C. 6 Upon analy- 
sis it was found to consist of the following: 

Soluble in pyridine 63.7 per cent 

Ash recovered from pyridine extract 3.8 per cent 

Ash not removed by pyridine 27.4 per cent 

CO 2 equivalent to CaO in ash 1.9 per cent 

Organic matter (by difference) 3.2 per cent 

Total 100.0 per cent 

The mineral constituents were composed of 5 i per cent silica (sand, 
diatoms, foraminifera and cells) and 34 per cent CaSO 4 . 




From "The Civilization of Babylonia and Assyria," J. B. Lippincott Co. 
FIG. 5. Bust of Manishtusu, King of Kish (3600 B.C.) with Eyes Set in Asphalt. 

An interesting ornament has been excavated from one of the 
graves of a Sumerian King at Ur 7 consisting of a statue of a ram 



8 



HISTORICAL REVIEW 



dating back to 3500-3100 B.C. as illustrated in Fig. 6. The head 
and legs of the ram, also the tree-trunk are carved out of wood over 
which gold foil has been cemented by means of asphalt. The back 
$nd flanks of the ram are coated with asphalt in which hair has been 
embedded. 

At Tell-Asmar in Eshnunna (3200 to 2900 B.C.). Excavations 




(From F. A. Brockman, Leipzig. Courtesy 
of New York Public Library) 

FIG. 6. Sumerian Statue of a Ram (3500-3100 B.C.) 

in 1931 at Tell-Asmar, 50 miles northeast of Baghdad, on the 
eastern bank of Diyala river (which joins the Tigris river directly 
south of Baghdad) have revealed the use of asphaltic mastic by the 
Sumerians for building purposes. 8 Similarly, at Khafaje, in the 
same vicinity, excavations have uncovered floors composed of a layer 
of asphalt mastic 3 to 6 cms. thick, likewise clay bricks bonded 
together with asphalt mastic. This mastic has been identified as 



USE OF ASPHALT BY THE SUMERIANS 



9 



asphalt (probably originating in the vicinity of Hit), mineral filler 
(loam, limestone and marl) and vegetable fibers (straw). This 




FIG. 7. Babylonian Pavements Excavated at Tell-Asmar. 




FIG. 8. Babylonian Stair Treads at 
Tell-Asmar. 




FIG. 9. Babylonian Baths Waterproofed 
with Asphalt-Mastic at Tell-Asmar. 



composition was used for bonding bricks in the construction of 
buildings and pavements (Fig. 7) ; for protecting exterior masonry 
surfaces; for troweling over the surface of interior floors and 



10 



HISTORICAL REVIEW 



stair treads (Fig. 8); and for waterproofing baths (Fig. 9), 
drains, etc. 

Lugal-daudu, King of Adab (about 3000 B.C.). In 1903-4, 
Dr. E. J. Banks, while excavating at Adab (known also as Bismaya, 
between the EuhctifiOJldJDuH^^ a marble statue 




of and J* Co* 

FIG. 10. Statue of Lugal-daudu, King of Adab (3000 B.C.) Showing Eyesockets Lined 

with Asphalt. 

of Lugal-daudu, King of Adab (Fig. 10), one of the early Sumer- 
ian rulers, who lived about 3000 B.C. 10 An inscription reveals 
the name of the city of Adab. The eyesockets are hollow, and 
still show the presence of asphalt, indicating that they were 
once inlaid with some substance, probably ivory or mother-of- 
pearl. The statue is now on exhibition at the Ottoman Museum 
in Istanbul. 11 



USE OF ASPHALT BY THE SUMERIANS 



11 



Another statue (Fig. n) originating about the same time (3000 
B.C.), known as the "Human-Headed Bull," is composed of black 
steatite, inlaid with small yellow shells imitating streaks, and held in 
place with asphalt. Many of the shells are intact, gripped firmly by 
the asphalt throughout fifty centuries of time and exposure, thus 
furnishing evidence of its remarkable adhesiveness and durability. 
This statue is now at the Louvre, Paris. 12 




From "The Civilization of Babylonia and Assyria," J. B. Ltppincott Co. 
FIG. ii. Human-Headed Bull (3000 B.C.) with Shells Inlaid in Asphalt. 

Entemena of Shirpula (about 2850 B.C.). An interesting spec- 
imen of Sumerian art was excavated at Lagash, near the mouth of 
the Euphrates, consisting of a sculptured votive offering dating back 
to Entemena, ruler or so-called "Patesi" of Shirpula (2850 B.C.), 
This bears as an inscription, the heraldic device of Lagash, by 
means of which we are enabled to fix its date and origin. The tablet 



12 



HISTORICAL REVIEW 



is an artificial composition of clay and asphalt (Fig. 12). It is also 
on exhibition at the Louvre. 13 

Ur-Nind, King of Lagash (about 2800 B.C.). In the city of 
Kish (Persia) there has been excavated the palace of King Ur-Nina, 
the foundations of which consist of plano-convex bricks cemented 
together with asphalt mortar. Similarly, in the ancient city of Nip- 
pur (about 60 miles south of Baghdad) excavations show Sumer- 
ian structures dating from this same period, composed of natural 




From "The Civilization of Babylonia and Assyria," J. B. Lippincott Co. 
FIG. 12. Heraldic Device of Lagash (2850 B.C.) Cast in Asphalt. 

stones joined together with asphalt mortar, including the "ziggurat" 
of Enlil. 

Ornaments and Sculptured Objects (2800 to 2500 B.C.). 
A number of specimens of sculpture involving the use of asphalt 
were excavated at Susa in the province of Susiana, by M. J. de 
Morgan's expedition of Paris. 14 These are in an excellent state 
of preservation, and by the inscriptions and characteristic orna- 



USE OF ASPHALT BY THE SUMERIANS 



13 



mentation are supposed to have originated between 2800 and 
2500 B.C. 

Figure 13 shows various small animals carved of alabaster 
having the eyes cemented in place with asphalt; Fig. 14, two decor- 
ated vases composed wholly of asphalt; and Fig. 15, a sculpture 






From "Memoires de la Delegation en Perse," by Edm. Pettier. 
FIG. 13. Sumerian Sculpture with Eyes Set in Asphalt. 

of an animal in primitive form, hewn from a mass of asphalt. The 
French chemist, Henri Le Chatelier, analyzed some of the jtsphalt, 
and found it to consist of the fol- 
lowing: 15 

Moisture, 2.8 per cent; asphalt, 
24.4 per cent; wax, 1.6 per cent; 
mineral matter, 71.2 per cent. The 
mineral matter was composed of: 
calcium carbonate, 45.2 per cent; 
calcium sulfate, 3.5 per cent; cal- 
cium phosphate, 0.8 per cent; iron, 
aluminium and silicon oxides, 21.7 
per cent. 

This is conclusive proof that 
the asphalt is a natural product 

composed of 25 per cent asphalt and 75 per cent mineral matter, 
similar to the material obtained in the locality at the present 

day. 

Small statues of Sumerian origin (about 2500 B.C.) have been 
unearthed in Mesopotamia, composed of white clay with wigs of 
asphalt and blobs of red paint on the cheeks. 16 

Gudea of Lagash (about 2700 B.C.) . Another relic, known as 
the "Libation Vase" (Fig. 16) is composed of green steatite, carved 



From "Memoires de la Delegation 
en Perse," by Edm. Pettier. 



p IG . 



4 . Persian Vases Hewn from 
Blocks of Asphalt. 



14 



HISTORICAL REVIEW 



in the form of strange mythical monsters, the effect of which is 
heightened by incrusted little shells set in asphalt, to represent the 




From "Memoires de la Delegation en Perse," by Edm. Pettier. 
FlG. 15. Primitive Animal Carved from Asphalt. 

scaly backs of winged serpents. The serpent was supposed to rep- 
resent the emblem of the god Ningish- 
zida, to whom the accompanying inscrip- 
tion shows the vase to be dedicated by 
Gudea, ruler of Patesi of Lagash. This 
is considered one of the best specimens 
of Sumerian sculpture, and represents 
the height of Sumerian art. It is also 
at the Louvre. 17 

Another inscription credited to Gu- 
dea states: 18 

From "The Civilization of Babylonia 

and Assyria," J. B. Lippincott Co. a* t i, r A.I_ TV /T J 

Asphalt from the Magda moun- 

Fiai6 Libation Vase Dedicated ta } ns j n lam wag transported to his 

to Gudea, Ruler of Lagash (2700 ^. / T , ,, r 

B.C.), Showing Shells Set In As- <~lty Ot JLagash, 
phalt. 

Tablets of Gilgamish (about 2500 

B.C.). In the epic of Gilgamish as revealed in the twelve inscribed 
stone tablets collected by Assur-bani-pal, king of Assyria (668-626 
B.C.), we find reference to the use of asphalt for building purposes. 
These tablets date back to about 2500 B.C. and constitute one of the 
most important pre-Babylonian literary records. In the eleventh 
tablet, Ut-Napishtim relates the w T ell-known story of the Babylonian 
flood, stating that he u smeared the inside of a boat with six sar 
(measures) of kupru (asphalt) and the outside with three sar. 




M19 



I USE OF ASPHALT BY PREHISTORIC RACES IN INDIA 15 

The Persian writer al-Kazwini 20 gives the following interesting 
information relative to the collection and treatment of asphalt found 
in ancient Persia : 

"There are two kinds of native asphalt. First the kind that 
oozes from certain mountains; second we have the kind that appears 
with water in certain pools. When boiled with the water and as 
long as they remain together, the asphalt is soft; but if we separate 
them, the asphalt hardens and becomes hard and dry. It is col- 
lected by means of matting and deposited on the shore. Then it is 
placed in a kettle under which a fire has been lit, and a certain 
amount of sand is added and a mix prepared by constant stirring. 
When the mix is ready, it is poured on the ground, where it cools 
and hardens." 

In ancient texts we are informed that asphalt mastic was always 
sold by volume, namely, by the so-called "gur," the measure used 
for grain, beer, etc., as is evidenced by the very name Ur. Crude 
asphalt, on the other hand, was always sold by weight, by the 
"mina" or "shekel," as were metals and other solid commodities. 

Bur-Sin, King of Ur (about 2500 B.C.) An ancient Sumerian 
chapel erected to the Moon God "Nin-Gal" has recently been 
excavated, in which the floors are composed of burnt bricks em- 
bedded in asphalt mastic which still shows impressions of reeds with 
which it must originally have been mixed, adorned with stone 
tablets, each of which bears the following inscription: 

"Bur-Sin, King of Ur, of Sumer and Accad, King of the four 
portions of the World, has constructed this for his Master Nin-Gal" 

Use of Asphalt by Pre-historic Races in India (about 3000 
B.C.). At excavations conducted in 1923 at Mohenjo-Daro, 
Harappa and Nal, in the Indus valley, northwestern India, evi- 
dences of an advanced form of civilization have been revealed. 21 
An asphalt mastic, composed of a mixture of asphalt, clay, gypsum 
and organic matter, was introduced between two brick walls in a 
layer about i-in. thick for waterproofing purposes. A bathing pool 
measuring 39 by 23 by 8 feet in depth has been unearthed, located 
in front of an ancient temple, probably for ritualistic cleansing pur- 
poses, containing a layer of the mastic on the outside of its walls and 
beneath its floor, 22 as illustrated in Figs. 17 and 18. 



16 



HISTORICAL REVIEW 



The mastic was found to have the following composition: 

Organic constituents 28.3 per cent 

Mineral constituents 71.7 per cent 



Total 100.0 per cent 

The organic constituents were 29.3% soluble in carbon disul-. 
fide and 85.5% in pyridine, and contained 7.1% sulfur. The 
mineral constituents contained: SiO 2 and insoluble: 55.1%; Fe 2 O 3 
and A1 2 O 3 : 11.296; CaSO*: 13.7^; CaO: 4.896; MgCO 3 : 4.296; 




Photo Archeol. Survey of India 
FIG. 17. Water Tank in Front of a Temple Excavated at Mohenjo Daro (Indus Valley). 

vanadium and nickel: traces. This mastic was also used for 
mosaic and inlaid work, as an adhesive for the application of orna- 
ments to statues, and as a protective coating for woodwork. Seep- 
ages of liquid asphalt, as well as rock asphalt deposits exist today 
in India, on the Basti river, near Isakhel (Kashmir) and in the 
Sierras in Hazara District. 

Use of Asphalt by the Early Egyptians (2500 to 1500 B.C.). 23 
The ancient Egyptians were the first to adopt the practice of em- 



USE OF ASPHALT BY THE EARLY EGYPTIANS 



17 



balmlng their dead rulers and wrapping the bodies in cloth which 
was coated with liquid, or melted, solid waterproofing substances, 
including balsams, oleb-resins, gum-resins, true resins, wood-tar 
pitch (obtained during the process of charcoal making), and fre- 
quently with natural asphalt, although Alfred Lucas, formerly di- 
rector of the Chemical Department of Egypt, has recently con- 
tended that he has been unable to detect asphalt in the black 
substance covering embalmed mummies, and concludes that resin 




Photo Archeol. Survey of India 
FIG. 18. Wall of Water Tank at Mohenjo Daro, Showing the Bituminous Layer. 

employed for this purpose. Strabo 24 informs us that "the 
Egyptians used the Dead Sea asphalt for embalming their dead," 
and this practice is also alluded to by Diodorus Siculus, Pliny the 
Elder, Dioscorides, and other writers (loc. cit). The preserved 
remains are known as "mummies" (Fig. 19). 

Before 1000 or 900 B.C. asphalt was rarely used in mummifi- 
cation, except to coat the cloth wrappings and thereby protect the 
body from the elements. After the viscera had been removed, the 
cavities were filled with a mixture of resins and spices, the corpse 



18 



HISTORICAL REVIEW 



immersed in a bath of potash or soda, dried, and finally wrapped 
From 500 to about 40 B.C. (i.e. in Roman times), asphalt was 
generally used both to fill the corpse cavities, as well as to coat the 
cloth wrappings. 25 The word u mumia" first made its appearance 
in Arabian and Byzantine literature about 1000 A.D., 26 signifying 
"bitumen." In Persian it acquired the meaning "paraffin wax," 
and in Syriac alluded to "substances used for mummification." 

The product "mumia" was used in prescriptions, as early as the 
1 2th century, by the famous Arabian physician Al Magor, for the 




FIG. 19. Mummy Preserved with Asphalt 

treatment of contusions and wounds. Its production soon became 
a special industry in the hands of the Alexandrian Jews. As the 
supply of mummies was of course limited, other expedients came 
into vogue. The corpses of slaves or criminals were filled with 
asphalt, swathed and artificially aged in the sun. This deception 
continued for several centuries until in 1564 A.D., it was exposed 
after a journey into Egypt by the French physician, Guy de la Fon- 
taine, and as a result, this trade became extinct in the iyth century. 
The earliest mummies in existence concerning which we have 
authentic data, date back to the Sixth Egyptian Dynasty (about 
2500 B.C.). The earliest specimens include the mummy of Seker- 



I USE OF ASPHALT IN BIBLICAL TIMES 19 

em-sa-f, unearthed at Sakkarah in 1881, and exhibited at Giza, 
near Cairo, 27 and the mummy of King Merenre, now at the Boulak 
Museum, Cairo. 28 

Tut-ankh-amen (or Tutenkhamun), the boy Pharaoh, who ruled 
Egypt about 2000 B.C. and whose treasure-filled tomb was discov- 
ered by Lord Carnarvon of England in 1923, contained two statues 
of the Pharaoh, a black box, a figure of a swan, a couch, an ancient 
chariot, and numerous other wooden objects preserved by impreg- 
nation with asphalt. 

Use of Asphalt in Biblical Times (2500 to 1500 B.C.). 29 Some 
contend that Noah used asphalt in the construction of the Ark 
(Genesis VI, 4). The Biblical text reads, that it was treated with 
"pitch" within and without: "bituminabis earn bituminae" (Vul- 
gate). There is little doubt but that asphalt was used for this 
purpose, since it is well known that canoes and dugouts in the early 
days were made water-tight in the same way. In fact, a number 
of primitive tribes to-day adopt the same procedure. If asphalt 
was actually used by Noah, the date would be fixed at approximately 
2500 B.C., which is usually assigned to the Deluge. 

We find numerous other references in the scriptures to sub- 
stances corresponding to what we now know to be asphalt. The 
Book of Genesis (XI, 3) in describing the building of the Tower of 
Babel (about 2000 B.C.) states ". . . and they had brick for stone, 
and slime had they for mortar." There seems to be no question 
but that the so-called "slime" alludes to asphalt, since the word 
translated as "slime" in the English version (1568), occurs as 
d<r<aXros in the Septuagint, and as "bitumen" in the Vulgate. 

In the Septuagint, or Greek version of the Bible, this word is 
translated as "asphaltos," and in the Vulgate or Latin version, as 
"bitumen." In the Bishop's Bible of 1568 and in subsequent trans- 
lations into English, the word is given as "slime." In the Douay 
translation of 1600, it is "bitume," while in Luther's German ver- 
sion, it appears as "Thon," the German word for clay. 

Similarly, in Genesis (XIV, 10) we are informed that the Vale 
of Siddim "was full of 5/m^pits," referring no doubt to exudations 
of liquid asphalt. Moreover, it is pointed out by certain authorities 
that the area described as the Vale of Siddim corresponds to our 
present Dead Sea, from which asphalt is still obtained. 



20 



HISTORICAL REVIEW 



Again we are told (Exodus II, 3) that in constructing the basket 
of bulrushes in which Moses was placed, it was daubed "with slime 
and with pitch" This took place about 1500 B.C. 30 As was pointed 
out previously, this constituted an early method of constructing 
boats. Even at the present time, boats known as "guffas" as illus- 
trated in Fig. 20 are constructed of woven reeds caulked with as- 




FIG. 20. The Guffa, or Coracle, Used for Centuries in Parts of the Near East. 

phalt, 31 and are used to ferry passengers and merchandise across 
the Tigris river at Baghdad. 

While excavating at the ancient Biblical city of Jericho in Pales- 
tine, 32 brick walls were found in which asphalt mastic was used as 
mortar, dating back to about 2500-2100 B.C. 

It is also contended that the glance pitch deposit known as u Suk- 
El-Chan," on the western slope of Mount Hermon in the upper 
Jordan valley, near Hasbaya (loc. cit.) has been worked since about 
1600 B.C. 

Use of Asphalt by the Babylonians (2500 to 538 B.C.). Baby- 
Ionia was the name given to the plain of the Tigris and Euphrates 



I USE OF ASPHALT BY THE BABYLONIANS 21 

rivers, now forming the modern province of Irak. The Babylonians 
were well versed in the art of building, and each monarch commemo- 
rated his reign and perpetuated his name by constructing some vast 
engineering work. Certain kings built roadways, others built re- 
taining walls to impound the waters of the Euphrates, and still others 
mighty battlements and palaces. Such facts were indelibly recorded 
by inscriptions on the bricks used for the purpose, many of which 
are still in existence. The bricks were of the so-called "plano- 
convex" type, being formed by hand, with one side flat and the 
other face convex and then kiln burnt. Bitumen was used as mor- 
tar from very early times. Sand, gravel or clay were employed in 
preparing these mastics. Due to the porous nature of the bricks, 
the asphalt was partially absorbed, resulting in a very strong bond. 
At first, the spaces between the bricks was filled with a 3 to 6 cm. 
layer of mastic, but in later periods there was a tendency to dimin- 
ish the space. 

Asphalt-coated tree trunks, e.g. poplar, were often used to rein- 
force wall corners and joints, as for instance in the temple tower of 
Ninmach in Babylon. In vaults or arches a mastic-loam composition 
was used as mortar for the bricks, and the keystone was usually 
dipped in asphalt before being set in place. Reuther reports that 
bituminous paint was applied to the outer walls of buildings in 
Babylon over a loam plaster, first primed with a gypsum distemper. 
Asphalt was also used to waterproof brick basins at Ur and Erech. 83 

King Khammurabi (about 2200 B.C.). The use of bitumi- 
nous mortar was said to have been introduced in the city of Babylon 
by King Khammurabi (Amraphel of the Bible). Robert Koldewey 
reports that when excavating in Babylon, he found "it was exceed- 
ingly difficult to separate the brick courses from each other." 34 
This \vas also confirmed by A. H. Layard, who states that "Bricks 
bonded with asphalt have remained immovably in place for thou- 
sands of years." 35 

Queen S emir amis (about 700 B.C.) Queen Semiramis is 
stated to have built a tunnel under the Euphrates at Babylon, about 
1000 meters long, of burnt bricks coated with asphalt as mortar. 36 
The asphalt thus functioned as a waterproofing agent, very much 
in the same manner as it is used to-day. 

King Nabopolassar (625 to 604 B.C.). Nabopolassar is cred- 



22 HISTORICAL REVIEW I 

ited with having built a palace on a platform consisting of ten 
courses of burnt bricks set with an asphalt mortar and surfaced 
with a layer of asphalt mastic. One of his inscriptions states : 

U I made a Nabalu and laid its foundations against the bosom of 
the underworld, on the surface of the water, in bitumen and brick. 
I raised its roof and connected the terrace with the palace. With 
bitumen and brick, I made it tall like unto wooded mountains." 

According to his son Nebuchadnezzer, he is given the credit to 
have laid the first asphalt block pavement in Babylon. 

King Nebuchadnezzar (604 to 561 B.C.). Of all the Baby- 
lonian rulers, Nebuchadnezzar was the most progressive, and is 
stated to have reconstructed the entire city. The bricks bore in- 
scriptions relating to his work, and several refer specifically to the 
use of asphalt. One found in the so-called "Procession Street" 
(Aiburshabu) which led from his palace to the North wall, reads as 
follows : sr 

"Nebuchadnezzar, King of Babylon, he who made Esaglia and 
Ezida glorious, son of Nabopolassar, King of Babylon. The streets 
of Babylon, the Procession Street of Nabu and Marduk, my lords, 
which Nabopolassar, King of Babylon, the father who begot me, had 
made a road glistening with asphalt and burnt bricks; I, the wise 
suppliant who fears their lordships, placed above the bitumen and 
burnt bricks, a mighty superstructure of shining dust, made them 
strong within with bitumen and burnt bricks as a high-lying road. 
Nabu and Marduk, when you traverse these streets in joy, may bene- 
fits for me rest upon your lips; life for distant days, and well-being 
for the body. Before you I will advance upon them. May I attain 
eternal age!" 

This street was constructed with stone slabs brought from distant 
parts, set in a bituminous mortar, the interstices being very narrow 
at the surface and widening towards the base of the stones. The 
foundation consisted of three or more courses of bricks joined to- 
gether with bituminous mortar. 

This would seem to be the forerunner of the present-day pave- 
ment composed of stone blocks set in asphalt. It seems strange that 
the art should have become lost to mankind, only to be rediscovered 
in the nineteenth century A.D. 

The most comprehensive relic left by Nebuchadnezzar is known 



I USE OF ASPHALT BY THE BABYLONIANS 23 

as the "Large Inscribed Stone Tablet" (sometimes referred to as 
the "East India House Inscription"), which contains a detailed ac- 
count of his building activities. A translation by Fr. Delitsch 38 
reads in part as follows (Column 7, lines 34 et seq.) : 

"In Babil, my favorite city that I love, was the palace, the house, 
the marvel of mankind, the center of the land, the dwelling of 
majesty, upon the Babil place in Babil, from Imgur-Bel to the eastern 
canal Libil-Higalla ; from the bank of the Euphrates to Aiburshabu, 
which Nabopolassar, King of Babylon, my father, my begetter, built 
of crude bricks, and dwelt in it In consequence of high waters, its 
foundations had become weak, and owing to the filling up of the 
streets of Babil, the gateway of that palace had become too low. I 
tore down its walls of dried brick, and laid its corner-stone bare, and 
reached the depth of the waters. Facing the water, I laid its foun- 
dation firmly, and raised it mountain high with bitumen and burnt 
brick. Mighty cedars, I caused to be laid down at length for its 
roofing. . . . For protection, I built two massive walls of asphalt 
and brick, 490 ells beyond Nimitti-Bel. Between them I erected a 
structure of bricks on which I built my kingly dwelling of asphalt and 
bricks. This I surrounded with a massive wall of asphalt and burnt 
bricks, and made upon it a lofty foundation for my royal dwelling 
of asphalt and burnt bricks" 

It thus appears that Nebuchadnezzar profited by the experience 
of his father, and instead of building a retaining wall of dried clay 
bricks, which had failed to hold back the Euphrates due to its lack 
of waterproof properties, he resorted to the use of burnt bricks and 
asphalt, and apparently with satisfactory results. 

Robert Koldewey's investigations indicate that the method of 
constructing walls in Babylonia and Nineveh consisted in laying in 
rotation, first a course of bricks, then a layer of asphalt, then a layer 
of clay and then another course of bricks. 39 The joints in each 
course were composed of asphalt and clay. In every fifth course, the 
clay was replaced by a matting of reeds. This matting is now en- 
tirely rotted and gone, but its impression is clearly recognizable in 
the asphalt. An attempt to separate the courses to prevent adhesion 
is thus apparent, but the reason is not obvious. Only in one locality 
(Temple of Borsippa) does it appear that asphalt has been used in 
direct contact with the bricks, where they still hold together in a 
firm mass. 



24 



HISTORICAL REVIEW 



It is probable that the asphalt used by the Babylonians was de- 
rived from springs similar to the ones still found in Mesopotamia, 
of which Fig. 21 is a typical example of an asphalt spring at Hit. 
Deposits of pure asphalt are found to-day at various localities in 
this region, including Ain Mamurah, Ain-el-Maraj, Al-Kuwait 
(Arabia), Bushire (Iran), and Bundar Abbas (Iran). 

Figure 22 shows the present appearance of the brick floor of 
Nebuchadnezzar's Throne Hall, Babylon, looking towards the 




From "Light on the Old Testament," by Prof. A. T. Clay. 
FIG. 21. Asphalt Spring in Mesopotamia. 

Euphrates. The burnt bricks bearing the name of Nebuchadnezzar 
(of which one is shown in the foreground) were laid in asphalt, and 
are still so firmly jointed together to-day, that it is impossible to 
part them without destroying their integrity. 40 

King Nebuchadnezzar also built a bridge across the Euphrates 
near Babylon, 370 feet long. The piers were constructed of burnt 
bricks embedded in asphalt mastic, the bases of which were pro- 
tected with a superficial coating of asphalt. He also constructed 
large sewers ("cloacae") for draining the city of Babylon, lined 
with blocks composed of a mixture of asphalt, loam and gravel. 



I 



USE OF ASPHALT BY THE ASSYRIANS 



25 



The use of bituminous mortar was abandoned in Babylon 
towards the end of Nebuchadnezzar's reign, in favor of lime mor- 
tar to which varying amounts of asphalt were added. After the 
fall of Babylon (538 B.C.) even the addition of asphalt was dis- 
continued. In the ensuing Persian period (538 to 300 B.C.), the 




Copyright by Underwood & Underwood, N. Y. 



FIG. 22. Floor of Nebuchadnezzar's Temple as it Appears To-day, Showing Blocks 

Joined by Means of Asphalt. 

lime was replaced in turn w r ith clay as mortar, and this resulted in a 
retrogression in the building art. 

Use of Asphalt by the Assyrians (1400 to 607 B.C.). 41 The 
name Assyria was derived from the city of Assur (now Kalah 
Shargat) situated on the right bank of the Tigris, midway between 
the Greater and Lesser Zab rivers. Assur was finally supplanted 



26 HISTORICAL REVIEW I 

by Nineveh as capital (Nebi Yanus and Kuyunjik) some 60 miles 
farther north. 

King Adad-Nirari I (about 1300 B.C.). This monarch is stated 
to have built an embankment i mile long along the banks of the 
Tigris, in which the stones were joined together with an asphaltic 
mortar. W. Andrae reports that tablets have been found in the 
embankment at Assur, recording the fact that the asphalt ("kupru" : 
pitch) used was mined at Ubase (present Quala Shargat), and in 
reference to the mortar states that "After 3300 years, it still faith- 
fully fulfils its purpose." 42 Andrae likewise refers to an ancient 
temple mound excavated at the former site of Erech, dating back 
to this same period, which was constructed of courses of dried clay 
bricks bound together with a mortar composed of asphalt mixed 
with clay. It is interesting to note in passing, that in the ancient 
Assyrian moral code we find reference to asphalt, which was pre- 
scribed to be poured onto the heads of delinquents in a molten 
state. 

King Tukulti-Ninurta 11 (890 to 884 B.C.). This King, in his 
annals makes reference to the fact: 43 

"In front of Hit, by the bitumen springs the place of Usmeta 
Stones where the gods speak I spent the night." 

King Sargon (722 to 705 B.C.). The following inscription oc- 
curs on the bricks of the so-called "Sargon Wall" of Babylon, built 
by King Sargon, founder of the last and most illustrious Assyrian 
dynasty, as it has been translated by Fr. Delitsch : 44 

"To Marduk, the Great Lord, the divine Creator, who inhabits 
Esagila, the Lord of Babil, his lord Sargon, the mighty king, King 
of the land of Assur, King of all, governor of Babil, King of Sumer 
and Akkad, the nourisher of Esagila and Ezida. To build Imurg- 
Bel was his desire; he caused burnt brick of pure JKiru (?) to be 
struck, built a kar ( ?) with tar and asphalt on the side of the Ishtar 
Gate to the bank of the Euphrates in the depth of the water, and 
founded Imgur-Bel and Nimitti-Bel mountain high, firm upon it. 
This work may Marduk, the great Lord, graciously behold, and 
grant Sargon, the prince who cherishes him, life! Like the foun- 
dation stone of the Sacred City, may the years of his reign endure. " 

"Imgur-Bel" was the name given to the inner wall of Babylon, 
and "Nimitti-Ber to the outer. ^ 



I REFERENCES BY GREEK AND ROMAN WRITERS 27 

King Sennacherib (704 to 682 B.C.). One of this King's in- 
scriptions 45 informs us that he : 

"Covered the bed of the diverted river Telbiti with rush matting 
at the bottom and quarried stone on top, cemented together with 
natural pitch (asphalt). I thus had a stretch of land 454 ells long 
and 289 ells wide, raised out of the water and changed into dry 
land" (Inscription No. 6). 

The year 607 B.C. marked the destruction of Nineveh and the 
end of the Assyrian empire. 

Use of Asphalt in Constructing Lake-Dwellings (about 1000 
B.C.). In the bronze-age, dwellings were constructed on piles in 
lakes close to the shore the better to protect the inhabitants from 
the ravages of wild animals and attacks from marauders. Excava- 
tions have shown that the wooden piles were preserved from decay 
by coating with asphalt. Remains preserved in this manner have 
been found in Switzerland, in the lakes of Bourget, Geneva, N^u- 
chatel, Bienne, Zurich and Constance. 46 

References to Bituminous Substances by Greek and Roman 
Writers (500 B.C. to 817 A.D.) 

Herodotus (484 to 425 B.C.). The Greek historian Herodo- 
tus, in his treatise "Historiarum" 47 refers to deposits of asphalt at 
Hit (the present town of Kirkuk in Mesopotamia) as follows: 

"There is a city called Is (Hit), eight days' journey from Baby- 
lon, where a little river flows, also named Is, a tributary stream of 
the river Euphrates. From the source of this river many 'gouts' 
of asphalt rise with the water; and from thence the asphalt is 
brought for the walls of Babylon." 

Many references occur in the earliest writings to Hit (Accadian 
"Id," Greek "Is"). A more recent though interesting description 
of the asphalt deposit at Hit is furnished by a British traveler 
George Rawlinson ( I745), 48 who described his visit to that locality 
as follows: 

"Having spent three days or better among the ruins of old 
Babylon, we came into a town called Hit, inhabited only by Arabians, 
but very ruinous. Near unto this town is a valley of pitch, very 
marvelous to behold, and a thing almost incredible, wherein are 
many springs throwing out abundantly a kind of black substance, 



28 HISTORICAL REVIEW I 

like unto tar and pitch, which serveth all the countries thereabouts 
to make staunch their barks and boats. Every one of which springs 
maketh a noise like a smith's forge in puffing out the matter, which 
never ceaseth night or day, and the noise is heard a mile off, swal- 
lowing all the weighty things that come upon it. The Moors call it 
the Mouth of Hell." 

A translation of a tablet unearthed at Karnak 49 reveals the 
fact that part of the tribute paid Thothmes III (Tethmosis III), 
about 1500 B.C. from Mesopotamian cities consisted of 2040 minae 
(about 1000 kg.) of "zift" (Arabic for native asphalt), sent by 
the ruler of Is (Hit), 50 but the foregoing has been controverted. 

Herodotus also states (VI, 119) that asphalt was obtained 
from wells near Ardericca (near the present town of Kirab) in the 
land of Cissia (now Persia) : 

"At Ardericca, 210 stadia from Susa, there is a well another 
40 stadia away, which produces three different substances, since 
asphalt, salt and oil are drawn up from it. ... It assumes three 
different forms : the asphalt and the salt immediately become solid, 
but the oil they collect, and the Persians call it Rhadinance; it is 
black and emits a strong odor." 

At Elam, in the province of Susiana in Persia, asphalt is still 
collected in this crude manner. 

Herodotus refers (IV, 195) to a deposit of pure, soft asphalt 
at Zacynthus (now Zante), on the Greek coast, as follows: 

"I myself have seen the pitch drawn up out a pool of water in 
Zacynthus, and there are several pools there, the largest of which 
is 70 orgyoe (i- e - fathoms) long and broad, and 2 orgyoe in depth. 
Into this, they let down a pole with a myrtle branch fastened to its 
end, and then draw up the pitch adhering to the myrtle. It has the 
smell of asphalt, but in other respects is better than the pitch of 
Pieria (now Thessalonica). Then they pour it into a pit that has 
been dug near the pool; and when much is collected, they fill their 
vessels from the pit." 

Herodotus was the first writer to describe the construction of 
small round boats woven together of reeds, like baskets, covered on 
the outside with hides, and waterproofed with a coating of natural 
asphalt, similar to the present-day "guffas" found in Mesopotamia 
(I, 194). He also described the use of bituminous mortar, com- 



I REFERENCES BY GREEK AND ROMAN WRITERS 29 

posed of asphalt and straw, for joining together stones and clay 
bricks in building masonry walls at Media. 

Thucydides (471 to 401 B.C.). The Greek hsitorian Thu- 
cydides 51 refers to the use of petroleum for military purposes and 
describes a mixture of asphalt and sulfur, which was used to ignite 
fascines piled against the wooden walls in the sieges of Plataea 
and Delium. 

Hippocrates (460 to 377 B.C.). This Greek philosopher and 
physician 52 refers to several of the asphalt deposits already men- 
tioned. 

Xenophon (430 to 357 B.C.). The Greek historian Xeno- 
phon 53 describes a wall built in Media, composed of burnt bricks 
cemented together with asphalt, similar to the method of construc- 
tion used in Babylon. 

Aristotle (384 to 322 B.C.). This Greek writer and philoso- 
pher 54 states : 

''Inflammable oils rise in large quantities in the soil of Persia, 
and in smaller quantities in Sicily, where they often have the distinct 
odor of cedar resin. Thick, dark and viscous oils flow beside nat- 
ural pitch and asphalt in Macedonia, Thrace and Illyria (Selenitza 
in Albania) from the hot, often burning soil, smelling of sulfur and 
bitumen, and diffuse stinking, choking and sometimes deadly fumes. " 

Theophrastus (372 to 288 B.C.). This Greek writer 55 de- 
scribes the production of wood tar, which he states was an estab- 
lished industry. He likewise gives a comprehensive account of 
several occurrences of asphalt, and refers to: 

"An earth in Cilicia (present Turkey-in-Asia ) , which becomes 
viscous on heating." 

Antigonus (about 311 B.C.). We are informed 66 that Antig- 
onus of Macedonia in 311 B.C. sent Hieronymus of Cardia with 
an army to capture the asphalt works at the Dead Sea from the 
Nabataeans. This deposit seems to have been greatly prized. 
Later, Ptolemy II (309-246 B.C.) in turn, captured the Dead Sea 
asphalt works. It then passed on to the Seleucids, from whom 
Antony took it and presented it to Cleopatra. The latter leased it 
to Malchus, the Nabataean, in 36 B.C., who in 32-31 B.C. failed to 



30 HISTORICAL REVIEW I 

pay rent and was accordingly punished by Herod. The subsequent 
history of this most interesting deposit is lost in obscurity. 

Hannibal (247 to 183 B.C.). The Carthaginian general Han- 
nibal is said to have used asphalt in compounding the so-called Greek 
Fire ( u lgnae Vestoe"), which was claimed to burn so fiercely, that 
even water would not extinguish it, and was used extensively by him 
in warfare. 

Vergil (70 to 19 B.C.). This Roman poet 57 refers to the me- 
dicinal use of bitumen, applied externally as a cure for scabies. 

Strabo (63 B.C. to 24 A.D.}. The Greek geographer Strabo 58 
refers in detail to the Dead Sea asphalt deposit This was termed 
u Lacus Asphaltites" by the classical writers, and the asphalt derived 
therefrom, as "Bitumen Judaicum." Strabo states (XVI, 740) : 

"The Dead Sea is full of asphalt. It comes to the surface ir- 
regularly at the center, with noisy disturbance of the water, which 
appears as though it were boiling. The visible portion of the 
asphalt lumps is round and has the form of a hillock. Much sooty 
matter accompanies the gaseous emanation, which tarnishes copper, 
silver and all bright metals, and even causes gold to rust." 

He adds further (XVI, 764) : 

"The asphalt remains on the surface of the water, owing to its 
salty nature. People go in rafts to the asphalt, hack it to pieces, 
and take as much of it away with them as they can." 

He also offers the following interesting theory regarding the 
origin and formation of Dead Sea asphalt (XVI, 763) : 

"Asphalt is a lumpy earth, which has been liquefied by heat and 
again comes forth and spreads out, and eventually becomes con- 
verted into a dense, solid mass by the cold sea water, so that it 
must be worked with knives and axes. Undoubtedly, this occurs in 
the center of the lake, since the fire originates there and likewise 
the asphalt. The asphalt is generated irregularly, since the move- 
ment of the fire, the force of the wind, etc., have no marked regu- 
larity." 

Strabo has the following to offer regarding Babylonian asphalt 
(I, 16): 

"Poseidonius (died 51 B.C.) declares that there are wells of 
black and also white naphtha in Babylonia. The white naphtha, 



I REFERENCES BY GREEK AND ROMAN WRITERS 31 

which attracts fire, is composed of liquid sulfur (?); the black 
naphtha is simply liquid black asphalt, which can be burnt in lamps 
instead of olive oil." 

He states further (XVI, 743): 

'There is much asphalt in Babylonia, about which Erathosthenes 
(of Alexandria, 276 to 194 B.C.) has the following to say: "The 
liquid, which is called naphtha, is found in the region around Susa. 
The more solid material, which may become hard, occurs in Baby- 
lonia. The source is near the Euphrates. When this river over- 
flows its banks, through the melting of the snow on the mountains, 
this well also overflows and wends its way to the river. With it 
come large lumps of asphalt which is very suitable for use in Cement- 
ing bricks for house building. Others say that the liquid kind also 
occurs in Babylonia. I have already said how useful the solid kind 
is for the building of houses. It is said that ships are also made of 
it and that if they are coated with it, they will become watertight'." 

Strabo refers (XVI, 738) to the use of asphalt mortar, both 
for constructing walls of houses and for waterproofing tunnels. He 
observes (VII, 316) : 

"Asphalt from Rhodes requires more olive oil for cutting, than 
that from Pieria (Thessalonica)." 

He informs us that "pissasphaltos" [derived from the Greek 
words "pissa" (pix or pitch) and "asphaltos" (asphalt)] 59 occurs 
in the neighborhood of Epidamnos (or Dirrachion) on the main- 
land of Albania, stating (VII, 316) : 

"In the country of the Apolloniates at a place called Nymph- 
aeum, there occurs a rock, at the base of which, fire gushes forth, 
accompanied by streams of hot water and melted asphalt, and un- 
doubtedly it is the mass of asphalt that burns. This occurrence is 
found near the summit. The mass carried away by the water is 
eventually recovered, since it is again converted into asphalt, which 
as Poseidonius has noted, may be dug out of the earth on a hill in 
the vicinity." 

This most likely alludes to the present-day deposit of Selenitzia 
in Albania. 

Strabo also refers to the use of asphalt paints, in respect to 
which he comments (XVI, 739) : 

"For want of wood for building, only the beams and stays in 
houses are made of the wood of the date-palm. The stays are stif- 



32 HISTORICAL REVIEW I 

fener with cord made of plaited rushes. Then everything is plas- 
tered and painted and the doors are coated with asphalt." 

Diodorus Siculus (about 50 A.D.}. This Greek historian 60 
also describes the Dead Sea deposit (XIX, t. 98, Chap. 2) as 
follows : 

" It is a large sea which yields up much asphalt and from which 
a by no means negligible revenue is derived. The sea is about 500 
stadia in length and 60 stadia wide. The water stinks and is exceed- 
ingly bitter, so that fish cannot live in it, nor do any other creatures 
occur in it. Although large rivers of very fresh water flow into it, 
the sea remains bitter. Every year a large quantity of asphalt in 
pieces more than 3 plethra (no yards) float in the middle of the 
sea. The advent of asphalt is heralded 20 days before its arrival, 
for all around the sea the stench is wafted by the wind over many 
stadia, and all the silver, gold and copper in the neighborhood be- 
come tarnished, but the tarnish disappears again when the asphalt 
rises to the surface. The district in the vicinity, which is readily 
inflammable, and which is pervaded by an unpleasant odor, makes 
the people's bodies ill and they die young." 61 

In connection with the Babylonian asphalt deposits, he states 
(II, Chap. 12): 

u Of all the many wonders occurring in Babylonia the most 
astounding consists of the large deposits of asphalt which are found 
there. So much is found that it not only suffices for many and large 
buildings, but the surplus is used by the populace, who gather large 
quantities in various localities, which after drying is used as fuel in 
place of wood. In spite of the large number of inhabitants who thus 
consume the asphalt, its supply remains as inexhaustible as the water 
from the wells. 

He also alludes to the fact that in constructing the walls of the 
city of Media, the stones were cemented together with an asphalt 
mortar, as previously remarked by Herodotus and Xenophon. He 
refers to the use of asphalt for embalming the dead (XIX, t. 98, 
Chap. 2), stating: 

"The largest portion of the asphalt derived from the Dead Sea 
is exported to Egypt, where among other uses, it is employed to 
mummify dead bodies, for without the mixture of this substance 
with other aromatics, it would be difficult for them to preserve these 
for a long time from the corruption to which they are liable." 



I REFERENCES BY GREEK AND ROMAN WRITERS 33 

Vitruvms (about 50 A.D.}. The Roman architect Vitruvius, 
otherwise known as Marcus Vitruvius Pollio 62 refers to the pres- 
ence of asphalt in the neighborhood of Babylon, which he describes 
as being of a liquid consistency, and states further (VII, 3 and 8) : 

u Asphalt is found in Carthage and Ethiopia, and fluid and solid 
varieties are found in Arabia . . . likewise near Joppa in Syria. 
... In nomad Arabia are lakes of immense size producing much 
bitumen which is gathered by the neighboring tribes. This is not 
surprising, because there are many quarries of hard bitumen there. 
When a spring of water flows through this land, it draws the bitu- 
men with it, and passing along, the water disappears and deposits 
the bitumen." 

He likewise refers (I, 5 and 8) to the Dead Sea occurrence, 
those at the city of Hit, also to the Albanian deposit, and mentions 
the use of asphalt mortar for constructing masonry walls at 
Media. 

Pliny the Elder (23 to 79 A.D.}. This Roman naturalist 63 
refers to Dead Sea asphalt (XXXV, 178) as u slimy bitumen" and 
states that a deposit is found in solid form "as an earth" in the vi- 
cinity of Sidon, which undoubtedly corresponds to the present Suk- 
el-Chan glance pitch mine (loc. cit. ). Pliny refers (VI, 99) to 
another deposit, most likely in the neighborhood of the present town 
of Bushire in Mesopotamia, stating: 

"Here flows the river Granis through Susiana, on the right bank 
of which the Deximontani dwell, who manipulate bitumen." 

Again, he refers (II, 235) to: 

"Petroleum wells at Astacensis in Parthia (northeastern Persia) 
capable of yielding asphalt." 

Pliny describes (XXXV, 178) how the natives of Sicily gather 
asphalt, as follows: 

"The inhabitants gather the asphalt from the surface of pools, 
by stirring with branches, to which it will easily adhere." 

He comments (VII, 65 ) upon the high ductility of good asphalt: 

"Asphalt that is elastic and cohesive cannot be split apart, since 
it adheres to all objects that come in contact with it. It will draw 
out into long threads when anything is dipped into the sticky mass," 



34 HISTORICAL REVIEW I 

Again (XXXV, 180): 

"Bitumen is prized most highly when it is bright and heavy; 
and becomes less bright when mixed with pitch. It has the same 
properties as sulfur; it cracks, but heals itself, since the cracks again 

close up." 

* * 

He states further that: 

"The best quality floats on the surface when the mass is^ boiled 
. . . and liquid bitumen is burnt in lamps in place of olive oil" 

Pliny alludes to "pissasphaltos" (XXIV, 41; XXXV, 182)' as 
follows : 

"A mixture of pitch and asphalt being termed pissasphaltos. 1 ' 

He refers to "ampelitis," i.e. mineral wax (XXXIV, 194)) 
stating : 

"Ampelitis greatly resembles bitumen, and like bitumen becomes 
liquid when it has absorbed oil." 

He further informs us that "gagates" (asphaltite or jet) are 
found in Lycia (XXXVI, 141). 

Pliny refers to the production of wood tar (XIV, 122 and 127; 
XVI, 38 and 52) as follows: 

"Stacking a large pile of wood, covering it with a layer of earth 
or sods and then setting fire to the wood. The tar produced in this 
manner is drawn off through a drain 16 ells long leading from under 
the stack." 

He also alludes to the production of wood-tar pitch (XVI, 52) 
as follows: 

"The boiling of pitch (Latin: 'picem coquere' ) derived from 
wood tar." 

Likewise, that (XV, 8; XXIV, 24) : 

"Tar oil can be obtained by stretching a hide over a cauldron 
containing boiling pitch, and then wringing out the condensed liquid." 

He refers to the use of wood tar and wood-tar pitch for water- 
proofing pottery (XIV, 134; XV, 62), for calking ships (XVI, 56 
and 158), and as a paint for roofs and walls (XXXV, 41; 
XXXVI, 1 66). 



I REFERENCES BY GREEK AND ROMAN WRITERS 35 

Pliny refers to the use of asphalt in warfare as follows (CIV) : 

u The attack of Lucullus on the city of Samosata was repelled 
with the assistance of burning maltha. ... In the city of Samosata 
in Commagene, there is a body of water on the surface of which 
there was ignited a mass of slime called maltha. When this slime 
comes in contact with any solid bodies, it adheres to them and fol- 
lows those that retreat Thus as the city was besieged by Lucullus, 
the inhabitants ignited the walls and drove back the soldiers and 
destroyed their weapons. Experiments have proven that the burn- 
ing slime can only be extinguished with damp earth." 

He comments (XXXIV, 15) on the use of asphalt as a paint: 

"The ancients coated. their bronze monuments wjth bitumen, 
which makes it all the more remarkable to remember that they pre- 
ferred to cover them with gold. I do not know whether it is a 
Roman invention, although it is said that it was done at Rome first." 

And again (XXXV, 183): 

"Copper house utensils are painted with bitumen to make them 
more resistant to heat and flame. . . . Iron workers use it in their 
workshops for varnishing iron, for the heads of nails, and for many 
other purposes." 

He also refers (XIV, 20) to the use of asphalt: 

"To coat the inside of wine casks and water receptacles." 

Pliny describes the use of asphalt for medicinal purposes 
(XXXV, 1 80 and 182) and recommends it for curing boils, inflam- 
mation of the eyes, coughs, asthma, blindness, epilepsy, etc. He tells 
us that it was sold under the name mumia, which we are informed 
was actually scraped from the mummies taken from tombs. Its 
alleged curative properties w r ere explained by the fact that it pre- 
served the dead for so many centuries. 64 

Josephus Flavins (37 to 95 A.D.}. This Roman historian 66 
referred to Dead Sea asphalt stating: 

"The changes in the color of the Dead Sea are astonishing, since 
it alters three times daily and when the sun's rays change their direc- 
tion they are reflected irregularly." 

He also describes the use of bitumen in medicine as a remedy 
for trachoma, leprosy, gout and eczema. 

Plutarch (about 46 A.D.}. This Greek historian Plutarch 66 
informs us : 



36 HISTORICAL REVIEW I 

U A Macedonian named Proxenus, who had charge of the King's 
equipage, on opening the ground by the river Oxus (present Turko- 
man Republic) in order to pitch his master's tent, discovered a spring 
of gross oily liquor, which after the surface was taken off came 
perfectly clear and neither in taste nor smell differed from olive oil, 
nor was it inferior to it in smoothness and brightness, though there 
was no olive tree in that country. It is said indeed, that the water 
of the Oxus is of so unctuous a quality, that it makes the skin of 
those who bathe in it smooth and shining." 

Tacitus (55 to 117 A.D.}. The Roman historian states 67 in 
reference to Dead Sea asphalt: 

"Those whose calling is to gather asphalt, draw one end into 
their boat, whereupon the balance of the mass will follow without 
effort. This is continued until the vessel is filled, whereupon the 
viscous mass is cut to pieces. . . . This unusual substance floats 
in heaps upon the Dead Sea and is either towed or pulled ashore 
by hand, where it is easily manipulated. When it is sufficiently 
dried, either by the heat of the sun or by the vapors of the earth, it 
becomes hard and may be broken up into pieces, as wood or stone, 
by means of chisels or the force of axes. . . . The hardening may 
be hastened by wetting with vinegar until it acquires the desired 
cohesion." 



Aelian (Aelianus Claudius] (about laoA.D.). This Roman 
writer and rhetorician refers to various sources of asphalt 68 

Dioscorides (about 150 A.D.). The Greek physician Dioscori- 
des 69 states (I, 83) that there is a source of asphalt, referred to 
by him as "Lacus Asphaltites," at Sidon, which is assumed to refer 
to Siddim, i.e., to the Dead Sea deposit. He states further that: 

"Asphalt is found in its liquid state at Acragantium (the present 
Agrigento) in Sicily. It floats on the surface of the springs. It 
is a kind of liquid bitumen and is used in lamps in place of olive oil." 

He also alludes to Albanian asphalt under the term "pissasphal- 
tos" as follows (I, 84) : 

"In the vicinity of Epidamnos (i.e. Dirrachion in Albania), 
there is found a substance called 'pissasphaltos.' It comes down 
from the Ceraunic mountains and is carried along by the force of 
the water and deposited on the banks of the rivers, where it is found 
in lumps. It smells of pitch mixed with asphalt." 



I REFERENCES BY GREEK AND ROMAN WRITERS 37 

In reference to Indian asphalt, presumably referring to the de- 
posit at the Basti river, near Isakhel, India, in the upper Indus Val- 
ley, he comments (I, 83) : 

"Bitumen obtained in India is prized most highly, but they do 
not disclose the locality where it is found. It is so desirable because 
of its purple hue, its heavy weight and characteristic strong odor. 
The dark and impure varieties of asphalt are full of faults, since 
they have been mixed with pitch, and they come from Phoenicia, 
Babylon, Zacynthos and Sidon." 

He states that asphalt may be refined: 

"By boiling off the fluid constituents, which make the material 
so inflammable." 

Dioscorides also informs us that: 

"The name mumia is given to the drug called 'Bitumen of 
Judea,' and to the mumia of the tombs, found in great numbers in 
Egypt, and which is nothing more than a mixture which the Byzan- 
tine Greeks useci formerly for embalming their dead, in order that 
the bodies might remain in the state in which they were buried, and 
experience neither decay nor change. Bitumen of Judea is the sub- 
stance which is obtained from the Asphaltites Lake." 

He mentions (V, 181) that "ampelitis" comes from Selenica, 
and "gagates" from Lycia (V, 146) ; also that (I, 85) : 

"Asphalt is recommended as a panacea against skin afflictions." 

Dion Cassius (155 to 230 A.D.}. This Roman historian 
states : 70 

"There is Babylon, Trajan saw the asphalt with which the walls 
of Babylon had been built. Together with bricks or stones, it pro- 
duces such strength that the walls made of it are stronger than rock 
and any kind of iron." 

Philostratus ( The Elder] (about 200 A.D.). This Athenian 
writer 71 refers (I, 23) to asphalt deposits near Ardericca (near 
the present town of Kirab) in Cissia (Iran). He states that in 
the land of Cissia: 

"The soil is drenched with pitch and is bitter to plant in. . . ." 

and warns : 

"Against drinking water which has been in contact with bitumen, 
since this will cause the intestines to close up, owing to the water 
taking up traces of bitumen." 

although he goes on to say ("Tetrabiblos," I, 2 and 49) : 



38 HISTORICAL REVIEW I 

"That the drinking of bituminous water is the best remedy for 
dropsy." 

He also describes : 

"An oil which once set afire, cannot be extinguished, and which 
Indian kings use to burn down walls and capture cities." 

Geoponica (200 to 300 A.D.}. The "Geoponica" 72 consisted 
of a collection of writings on husbandry and agriculture by various 
Greek and Roman writers of the third and fourth centuries, includ- 
ing Gargilius Martialis of Mauretania and Palladius of Rome. In 
this treatise we are informed that a mixture of bitumen and oil 
served to alleviate wounds in trees (XIII, 10 and 7) ; that rings of 
bituminous mastic were made around tree trunks for protection 
against ants; that bitumen mixed with sulfur was burned under trees 
and bushes to kill caterpillars and other harmful insects, also for 
disinfecting the cages of birds (XIV, u, 4) ; that fowls would lay 
bigger eggs if rubbed with a mixture of bitumen, resin and sulfur 
(XIV, n); that a mixture of bitumen and various spices served 
for the treatment of cattle plague (XVII, 16) ; and lastly, that bi- 
tumen relieved sufferers of diarrhoea (XVII, 16, i). 

Afrlcanus (about 300 A.D.}. This Greek writer, in his treatise 
"Kestoi" 73 on agriculture, natural history, military science, etc., de- 
scribes a mixture consisting of: 

"Sulfur, natural resin (i.e. asphalt), salt and quicklime, which 
by careful mixing, the addition of the lime last, and enclosing the 
whole in a bronze vessel to exclude humidity, air and light, will 
ignite spontaneously by the simple addition of water or dew." 

Ammianus Marcellmus (330 to 395 A.D.}. This Roman his- 
torian states, 74 probably in reference to the region of Quara and 
Quala Shergat in Iraq : 

"In Assyria there is asphalt in the lake called Sosingite, in the 
bed of which the Tigris is absorbed, which flows on underground to 
rise to the surface again at a great distance away. Naphtha also 
occurs here; this greatly resembles asphalt and is very viscous and 
sticky. Even if a very small bird alights on it, it is drawn down, it 
can no longer fly and it disappears into the depths. ^ Once this kind 
of substance begins to burn, human intelligence will find no other 



I ABOUT 1248 A.D. PIERRE DE JOINVILLE 39 

means of quenching it than by earth. A big cleft will be seen in 
these districts from which mortally fatal fumes rise up, the heavy 
odor of which will kill any living creature coming within its reach." 

Theophanes (758 to 817 A.D.}. The Greek writer Theopha- 
nes, in his treatise "Chronicles," states: 

"The principle of spontaneous ignition by contact with water 
was brought to its highest practical application by the Greek archi- 
tect Kallinikos residing in Byzantium about 650 A.D., as a fugitive 
from the Arabs of the Syrian town of Heliopolis, and who was the 
real inventor of 'Greek Fire'." 75 

This seems strange, in view of the earlier disclosures by Thu- 
cydides(47i~40i B.C.), Hannibal (247-183 B.C.), Pliny the Elder 
(23-79 A.D.), Philostratus (about 200 A.D.), and others. 

About 950 A.D. Abu-L-Hasan Masudi. The Persian writer 
Masudi, in his "Annals" 76 refers to "oleum de gagantis," which is 
an oily product derived from natural asphalt by a process termed 
"distillatio per decensorium" which was carried out in two superim- 
posed jars separated by a screen or sieve. The upper jar, filled with 
the material under treatment, was heated by a fire and the oily dis- 
tillate allowed to drip through the screen into the bottom jar im- 
bedded in damp soil. Medieval writers frequently refer to rock 
asphalts and asphaltites under the name "gagates," which was de- 
rived from the river Gagas or Gages in Lycia, Asia Minor, at the 
mouth of which there was stated to be a deposit of hard asphalt. 
Gagates were used as a means of exorcising evil spirits, in which 
connection Bishop Marbode of Rennes (1067-1123 A.D.) states in 
his treatise "Dactyliothecae" : 

"As an amulet it benefits dropsy, diluted with water it prevents 
loose teeth from falling out, whilst fumigation with gagates is good 
for epileptics. It remedies indigestion and constipation, cures magi- 
cal illusions and evil incantations, and is often used in love potions." 

About 985 A.D. Abd Al Mukaddasi. This writer refers 7r to: 

"Nafta and earth-pitch from Transoxania, Ferghana," 
which corresponds to the present Baku region. 

About 1248 A.D. Pierre de Joinville. De Joinville, who ac- 
companied King Louix IX on his Sixth Crusade to Damiette, re- 
fers 78 to the use of Greek Fire, stating that: 



40 HISTORICAL REVIEW I 

"Every man touched by it believed himself lost, every ship at- 
tacked was devoured by flames." 

About 1300 A.D. Marco Polo. This Venetian traveler de- 
scribed 70 seepages of liquid asphalt at Baku on the Caspian Sea. 
He also mentioned the existence of an ancient fire-temple erected 
about the flaming streams of gas and oil, which we are informed 
constituted a place of Hindoo pilgrimage. 

About 1350 A.D. Sir John Mandeville. This British writer 
states (Chap. XXX): 80 

"And two myle from Jericho is flom Jordan and you shall wcte 
the Dead Sea is right bitter, and this water casteth out a thing 
called asphatum, as great pieces as a horse." 

1494-1555. Georg Agricola. This well known German metal- 
lurgist states : 81 

"Bitumen is produced from mineral waters containing oil, also 
from liquid bitumen, and from rocks containing bitumen. . . . 
Liquid bitumen sometimes floats in large quantities on the surface of 
wells, brooks and rivers, and is collected with buckets or other pots. 
Small quantities are collected by means of feathers, linen towels 
and the like. The bitumen easily adheres to these objects, and is 
collected in big copper or iron vessels and the lighter fractions evap- 
orated by heating. The residual oil is used for different purposes 
and some people mix it with pitch, others with used axle oil to make 
it thinner. The bitumen does not harden, even during the time of 
its heating in the vessels. Rocks which contain bitumen are treated 
in the same way as those which contain sulfur, by heating them in 
vessels with a sieve bottom. This, however, is not the common 
practice, because the bitumen prepared in this way is not very valu- 
able." This process is illustrated in Fig. 23. 

Agricola also refers to asphaltic crude-oil seepages at Wietze, 
near Hannover, Germany, and mentions the use of "heavy petro- 
leum to protect woodwork from rain." 

1498. Christopher Columbus. On his third voyage to America 
on July 31, 1498, Columbus discovered the island of Trinidad, 
where it has been stated: 82 "He careened his galleons and caulked 
their storm-racked seams with this natural waterproofing material," 
referring to asphalt derived from Trinidad Lake, 



I 1563. CESAR FREDERICKE 41 

About 1500. Use of Asphalt in Peru. It has been established 
that the Incas of Peru constructed an elaborate system of highways, 
some of which were paved with a composition not unlike modern 
bituminous macadam. 

1535. Discovery of Asphalt in Cuba. G. F. Oviedo y Valdes 
of Spain describes 83 a spring of semi-liquid asphalt in the Province 
Puerto Principe, near the coast of Cuba, which was used for paint- 
ing the hulls of ships. Another occurrence is mentioned on the 




From Agricola 
FIG. 23. -Smelting Bitumen from Bituminous Rock. 

shore of Havana harbor, used for similar purposes. He tells us 
that asphaltic petroleum was used to protect woodwork and ma- 
sonry in Cuba as early as 1550 A.D. 

1563. Cesar Fredericke. This writer in his publication "Voy- 
age to the East Indies," states : 

"These barks of the Tigris have no pumps in them, because of 
the great abundance of pitch, which they have to pitch them with all. 
This pitch they have in abundance two days' journey from Babylon. 
Near unto the river Euphrates, there is a city called Heit (Hit), 
near unto which city there is a great plaine full of pitch, very mar- 



42 HISTORICAL REVIEW 1 

vellous to beholde, and a thing almost incredible that out of a hole 
in the earth, which continually throweth out pitch into the aire with 
continuall smoake ; this pitch is thrown with such a force that being 
hot it falleth like as it were sprinckled over all the plame in such 
abundance that the plaine is always full of pitch. The Mores and 
the Arabians of that place say that that hole is the mouth of hell, 
and in truth it is a thing very notable to be marked. And by this 
pitch the whole of the people have their benefit to pitch their barks. 

1595. Sir Walter Raleigh. Sir Walter Raleigh 84 gives a record 
of his voyage of exploration to the east coast of South America in 
1595, wherein he describes his visit to the Island of Trinidad, and 
gives an account of the so-called "Pitch Lake," of which he wrote: 

"March 22, 1595 At this point called Tierra de Brea or Piche, 
there is that abundance of stone pitch, that all the ships of the 
world may be therewith laden from thence, and wee made trial of 
it in trimming our shippes to be most excellent goode and melteth not 
with the sunne as the pitch of Norway, and therefore for shippes 
trading the south parts very profitable." 

1599. First Classification of Bituminous Substances. Andreas 
Libavius refers to the uses of asphalt, and classified it with mineral 
oil, amber and pitch. He endeavored to trace the connection be- 
tween asphalt and petroleum, and gives a record of the earliest 
literature on asphalt including the works of Pliny, Dioscorides, 
ftippocrates and others. 85 

1608. William Shakespeare. In his play "Pericles" written in 
1608, by Shakespeare (1564-1616), occurs the passage: "We have 
a chest beneath the hatches, caulked and bitumened ready." 

1656. Early Dictionary Definition of "Bitumen." In one of 
the earliest dictionaries of the English language, "Thomas Blount's 
Glossary," bitumen is defined as: 

"A kind of clay or slime naturally clammy, like pitch, growing 
in certain countries of Asia." 

It is interesting to note the connection between this interpreta- 
tion of the word, and the reference to "slime" and "slimepit" in 
"Genesis." 

1660. John Milton. In "Paradise Lost," written about 1660 
by Milton (1608-1674), we read: "Blazing cressets fed with 
naphtha and asphalts"; and again: "The plain, whereon a black 



I 1712-1730. VAL DE TRACERS, LIMMER, SEYSSEL DEPOSITS 43 

bituminous gurge boils out from underground the mouth of hell." 
1661. Commercial Production of Wood Tar. The earliest ref- 
erence to the production of wood tar on a large scale by the dry 
distillation of wood, occurs in Robert Boyle's "Chemistra Scepticus," 
1 66 1. This industry is said to have been first practiced in Norway 
and Sweden. 

1672. First Accurate Description of Persian Asphalt Deposits. 
Dr. J. Fryer accurately describes the occurrences of asphalt in the 
East Indies and Persia, in his book u Nine Years' Travels" (1672 
i68i). 86 . 

1673. Discovery of Elaterite. The first description of elater- 
ite, originally found at Castleton in Derbyshire, England, under 
the name "Elastic Bitumen," is given by M. Lister in the Philo- 
sophical Magazine and Journal of Science ^ London, 1673 (p. 
6179). 

1681. Discovery of Coal Tar and Coal-Tar Pitch. In a patent 
(No. 214) taken out in England on August 19, 1681, by Joachim 
Becher and Henry Serle, entitled "A new way of makeing pitch, and 
tarre out of pit coale, never before found out or used by any other," 
we find the first description of coal tar and coal-tar pitch, as well as 
their methods of production. 

1691. Discovery of Illuminating Gas from Coal. Dr. John 
Clayton, dean of Kildare, England, experimented with the inflam- 
mable gas obtained on heating coal in a closed retort. He filled 
bladders with this gas and demonstrated that it burnt with a lumi- 
nous flame. 

1694. Discovery of Shale Tar and Shale-Tar Pitch. British 
Patent No. 330, of 1694 (Jan. 29), entitled 4< Pitch, tar and oyle, 
out of a kind of stone from Shropshire," granted Martin Eele, 
Thomas Hancock and William Portlock, contains the earliest record 
of the manufacture of shale tar and shale-tar pitch. 

1712-1730. Discovery of Val de Travers, Limmer and Seyssel 
Asphalt Deposits. The asphalt deposit at the Val de Travers in 
the Jura Mountains, Canton of Neuchatel, Switzerland, was dis- 
covered by the Greek Doctor Eirinis d'Eyrinys in 1712, and de- 
scribed in detail. 87 

Some give Eyrinys the credit of having likewise discovered the 
Limmer asphalt deposit near Hanover, Germany, in 1730, but this 



44 HISTORICAL REVIEW J 

has not been definitely established. A third discovery of asphalt by 
Eyrinys, in 1735, at Seyssel in the Rhone Valley, Department of 
Ain, France, proved to be one of the most important deposits in 
Europe. This has been worked constantly up to the present time, 
and will be described later. 

1772. First Use of Tar for Flat Roofs. Recent researches 
ascribe P. J. Marperger of Berngau, near Neumarkt (in the vicin- 
ity of Niirnberg, Germany) as the originator of tarred roofs. He 
described the following method of covering flat roofs: the wooden 
boards were first caulked with oakum, then sprinkled alternately 
with tar and a mixture of fine sand with iron slag, until after three 
or four such treatments a fairly thick protective covering was ob- 
tained. 88 

1746. Invention of the Process of Refining Coal Tar. On 
Dec. 2, 1746, a patent (No. 619) was granted in England to Henry 
Haskins disclosing: "A new method for extracting a spirit or oil 
from tar, and from the same process obtaining a very good pitch;" 
consisting of our present process of fractional distillation in a closed 
retort connected with a worm condenser. 

1752. Samuel Foote. The English dramatist Foote (1720- 
1777) writes in his book "Taste," published in 1752, of the "salu- 
tary application of the asphaltum pot" for preserving the beautify- 
ing qualities of the complexion. At this time it was claimed by 
authorities to be. "a sure cure for ringworm, boils, gout, epilepsy, 
blindness, toothache and colic." 

1777. First Exposition of Modern Theory of the Origin of 
Asphalt. In his "Elements de Mineralogie," published in 1777 
LeSage 89 classified bitumens in the sequence : "Naphtha, petroleum, 
mineral pitch, maltha and asphalt," and regarded them all as origi- 
nating from petroleum oil. This closely conforms to the modern 
views regarding the classification and origin of bitumens. 

1788. Discovery of Lignite Tar. Krimitz in 1788 referred to 
the production of "a tar-like oil" upon destructively distillating 
"earth coal" (lignite). This was virtually the first description of 
the manufacture of lignite tar. 

1780-1790. Discovery of "Composition" or "Prepared" Roof- 
ing. Arvicl Faxe of Sweden 9d is given credit for having produced 
the first composition roofings between the years 1780 and 1790 in 



I 1815. COMMERCIAL EXPLOITATION OF COAL-TAR SOLVENTS 45 

the following crude manner : the roof boards were first covered with 
plain paper, impregnated with a mixture of copper and iron sul- 
fates, which, after being nailed in place, was coated with heated 
wood tar to make it 'waterproof, and then surfaced with various 
colored mineral earths. 

A newspaper published in Leipsic in the year 1791 credits 
Michael Kag of Miihldorf, Bavaria, with having produced an im- 
proved form of prepared roofing by saturating raw paper with var- 
nish, and coating the surfaces with a mineral powder. The product 
was also recommended as a substitute for leather in the soles of 
shoes. 

Similarly, the Magdeburg Zeitung on Nov. 16, 1822, contained 
a notice stating that paper impregnated with tar is being used to 
displace straw and wooden shingles for roofing purposes, and that 
the former may be made fire-resistant by treating the tar with 
unslaked lime and surfacing with sand. 

The manufacture of "tarred board" for roofing purposes, as 
practiced in Germany during the year 1828, was published by W. A. 
Lampadius. 01 

1792-1802. Manufacture of Coal Gas and Coal Tar on a Large 
Scale. Wm. Murdoch, of England, was the first to manufacture 
coal gas and coal tar on a large scale. 

1797-1802. Exploitation of Seyssel Asphalt in France. M. 
Secretan obtained a concession from the French Government to 
work the asphalt deposits at Seyssel on the Rhone, France, in the 
fifth year of the French Republic (1797). The venture, however, 
did not prove a success. The deposit was next taken over by Count 
de Sassenay, of France, in 1802, and actively exploited. A labora- 
tory was erected to investigate the uses of this asphalt, which was 
marketed in France under the name "rock asphalt mastic," and used 
for surfacing floors, bridges and sidewalks, also to a limited extent 
for waterproofing. The earliest experimental use was in the vicinity 
of Bordeaux and Lyons. 

1815. Commercial Exploitation of Coal-Tar Solvents. In 
1815, F. C. Accum, of England, obtained "naphtha" by subjecting 
coal tar to fractional distillation on a commercial scale. This distil- 
late was used in the manufacture of India rubber goocfc, for burn- 
ing in open lamps and for certain kinds of varnish. The tar which 



46 HISTORICAL REVIEW I 

remained behind had no particular value and was accordingly con- 
sumed as fuel. 

1820. Manufacture of Asphalt-saturated Packing Papers in 
Switzerland. The asphalt deposits previously discovered at Neu- 
chatel, Switzerland, were utilized in 1820 for impregnating porous 
paper, for use as tarpaulins, packing paper, imitation oil-cloth, etc., 
and the first factory was established in Geneva. 92 

1822. Discovery of Scheererite and Hatchettite. The mineral 
wax Scheererite was discovered in a bed of lignite (brown coal) at 
Uznach, near St. Gall in Switzerland, by Captain Scheerer, in 
i823. 93 In the same year the mineral wax hatchettite or hatchetine 
was discovered on the borders of Loch Fyne, in Argyllshire, Scot- 
land, and was named after the English chemist, C. Hatchctt. 94 

1830. Discovery of Paraffin Wax. The discovery of paraffin 
wax is credited to Carl von Reichcnbach, of Stuttgart, Germany, 
who was the first to describe its physical and chemical properties. 95 
He derived the material from lignite tar and christened it "paraffin" 
(parum affinis), because of its unusual resistance to chemicals. 

1832. Coal Tar First Used for Paving. The first stretch of 
tar-macadam pavement on record was laid in Gloucestershire, Eng- 
land, between 1832 and 1838. In this same connection, an inter- 
esting pioneer patent was granted to Cassell in 1834, describing the 
use of coal tar for surfacing roads, grouting, and the construction 
of tar-concrete paving blocks. 96 

1833. Discovery of Ozokerite. The first reference to the min- 
eral ozokerite was by E. F. Glocker 97 in 1833. lie discovered it 
near the town of Slanik in Moldavia, close to a deposit of lignite 
at the foot of the Carpathians. It was named from the Greek 
words signifying u to smell" and "wax," in allusion to its odor. 

1835. First Asphalt Mastic Foot Pavements Laid in Paris. 
It is recorded that on June 15, 1835, the first mastic pavement was 
laid at Pont Royal, Paris, composed of Scyssel asphalt. 98 

1836. Asphalt First Used in London for Foot Pavements. 
In 1836 we first hear of Seyssel asphalt being introduced from 
France to London for constructing foot paths. 99 

1837. Publication of First Exhaustive Treatise on the Chem- 
istry of Asphalt. The well-known treatise "Memoir sur la compo- 
sition des bitumes" was published by J. B. Boussingault in the year 



I 1850. DISCOVERY OF "ASPHALTIC COAL" IN NEW BRUNSWICK 47 

1837. It was the most exhaustive treatise on the subject which had 
yet appeared, and was the first to propose the use of the terms 
"petrolene" and "asphaltene" for the components of asphalt 100 

1837. Discovery of Bituminous Matter in the United States. 
In 1837 appeared the first report of an asphalt deposit in the United 
States in which semi-solid and solid bitumens were reported in the 
Connecticut valley at Farmington, Hartford (Rocky Hill), Berlin, 
Middletown and New Britain, Conn. 101 

1838. Discovery of Process for Preserving Wood with Coal- 
tar Creosote. In 1838 Bethell disclosed the use of coal-tar oil for 
impregnating wood. 102 

1838. Asphalt First Used in the United States for Foot Pave- 
ments. The earliest case on record of rock asphalt being used in 
the United States for sidewalks is in the portico of the old Mer- 
chants' Exchange Building, Philadelphia, in 1838. Seyssel asphalt 
was used for this purpose. 

1841. First Use of Wood Block Pavement. Wood blocks im- 
pregnated with coal tar were first used in England. 103 

1843. Bituminous Matters Discovered in New York State. 
L. C. Beck, in 1843, wrote a paper on the occurrence of bituminous 
matter in several of the New York limestones and sandstones. 104 

1844-1847. First Composition Roofing in the United States. 
Rev. Samuel M. Warren reported that in 1844-1845 roofs were 
first laid in Newark, N. J., consisting of square sheets of ship's 
sheathing paper treated with a mixture of pine tar and pine pitch, 
and surfaced with sand. In 1847 coa ^ tar was used as a substitute 
for the pine tar, to soften the pine pitch, and employed as a saturant 
for the paper. Fine gravel was next used to substitute the sand. 
The square sheets were dipped into the melted mixture by hand, 
sheet by sheet, and then the excess was pressed out The next step 
consisted in running the paper or felt in rolls through continuously 
operating saturators designed to saturate with tar. Finally, in 
Buffalo, N. Y., coal tar was distilled down to a roofing pitch, which 
was used to replace the more expensive mixture of pine pitch and 
coal tar. The foregoing constituted * the origin of the "tar-and- 
gravel roof," so extensively used to-day. 105 

1850. Discovery of "Asphaltic Coal" in New Brunswick, 
Nova Scotia. C. T. Jackson published the first accounts of Nova 



48 HISTORICAL REVIEW I 

Scotia "albertite" in the years 1850-1851. It was described as 
"Albert Coal." 106 

1852. First Modern Asphaltic Road. The first asphaltic road 
of which we have a record in comparatively modern times, was con- 
structed in 1852 from Paris to Perpignan, France, after the fashion 
of modern macadam construction, from Val de Travers rock- 
asphalt. 

1854. First Compressed Asphalt Roadway Laid in Paris. 
In 1854 a short stretch of compressed rock asphalt roadway was 
laid in Paris by M. Vaudrey. 107 This, we are told, was the outcome 
of observations previously made by a Swiss engineer, M. Merian, 
who in 1849 noted that fragments of rock asphalt which fell from 
the carts transporting the material from the mine at Val de Travers, 
to the nearby village, became compressed in summer under the 
wheels into a crude pavement of asphalt. M. Leon Malo in con- 
junction with M. Vaudrey and M. Homberg thereupon con : 
structed a stretch of roadway compacted with a roller in the 
Rue Bergere, Paris, which was maintained in good condition for 
sixty years. 108 

1858. First Modern Asphalt Pavement Laid in Paris. In 
1858 the first large area of asphalt roadway was constructed on the 
Palais Royal and on the Rue St. Honore in Paris. It was cortiposed 
of a foundation of concrete 6 in. thick surfaced with rock asphalt 
mastic obtained from the Val de Travers deposit, compressed to a 
layer about 2 in. thick. This constituted the earliest use of sheet 
asphalt pavement in its modern form. 

1863. Discovery of Grahamite in West Virginia. The first 
account of the West Virginia grahamite deposit is given by J. P. 
Lesley. 100 The material was described as a "rock asphalt," but was 
later named "grahamite" by Henry Wurtz, in honor of the Messrs. 
Graham, who were largely interested in the mine. 

1869. The First Compressed Asphalt Pavement in London. 
The first stretch of asphalt roadway in London was laid at Thread- 
needle Street near Finch Lane in May, 1869. It was composed of 
Val de Travers rock asphalt. 1 * 

1870-1873. First Asphalt Roadways in the United States. 
Some give the Belgian chemist, E. J. De Smedt, credit for having 
the first rock asphalt roadway in t u ~ TT ~ : ted States r contending 



I 1885. DISCOVERY OF UINTMITE (GILSONITE) IN UTAH 49 

that in 1870 a small experimental strip was laid with continental 
asphalt opposite the City Hall in Newark, N. J. In 1871 pavements 
were laid in Washington, D. C, in accordance with a patent granted 
to N. B. Abbott, 111 composed of a mixture of crushed rock and sand 
with coal-tar pitch and creosote oil, after a favorable report had 
been rendered by a special commission appointed by Congress. 
These pavements gave good service for over 15 years. Also in 
1871, a small stretch of pavement was laid in Battery Park, New 
York City, and according to T. H. Boorman, 112 in 1872 a larger 
stretch was laid at Union Square, composed of Val de Travers rock 
asphalt. It is also reported that in 1873 a similar pavement was 
laid in front of the Worth Monument, which remained in use until 
i886. 113 

1876. First Trinidad Asphalt Pavement Laid in the United 
States. According to Clifford Richardson 114 the first sheet asphalt 
pavement of Trinidad asphalt to be laid in the United States was on 
Pennsylvania Avenue, Washington, D. C. This was authorized by 
an act of Congress passed in 1876, Val de Travers rock asphalt 
being used from the Capitol to Sixth Street, and Trinidad asphalt 
for the remainder. The rock asphalt w r as subsequently pronounced 
to be too slippery and the Trinidad asphalt pavement a success. 

1880. Use of Asphalt "Chewing-gum" in Mexico. B. de 
Sahagun 115 informs us that the inhabitants of the coastal districts of 
Mexico, the Totonacs, collected asphalt ("tzacutli") in the Panuco 
river region and sold it to the Aztecs of the interior, who in turn 
compounded it with gum chicle ("txixtli") and used the mixture as 
chewing-gum ( "chapopotli" ) . 

1881. Use of Chemicals for Oxidizing Coal Tars and Petro- 
leum Asphalts. The first complete disclosure of the process for 
"oxidizing" bituminous materials was by E. J. De Smedt. 116 This 
process consisted in evaporating coal tar or asphalt in contact with 
substances capable of inducing oxidation (such as potassium per- 
manganate), "to give them greater tenacity and render them, or the 
pavement, or other compositions in which they enter, less brittle and 
less liable to be affected by air or water." 

1885. Discovery of Uintaite (Gilsonite) in Utah. Gilsonite, 
first known as "uintaite," was discovered in the Uinta Valley near 
Fort Duchesne, Utah, in 1885. It was first described by W. P. 



50 HISTORICAL REVIEW I 

Blake 11T and was later called "gilsonite," after S. H. Gilson, of 
Salt Lake City. 

1889. Discovery of Wurtzilite in Utah. W. P. Blake subse- 
quently discovered a deposit of wurtzilite not far from the source of 
gilsonite in the Uinta Valley, Wasatch County, Utah, between Salt 
Lake and the valley of*the Green river. 118 It was named after Dr. 
Henry Wurtz of New York. 

1891. Exploitation of the Bermudez Asphalt Deposit, Vene- 
zuela. According to Hippolyt Kohler and Edmund Graefe, 119 the 
Bermudez asphalt deposit in Venezuela was first developed in the 
year 1891 by the New York-Bermudez Company, and subsequently 
taken over by the Barber Asphalt Paving Co. A search of the lit- 
erature fails to reveal when this deposit was first discovered. 

1892. Use of Bermudez Asphalt on a Large Scale. Bermudez 
asphalt was first used extensively in Detroit, Mich., in 1892, and 
the year following in Washington, D. C With this start, it rapidly 
gained in popularity, and is to-day largely used as a road binder, as 
well as for sheet-asphalt pavements. 

1894. Use of Air for Oxidizing Petroleum Asphalt. A further 
development of the De Smedt process for oxidizing petroleum as- 
phalt was brought about by F. X. Byerley, of Cleveland, O., who 
blew air through asphaltic oils maintained at a temperature of 
600 F. 120 The resulting product, marketed under the name of 
"byerlite," attained great popularity. 



CHAPTER II 

TERMINOLOGY AND CLASSIFICATION OF BITUMINOUS 

SUBSTANCES 

One of the most baffling problems with which we have had to 
deal in recent years is fixing the definitions of the various bituminous 
substances, and the products in which they are used in the arts. 1 

The words "bitumen," "asphalt/' "resin," "tar," "pitch," 
"wax," have been in use for many centuries, most of them long 
before the advent of the English language. At first, very little was 
known regarding the properties of these substances, and, as a result, 
the early writers used these terms loosely, and, in many cases, inter- 
changeably. It is probable that each of these words at first related 
to the aggregate characteristics of some typical substance closely 
associated with the processes of daily life. As nothing of the chem- 
istry was known when these terms originated, they were at first 
differentiated solely by their physical characteristics. 

The words originally had but a limited meaning, but as new 
members of these groups of substances were discovered, the terms 
were extended in scope until the various expressions completely out- 
grew their original bounds. This resulted in a certain amount of 
overlapping and ambiguity. 

As the chemistry of these substance gradually became known, 
this means was likewise adopted to differentiate between them, but 
we are still compelled to rely principally upon the physical charac- 
teristics in arriving at a rational basis of terminology, as their chem- 
istry has been unravelled to but a limited extent. 

In defining a substance, we must rely on one or more of the fol- 
lowing criteria : 

Origin, Solubility, 

Physical Properties, Chemical Composition. 

The last three can be more or less readily ascertained from an 
examination of the substance itself. The origin, however, is not 

51 



52 TERMINOLOGY AND CLASSIFICATION II 

always apparent, but in certain cases may be deduced by inference. 
To base a definition solely upon a statement of the origin of a sub- 
stance would necessitate some prior knowledge concerning its source 
or mode of production. As such knowledge is not always available, 
a definition of this kind would be very limited in its scope. Unfor- 
tunately, this plan has often been followed by many of the leading 
technical societies in this country and abroad, in fixing the defini- 
tions of bituminous substances. 

A far better method consists in basing the definition upon the 
inherent characteristics of the substance itself, so as to permit of its 
identification without necessarily having prior knowledge concerning 
its origin. 

The four cardinal features forming this latter basis of nomencla- 
ture may be further elaborated as shown in Table I. 

In Table II the principal types of bituminous substances are 
classified according to the features enumerated in Table I. 

The definitions which follow are based upon this classification. 
Although reference is made to the origin of the substance, neverthe- 
less, this is but incidental, and with the exception of the generic 
terms, the definitions would be explicit even though this feature were 
omitted. 

Bituminous. Substances.* A class of native and pyrogenoust 
substances containing bitumens or pyrobitumens, or resembling 
them in their physical properties. 

SCOPE. This definition includes bitumens, pyrobitumens, py- 
rogenous distillates and tars, pyrogenous waxes and pyrogenous resi- 
dues (pitches and pyrogenous asphalts). 

Liquid Bituminous Materials. Those having a penetration at 
25 C. (77 F.), under a load of 50 g. applied for one second, 
of more than 350 (Test gb). 

Semi-Solid Bituminous Materials. Those having a penetration 

* The scope of the word "bituminous*' is based on the commonly accepted interpreta- 
tion of the suffix "ous," signifying: (i) to contain; (2) to resemble, to partake of the 
nature, to have the qualities (e.g., silicious: containing silica or resembling silica; 
resinous: containing or resembling resin; oleaginous: containing or resembling oil; cal- 
careous:, containing or resembling lime). Similarly, the word "bituminous" is construed 
to include substances, either containing more or less bitumen (or pyrobitumen), or else 
resembling them in their appearance or qualities. 

fThe expression "pyrogenous" implies that the substance was produced by means of 
heat or fire. 



II 



BITUMINOUS SUBSTANCES 



Origin 



Solubility 

Chemical 
Compo- 
sition 



Native 



Pyrogenous 



TABLE I 

r Mineral 
I Vegetable 
I Animal 



Factional distillation 
Destructive distillation 
Heating in a closed vessel 
Blowing with air. 





Color in Mass H 


r Light (white, yellow or brown) 
Dark (black) 




Consistency 
or Hardness 


Liquid 
Viscous 
Semi-solid 
Solid 




Fracture j 


Conchoid al 
Hackly 


Physical 

Properties 


Lustre j 


:Waxy 
Resinous 
Dull 



Feel 



Odor 



Volatility 



Fusibility 



f Adherent 
< Non-adherent 
I Unctuous (waxy) 

I Oily (petroleum-like) 
I Tarry 

f Volatile 

( Non-volatile 

f Fusible 

] Difficultly fusible 

I Infusible (melts only with decomposition) 



Non-mineral constituents soluble in carbon disulfide 

Hydrocarbons (compounds containing carbon and hydrogen) 
Oxygenated bodies (compounds containing carbon, hydrogen, and 

oxygen) 

Crystallizable paraffins (crystallize at low temperatures) 
Mineral matter (inorganic substances). 



at 25 C. (77 F.)> under a load of 100 g. applied for five seconds, 
of more than 10, and a penetration at 25 C. (77 F,) , under a load 
of 50 g. applied for one second, of not more than 350 (Test 9^). 

Solid Bituminous Materials. Those having a penetration at 
25 C. (77 F.), under a load of 100 g. applied for five seconds, of 
not more than 10 (Test 



54 



TERMINOLOGY AND CLASSIFICATION 



II 



ilii if ujs 

,. 8 a 8 3 rS ^ ^3.>'S w^-gw 




il ti 



J 



il I 



lti Jill 



I 



I 



I I 



II 



N 

3T3 






iJi 



3 

I 



Wo 



r? M's.a'gj'g 44 

H|8 ^ 



I 



i I 



I 






i 



I I 
* 







s 



II BITUMEN 55 

IT 

Bitumen,* A generic term applied to native substances of vari- 
able color, hardness and volatility; composed principally of hydro- 
carbons, substantially free from oxygenated bodies ; sometimes asso- 
ciated with mineral matter, the non-mineral constituents being fusible 
and largely soluble in carbon disulfide, yielding water-insoluble sul- 
fonation products. 

SCOPE. This definition includes petroleums, native asphalts, 
native mineral waxes and asphaltites (gilsonite, glance pitch and 
grahamite). 

Pyrobitumen.t A generic term, applied to native substances of 
dark color; comparatively hard and non-volatile; composed of hy- 
drocarbons, which may or may not contain oxygenated bodies; 
sometimes associated with mineral matter, the non-mineral constitu- 
ents being fusible and relatively insoluble in carbon disulfide. 

SCOPE. This definition includes the asphaltic pyrobitumens 
(elaterite, wurtzilite, albertite and impsonite) also the non-asphaltit 
pyrobitumens (peat, lignite, bituminous coal and anthracite coal) 
and their respective shales. 

Petroleum. A species of bitumen, of variable color, liquid con- 
sistency, having a characteristic odor; comparatively volatile; com- 
posed principally of hydrocarbons, substantially free from oxy- 
genated bodies; soluble in carbon disulfide, yielding water-insoluble 
stilfonation products. 

SCOPE. This definition includes non-asphaltic, semi-asphaltic 
and asphaltic petroleums. 

Mineral Wax. A term applied to a species of bitumen, also to 
certain pyrogenous substances; of variable color, viscous to solid 
consistency; having a characteristic lustre and unctuous feel; com- 
paratively non-volatile; composed principally of saturated hydro- 
carbons, substantially free from oxygenated bodies ; containing con- 
siderable crystallizable paraffins; sometimes associated with mineral 

* The interpretation of the term "bitumen" as employed in this treatise is entirely dis- 
sociated from the idea of solubility (in certain solvents for hydrocarbons), and has no 
connection whatsoever with the inappropriate expression "total bitumen," used in many 
contemporary text-books to designate the amount soluble in carbon disulfide, and which 
unfortunately is largely responsible for the existing confusion in terminology. 

fThe expression "pyrobitumen" implies that the substance when subjected to heat or 
fire will generate, or become transformed into bodies resembling bitumens (in their solu- 
bility and physical properties). 



56 TERMINOLOGY AND CLASSIFICATION II 

f 

matter, the non-mineral constituents being easily fusible and soluble 
in carbon disulfide, yielding water-insoluble sulfonation products. 

SCOPE. This definition is applied to crude and refined native 
mineral waxes, also to pyrogenous waxes. Crude native mineral 
waxes include ozokerite. Refined native mineral waxes include 
ceresine (refined ozokerite) and montan wax (extracted from lig- 
nite or pyropissite by means of solvents). Pyrogenous waxes in- 
clude the solid paraffins separated from non-asphaltic and semi- 
asphaltic petroleums, peat tar, lignite tar and shale tar. 

Asphalt. A term applied to a species of bitumen, also to certain 
pyrogenous substances of dark color, variable hardness, compara- 
tively non-volatile; composed principally of hydrocarbons, substan- 
tially free from oxygenated bodies; containing relatively little to 
no crystallizable paraffins; sometimes associated with mineral mat- 
ter, the non-mineral constituents being fusible, and largely soluble 
in carbon disulfide, yielding water-insoluble sulfonation products. 

SCOPE. This definition is applied to native asphalts and pyrog- 
enous asphalts. Native asphalts include asphalts occurring natur- 
ally in a pure or fairly pure state, also asphalts associated naturally 
with a substantial proportion of mineral matter.* The associated 
mineral matter may be sand, sandstone, limestone, clay, shale, etc. 
Pyrogenous asphalts include residues obtained from the distillation, 
blowing, etc., of petroleums (e.g., residual oil,t blown asphalts,t 
residua! asphalts,! sludge asphalt, 1 1 etc.), also from the pyrogenous 
treatment of wurtzilite (e.g., wurtzilite asphalt 1T). 

In Europe, the term "asphalte" is applied to unconsolidated 
limestone impregnated with asphalt, which softens and crumbles 
when subjected to a moderate heat (e.g., 125 to 1 60 F.), whereas 
the term "bituminous rock" is used to designate consolidated lime- 
stone rock impregnated with asphalt, which resists high tempera- 
tures (e.g., 1000 F. and over) without crumbling. 

Asphaltite. A species of bitumen, including dark-colored, com- 
paratively hard and non-volatile solids; composed principally of 

* Often termed "rock asphalts." 

f Produced by the dry distillation of non-asphaltic petroleum, the dry or steam dis- 
tillation of semi-asphaltic petroleum and the steam distillation of asphaltic petroleum. 

t Produced by blowing air through heated residual oils. 

Produced by the steam distillation of semi-asphaltic and asphaltic petroleums. 

|| Produced from the acid sludge obtained in the purification of petroleum distillates 
with sulfuric acid. 

fl Produced by depolymerizing wurtzilite in closed retorts. 



II TAR 67 

hydrocarbons, substantially free from oxygenated bodies and crys- 
tallizable paraffins; sometimes associated with mineral matter, the 
non-mineral constituents being difficultly fusible, and largely soluble 
in carbon disulfide, yielding water-insoluble sulfonation products. 

SCOPE. This definition includes gilsonite, glance pitch, and 
grahamite. 

Asphaltic Pyrobitumen. A species of pyrobitumen, including 
dark-colored, comparatively hard and non- volatile solids ; composed 
of hydrocarbons, substantially free from oxygenated bodies ; some- 
times associated with mineral matter, the non-mineral constituents 
being infusible and largely insoluble in carbon disulfide. 

SCOPE. This definition includes elaterite, wurtzilite, albertite, 
impsonite and the asphaltic pyrobituminous shales. 

Non-asphaltic Pyrobitumen. A species of pyrobitumen, inclucj- 
ing dark-colored, comparatively hard and non-volatile solids; com- 
posed of hydrocarbons, containing oxygenated bodies ; sometimes 
associated with mineral matter, the non-mineral constituents being 
infusible, and largely insoluble in carbon disulfide. 

SCOPE. This definition includes peat, lignite, cannel coal, bitu- 
minous coal, anthracite coal, and the non-asphaltic pyrobituminous 
shales. 

Tar. A term applied to pyrogenous condensates obtained in the 
destructive distillation of organic materials; of dark color, liquid 
consistency; having characteristic odors; comparatively volatile at 
high temperatures; composed principally of hydrocarbons, some- 
times associated with carbonaceous matter, the non-carbonaceous 
constituents being largely soluble in carbon disulfide, yielding water- 
soluble sulfonation products. 

SCOPE. This definition includes the volatile oily decomposition 
products obtained from the pyrogenous treatment of petroleum 
(water-gas tar and oil-gas tar), bones (bone-tar), wood and roots 
of coniferae (pine tar), hardwoods, such as oak, maple, birch, and 
beech (hardwood tar), peat (peat tar), lignite (lignite tar), bitu- 
minous coal (gas-w r orks coal tar, coke-oven coal tar, blast-furnace 
coal tar, producer-gas coal tar, etc.), and pyrobituminous shales 
(shale tar). 



58 TERMINOLOGY AND CLASSIFICATION II 

Pitch. A term applied to pyrogenous residues obtained in the 
distillation of organic materials; of dark color, viscous to solid con- 
sistency; comparatively non-volatile, fusible; composed principally 
of hydrocarbons; sometimes associated with carbonaceous matter, 
the non-carbonaceous constituents being largely soluble in carbon di- 
sulfide, yielding water-soluble sulfonation products. 

SCOPE. This definition includes residues obtained from the dis- 
tillation of tars (oil-gas-tar pitch, water-gas-tar pitch, bone-tar 
pitch, wood-tar pitch, peat-tar pitch, lignite-tar pitch, gas-works 
coal-tar pitch, coke-oven coal-tar pitch, blast-furnace coal-tar pitch, 
producer-gas coal-tar pitch, and shale-tar pitch) ; also from the dis- 
tillation of fusible organic substances, the process having been termi- 
nated before the formation of coke (rosin pitch and fatty-acid 
pitch) ; also anthracene pitch, naphthol pitch, cresol pitch, ozokerite 
pitch, montan pitch, rubber pitch, gutta-percha pitch, etc., known in 
Germany as "Immediate Pitches," i.e., produced directly (immedi- 
ately) on distillation, without the initial formation of tars, 2 

In Germany, the terms "Chemopeche" and "Chemoasphalte" 
are used to designate pitches and asphalts, respectively, which are 
produced as the result of chemical reactions, including the fol- 
lowing : 8 

(a) Precipitation products, resulting from the precipitation or 
selective extraction by means of solvents. 

(b) Oxygenated products, resulting from the treatment with 
air, oxygen, ozone, etc., at elevated temperatures, e.g. blown petro- 
leum asphalt, blown coal-tar pitch, etc. 

(c) Hydrogenated products, resulting from treatment with hy- 
drogen in the presence of a catalyst at elevated temperatures, and 
distillation of the resultant product. 

(d) Reaction with mineral acids (i.e., sulfuric, nitric, phos- 
phoric, etc.) and evaporation or distillation of the residue, e.g. 
sludge asphalt. 

(e) Reaction with alkalies and subsequent precipitation, extrac- 
tion, or distillation of the resultant product. 

(f) Reaction with sulfur or sulfur derivatives at elevated tem- 
peratures, e.g. sulfurized asphalts and pitches. 

(g) Reaction with halogens (e.g. chlorine, iodine, etc.). 
(h) Reaction with phosphorus and its derivatives. 

[i) Reaction with metallic salts; either solid salts at elevated 
temperatures, or aqueous solutions of metallic salts in refining op- 
erations, and separation of the resultant polymerized product 



II BITUMINOUS SUBSTANCES 59 

(j) Reaction with sundry chemicals (e.g. formaldehyde and its 
derivatives, furfurol, etc.). 

It will be noted that the terms "asphalt" and "mineral wax" 
are each applied indiscriminately to native and pyrogenous sub- 
stances. This is due to the fact that at the present time it is prac- 
tically impossible to distinguish between certain native and pyroge- 
nous asphalts or mineral waxes, either by physical or chemical means. 
It is probable that some method may be discovered for accomplish- 
ing this, in which event it would be of decided advantage to frame 
separate definitions to distinguish between native and pyrogenous 
substances respectively. With the knowledge available at present, 
however, this cannot readily be accomplished. We must be content, 
therefore, to apply the terms "asphalt" and "mineral wax" both to 
native substances and to manufactured (pyrogenous) products. 

In many of the early classifications, natural gas and marsh gas 
were included within the scope of the term "bitumen." As this 
stretches the meaning to an abnormal extent, the author deems it 
inadvisable to include natural gases in the definitions and classifica- 
tions given in this treatise. 

The terms "maltha" (derived from the Greek /*<IX0a), "brea" 
and "chapapote" (of Mexican Spanish origin), "goudron minerale" 
(French), "Bergteer" (German), "kir" (Russian), 4 and "mineral 
tar" (English), frequently found in contemporary classifications to 
designate the softer varieties of native asphalt, have been omitted 
for the sake of brevity. 

When it comes to classifying bituminous substances, the inter- 
pretation of the word "bitumen" represents the crux of the entire 
matter. An analysis of the views concerning the scope of this term, 
prevalent in America and abroad, shows that they may be grouped 
into four classes, which will be listed in the order of their breadth, 
commencing with the one having the narrowest scope : 

(a) Bitumens naturally occurring hydrocarbons. 

(b) Bitumens naturally occurring hydrocarbons, likewise resi- 

dues obtained from the distillation of petroleum (e.g., 
petroleum asphalts). 

(c) Bitumens naturally occurring hydrocarbons, likewise resi- 

dues obtained from the distillation of petroleum, likewise 
artificial hydrocarbon substances (e.g., tars and pitches). 



60 TERMINOLOGY AND CLASSIFICATION II 

(d) Bitumens only those components of (c) which are soluble 
in carbon disulfide. 

View (a) represents the layman's interpretation of the word, as 
is reflected in the principal dictionaries of both abroad and America. 
It is obvious from these definitions that the word ''bitumen'' has for 
generations been confined to hydrocarbon substances which occur 
in nature, and distinctly excludes hydrocarbon substances produced 

artificially. . 

View (b) is supported by the British Engineering Standards 
Association, also by Dr. Heinrich Mallison in Germany. This in- 
volves a slight departure from View (a), including as it does, resi- 
dues obtained from the distillation of petroleum. 

View (c) is still somewhat broader than (b), being extended to 
include tars and pitches. It is supported abroad by David Holde 
and Wilhelm Reiner and others. , 

View (d) has been adopted in principle by the American Society 
for Testing Materials, 5 and the American Standards Association. 

Now the question arises as to whether there is any need or justi- 
fication of extending the dictionary definitions embodied in View 
(a). In other words, has the scientific fraternity the right to change 
or modify what has been the common heritage of the people, without 
some particularly good reasons ? The only apparent justification for 
extending the scope of the word "bitumen" as reflected in Views (b) 
and (c) is to include certain products which have been developed 
and produced since the word was originally adopted such products 
as petroleum asphalts, tars and pitches. Parenthetically, there 
seems to be but little justification to extend the word "bitumen" 
to include petroleum asphalts (as outlined in View &), since the 
prpcess of distillation has a marked effect on the nature of the 
asphalt originally present in the petroleum. At the high end-tem- 
peratures at which the distillation process is conducted (600 to 
800 F.) a form of polymerization takes place, whereby asphalt-like 
substances are produced. In other words, the percentage of asphalt 
in the petroleum is increased under these conditions. It follows 
therefore, that the petroleum asphalts produced commercially, differ 
in their physical and chemical properties from the asphalt originally 
present in the petroleum, or separated in nature by a slow natural 
process of evaporation. 

If the word "bitumen" is broadened in accordance with View (c) 



H BITUMINOUS SUBSTANCES 61 

it will become synonymous with the word "bituminous substance" 
so that both expressions will have an identical meaning. 

Singularly, there seems to be but very little difference of opinion 
at the present time with respect to the expression * 'bituminous sub- 
stance." In this, the scientific fraternity seems to be in accord with 
the dictionary definitions. It is the consensus of opinion that the 
expression "bituminous substance" represents a form of substance 
which contains bitumens, or resembles bitumens, or constitutes the 
source of bitumens. This is based on a commonly accepted interpre- 
tation of the suffix "ous," signifying: 

i to contain; 

2 to resemble, to partake of the nature, or to have the qual- 
ities of. 

This raises the question as to whether or not language as it exists 
at present does not furnish us with sufficient tools to answer our 
needs. Is not the expression "bituminous" ("bituminous sub- 
stance") of sufficient breadth to include "bitumens" (i.e., naturally 
occurring hydrocarbons) as well as petroleum asphalts, tars and 
pitches? Is it not true that petroleum asphalts, tars and pitches 
resemble "bitumens" or partake of their nature in respect to their 
physical properties? Then why broaden the scope of the word "bi- 
tumen" so as to make it synonymous with the expression "bituminous 
substance"? The author can see no justification or necessity for so 
doing. 

Moreover, View (d) is so technical, that it is questionable 
whether the laity will ever accept it. Its proponents maintain that 
the only way to determine whether or not a substance is a "bitumen" 
is to subject it to chemical analysis, to find out what proportion is 
soluble in carbon disulfide. According to this view, the presence of 
any associated mineral constituents or hydrocarbons insoluble in 
carbon disulfide would disqualify the original substance as a "bitu- 
men" even though it occurred as such in nature. 

The author therefore advocates that the words "bitumen" and 
"bituminous substance" be defined in scope as expressed in View 
(a), which is exactly as they have been heretofore used and accepted 
in the language. He believes further that by using these two terms 
co- jointly, a satisfactory system of classification may be devised, 
which will answer adequately the needs of the scientific fraternity, 



62 



TERMINOLOGY AND CLASSIFICATION 



II 



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II 



BITUMINOUS SUBSTANCES 



63 




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64 TERMINOLOGY AND CLASSIFICATION II 

and at the same time be in complete harmony with the dictionary 
definitions as they now exist. 

With the foregoing in mind, the author has worked out a basis 
for classifying bituminous substances, including the most important 
members recognized commercially, which will be found in Table III. 



CHAPTER III 
CHEMISTRY OF BITUMINOUS SUBSTANCES 

Bituminous substances in general may be regarded as consisting 
of one or more of the following components: 

(A) The Non-mineral Matrix. 

(B) Associated Mineral Constituents. 

(C) Associated Non-mineral Constituents. 

Each component will be considered in turn. 

(A) COMPOSITION OF NON-MINERAL MATRIX 

The non-mineral matrix present in bituminous substances is a 
complex mixture of hydrocarbons together with their sulfur and 
nitrogen derivatives, and are frequently associated with mineral 
constituents in varying amounts. The non-mineral constituents are 
accordingly composed of the elements carbon and hydrogen, with 
more or less sulfur, nitrogen, and at times oxygen. The constituent 
hydrocarbons may either be saturated or unsaturated. Saturated 
hydrocarbons are those in which the carbon valence has been com- 
pletely taken up by hydrogen or other radicals, and are characterized 
by their resistance to reagents (e.g. acids and alkalies) and the dif- 
ficulty with which they form substitution compounds. Unsaturated 
hydrocarbons are those having free carbon valences, and have the 
property of forming additive compounds. 

Every member of the bituminous family is a homogeneous or 
heterogeneous mixture, consisting of a multitude of chemical sub- 
stances, each having a definite molecular composition. These con- 
stituent substances may be associated as a simple solution of liquids 
in liquids, or solids in liquids; or in the form of a colloidal solution; 
or as a solid solution of amorphous or crystalline solids; or as an 
emulsion of immiscible liquids; or as a suspension of insoluble sub- 
stances in a more or less liquid matrix; or combinations of two or 

more of the foregoing phases. 

65 



66 CHEMISTRY OF BITUMINOUS SUBSTANCES III 

It is contended that the characteristic dark color of asphalts is 
due to the liberation of colloidal carbon under the influence of heat, 
which is then adsorbed by the hydrocarbons. 1 The colloidal nature 
of asphalt is confirmed by the Tyndall effect, the Brownian move- 
ment observed under the ultra-microscope even in dilute solutions, 
the fact that on distillation no trace of asphaltic or coal-like sub- 
stances are found in the distillate, and the further fact that asphal- 
tenes retain hydrogen even at 800 F. 

F. J. Nellensteyn regards asphalt as a protected u lyophobe sol," 
or an extremely stable u carbon-oleosole," in the form of a "system" 
consisting of three components, viz. : 

(1) The "medium" (corresponding to the so-called "petro- 
lenes" or "oily constituents"). 

(2) The "lyophilic portion" or protective bodies (correspond- 
ing to the so-called "asphaltic resins"). 

(3) The "lyophobic portion," composed of colloidal particles 
or ultra-microns of elemental carbon. 

An adsorption relation exists between components (2) and (3), 
forming a "disperse phase" and constituting the so-called "asphalt 
micelle" (corresponding to the "asphaltenes"). According to this 
hypothesis, the asphalt constituents may be classified into the fol- 
lowing systems : 

Petrolenes (malthenes) and oily constituents = oily medium. 
Asphaltous acids plus asphaltous acid anhydrides plus asphaltic 

resins = small amount of carbon with very large amount of 

protective bodies. 

Asphaltenes == carbon with protective bodies. 
Carbenes = carbon with small amount of protective bodies. 
Pyrobitumens = carbon with very little protective bodies. 

The stability of the "system" depends upon the respective sur- 
face tensions of the "medium" and "micelle." Changes in the sta- 
bility, including "flocculative" and "peptizing" reactions, give rise to 
a "reversible flocculation." If, however, the micelle itself is de- 
stroyed and cannot be directly repeptized, the substance is said to 
have undergone an "irreversible flocculation." The latter is caused 
by chemical reactions (e.g. iodine, chlorine, etc.) ; by heat; or by 
exhaustive extraction of asphaltenes with different solvents of suc- 
cessively higher surface-tension. In natural asphalts associated with 



Ill 



(A) COMPOSITION OF NON-MINERAL MATRIX 



67 



colloidal mineral matter (e.g. Trinidad asphalt), the ultra-microns 
present in the micelle consist partly of elemental carbon and partly 
of inorganic material. Adding finely divided fillers to asphalt may 
result in the formation of such micelles. 

The properties of asphalts depend upon the concentration of the 
disperse phase, its degree of subdivision, as well as the properties of 
the medium. The combination of these functions leads from the 
crude petroleum, through the soft and viscous asphalts, over to the 
asphaltites. For the mechanism of this col- 
loidal system in its transition from petro- 
leum to the hard asphalts and asphaltites, 
the following theory may be developed, in 
which the underlying idea is clearly illus- 
trated. In Fig. 24 the black points and 
areas represent the "asphalt micelles," the 
white points and areas the "oily medium." 
In region A, the asphalt micelles are pres- 
ent in such slight amount and in such a high 
degree of subdivision that they exist in the 
oily medium in the form of a molecularly 
dispersed solution. This region corre- 
sponds to the characteristics of crude petro- 
leum before it is subjected to distillation 
in the preparation of residual asphalt. 
In the distillation process, the concen- 
tration of the oily medium gradually 
diminishes, and the particle size of the 
dispersed phase (asphalt micelles) cor- 
respondingly increases, until they assume 
a dimension larger than molecular, and 




FIG. 24. Formation of As- 
phalts Illustrated Diagram- 
matical ly. 



eventually reach the 
state of a colloidal dispersion. The gradual enlargement of the 
micelles, or the increase in their number (through continued distil- 
lation) is illustrated by regions B, C, D and E, which represent the 
disperse systems of soft to moderately hard asphalts. Further re- 
duction of the oily phase causes constantly greater reduction of the 
distances of the micelles from one another, and accordingly leads to 
the agglomeration of the asphalt micelles, as shown in region F. 
We then come into the range of hard asphalts and the reversal of 



68 CHEMISTRY OF BITUMINOUS SUBSTANCES III 

phases. If the reduction of the oily medium continues further, then 
the aggregates of the micelles become so large and their number in- 
creases to a degree that they eventually fuse together, resulting in 
the asphalt micelles forming the continuous phase and the oily con- 
stituents the disperse phase, as illustrated in regions V, W, X and Y. 
If the process continues sufficiently far, the system will finally consist 
only of asphalt micelles, as shown in region Z. Regions V to Z em- 
brace the hard, high fusing-point asphalts and asphaltites. 

It is a comparatively simple matter to ascertain by analytical 
methods the percentage by weight of the elements present. This is 
termed the ultimate analysis, in contra-distiriction to the molecular 
composition. 

The greatest percentage of carbon found in any bituminous sub- 
stance is in the case of anthracite coal, which runs as high as 98 
per cent The smallest percentage is contained in certain peats, 
which run as low as 50 per cent. With the exception of the non- 
asphaltic pyrobitumens, carbon ranges from 85 to 95 per cent. 

Hydrogen never exceeds 15 per cent. In the paraffin series of 
hydrocarbons, the carbon is combined with as much hydrogen as 
possible, and this accordingly contains the largest percentage of 
hydrogen and the smallest percentage of carbon. The lowest mem- 
ber of this series CtL, a gas, contains 75 per cent of carbon and 25 
per cent of hydrogen. The member C 3 oHe2 contains 85.31 per cent 
of carbon and 14.69 per cent of hydrogen. In the olefin series 
CnHU, the relation of carbon to hydrogen is constant, and figures : 
carbon 85.71 per cent and hydrogen 14.29 per cent. 

The percentage of sulfur varies considerably. Waxes, coal tar 
and coal-tar pitch, pine tar arid pine-tar pitch, hardwood tar and 
hardwood-tar pitch, also fatty-acid pitch are practically free from 
sulfur. In petroleum, the sulfur varies from a trace to 5 per cent 
as a maximum. Mexican petroleum contains between 3 and 5 per 
cent; Trinidad, Venezuela and California petroleums contain be- 
tween l / 2 and 4 per cent; semi-asphaltic petroleums including the 
Mid-continental and Texas oils contain from a trace to 2]/2 per cent 
Paraffinaceous petroleums contain merely a trace. Residual oils 
contain from a trace to 5 per cent. Residual asphalts, blown as- 
phalts, sludge asphalts, native asphalts, asphaltites, asphaltic pyro- 
bitumens and non-asphaltic pyrobitumens contain from a trace to ifr 



Ill (A) COMPOSITION OF NON-MINERAL MATRIX 69 

per cent sulfur. Tars and pitches derived from non-asphaltic pyro- 
bitumens contain from a trace to I J4 per cent 

Nitrogen is rarely present in excess of 2 per cent. Mineral 
waxes are free from nitrogen. Petroleum asphalt, asphaltites and 
pyrobitumens contain from a trace to 1.7 per cent nitrogen. Tars 
and pitches contain from o to I per cent. 

Oxygen rarely exceeds 5 per cent, except in the case of non- 
asphaltic pyrobitumens which contain up to 45 per cent of oxygen. 

At the present time but a comparatively small number of dis- 
tinct chemical substances have been identified in bituminous com- 
plexes. A vast amount of research work must yet be accomplished. 
Although hundreds of substances of definite molecular composition 
have been identified in petroleums, native mineral waxes, pyrogenous 
waxes and certain tars, comparatively little is known regarding the 
innumerable non-mineral molecular substances present in native as- 
phalts, asphaltites, asphaltic pyrobitumens, non-asphaltic pyrobitu- 
mens, pyrogenous asphalts and pitches. 

The chemistry of bituminous substances is further complicated 
by the fact that commercial specimens of any given material are 
rarely alike in composition. In some, certain chemical bodies pre- 
dominate ; in others, they may be present in smaller amounts ; while 
in still others they may be absent. Thus two shipments of any 
given member of the bituminous family are apt to fluctuate widely 
in composition and physical properties, even when emanating from 
the same source. Again, a native bituminous substance derived 
from a single deposit will often vary, depending upon the degree of 
exposure and extent of metamorphosis. Native bituminous sub- 
stances are in a constant state of transition, as the result of their 
age and environment. Pyrogenous bituminous substances show a 
marked variation in composition and physical properties, depending 
upon the raw materials used in their production and the exact con- 
ditions to which they have been subjected in their processes of manu- 
facture, including the temperature, length of treatment, etc. Bitu- 
minous substances should not therefore be compared with vegetable 
or animal fats or oils, which in the case of any given material will 
run fairly uniform in composition and physical properties. 

In certain instances, comparatively simple tests have been de- 
vised for identifying single chemical bodies present, whereas in other 



70 CHEM1STR? OF BITUMINOUS SUBSTANCES III 

cases the ultimate analysis of the material will furnish a clue to the 
identity of the substance under examination. 

Various methods have been proposed to separate bituminous 
substances into their constituents, including fractional distillation 
under reduced pressure, 2 the selective action of solvents, 3 the use of 
adsorption media, 4 and combinations of the foregoing. 

(B) COMPOSITION OF ASSOCIATED MINERAL CONSTITUENTS 

The mineral constituents may be present in one or more of the 
following typical forms : 

1. As consolidated mineral particles consisting of a porous rock 
impregnated with the bituminous constituents. This type is exem- 
plified by the so-called u rock asphalts," which are usually composed 
of a fine-grained limestone or sandstone matrix, carrying the asphalt 
in its voids. 

2. As unconsolidated mineral particles admixed mechanically 
with the bituminous constituents. This is typified by the numerous 
deposits of impure native asphalts and asphaltites, in which the 
bituminous constituents are associated with more or less detritus 
derived from the surrounding soil ; also blast-furnace tar and pitch 
which carry a proportion of mineral dust carried over mechanically 
by the furnace gases as well as metallic compounds which result from 
the corrosion of pipe lines and containers used in storage and 

transport. 

The principal unconsolidated mineral constituents present in na- 
tive asphalts and asphaltites consist of calcium carbonate, magnesium 
carbonate, calcium sulfate, dolomite, clay, silica and the various 
silicates, iron sulfide, etc. 

3. As colloidal mineral particles held in suspension by the bitu- 
minous constituents. Trinidad Lake asphalt is typical of this group, 
and is characterized by the presence of colloidal clay and silica 
which are not removable by filtration and are^ readily discernible 
when viewed under an ultra-microscope. 5 Richardson makes a 
special virtue of the fact that refined Trinidad asphalt contains nat- 
urally about 27 per cent filler composed largely of "colloidal" 
particles. 

4. As mineral matter held in chemical combination by the non- 
mineral (i.e., pure bituminous) constituents. This group differs 
from the foregoing, inasmuch as it relates to a chemical union of the 
mineral and non-mineral components. Many native asphalts carry 
small percentages of iron and aluminium, but it is as yet a mooted 
question whether these are present as colloidal particles, or united 



Ill (C) ASSOCIATED NON-MINERAL CONSTITUENTS 71 

chemically with the bituminous matter. Most residual and blown 
petroleum asphalts contain a trace of iron, derived from the stills in 
which they are refined. Fatty-acid pitch, wood-tar pitch, bone-tar 
pitch and rosin pitch carry a substantial amount of iron or copper, 
depending upon whether they have been produced in an iron or 
copper still. Sludge asphalts bear a trace of combined lead derived 
from the lead containers in which they have been treated. 

Rare elements are also normally associated with certain native 
asphalts and asphaltites. Thus the following proportions of nickel, 
expressed in parts per million, have been reported : 6 Trinidad as- 
phalt 194, Swiss asphalt 120, gilsonite 133, residual asphalt from 
U. S. petroleum 240, crude U. S. petroleums i to 93 parts, ozokerite 
trace to nil. Vanadium is present in most varieties of petroleum and 
asphalt, 7 and has also been reported in Argentine grahamite 8 and 
Peruvian impsonite. 9 Vanadium occurs in the more asphaltic crudes, 
but is not present in any quantity in non-asphaltic (i.e., paraffin- 
aceous) crudes. A high vanadium content is generally associated 
with a high nickel content. 10 Uranium has similarly been reported 
in glance pitch found in Utah, 11 and molybdenum in asphaltic petro- 
leum 12 and Holzheim (Swabian) oil shales. 



(C) COMPOSITION OF ASSOCIATED NON-MINERAL 
CONSTITUENTS 

Native asphalts often contain non-mineral impurities in the form 
of decayed vegetable substances of peat-like nature, which were 
originally present in the soil, now associated with the asphalt. These 
substances are derivatives of humic, or ulmic, crenic, etc., acids. 

Certain tars and pitches as well as residual asphalts, which have 
been overheated in their process of manufacture, will carry variable 
amounts of so-called u free carbon." This in reality consists of 
hydrocarbon derivatives, polymerized under the influence of heat 
to an insoluble modification, similar in certain respects to bitumi- 
nous coal. It is probable that the "free carbon" may under certain 
conditions consist in part of amorphous carbon, similar to lamp- 
black. R. Hodurek has demonstrated that tars inherently contain 
certain insoluble constituents which may be removed by filtration 
(which he designates "Carbon I") and that other substances ("Car- 
bon II") are formed by precipitation upon dissolving the tar in 
solvents, the quantity being dependent upon the particular solvent 
employed. 14 



72 CHEMISTRY OF BITUMINOUS SUBSTANCES III 

(D) BEHAVIOR WITH SOLVENTS 

This question will be taken up in detail in Chapter XXVI. 
(E) BEHAVIOR ON SUBJECTING TO HEAT 

On heating bitumens, the following reactions take place : at low 
temperatures they commence to distil without decomposition. Con- 
tinued heating causes a rapid change in penetration and viscosity 
during the first few days or weeks, whereas the flash-point is least 
affected. The fusing-point changes regularly but markedly. There 
is a general decrease in acidity (i.e., acid value) which finally attains 
a constant figure. 16 As the temperature increases, a certain amount 
of cracking takes place, resulting in the depolymerization of both the 
distillate and residue. At still higher temperatures, the distillate 
continues to deploymerize, whereas the residue commences to polym- 
erize with the formation of asphalt-like bodies. Beyond this, the 
residue again undergoes depolymerization with the evolution of a 
certain amount of fixed gases, likewise the formation of carbenes, 
free carbon, and eventually elemental carbon. Thus in the case of 
non-asphaltic and semi-asphaltic petroleums, polymerization takes 
place when the residue in the still reaches 600 to 800 F., whereby 
asphalt-like substances are produced. In other words the percentage 
of asphalt in petroleum is actually increased under these conditions. 
Beyond this temperature, cracking takes place, in which the asphalt 
is destructively distilled and decomposed into simpler molecules, 
yielding gases, liquid distillates and a residue of coke. 16 

The asphaltic pyrobitumens behave differently. When heated 
to between 600 and 800 F., they undergo "cracking." This is in 
reality a form of depolymerization in which complex molecules are 
broken down into simpler ones. As a result, the original substance, 
which is practically insoluble in organic solvents, increases materially 
in! solubility. Elaterite and wurtzilite depolymerize and become 
completely soluble in benzol and carbon disulfide. Albertite is more 
difficult to depolymerize than elaterite or wurtzilite, requiring a 
higher temperature and an increased time of treatment. On the 
other hand, impsonite depolymerizes only slightly under these con- 
ditions. If heated to higher temperatures, the asphaltic pyrobitu- 
mens suffer destructive distillation, leaving a residue of coke. The 
depolymerization is similar to the action which takes place on melt- 



Ill 



(E) BEHAVIOR ON SUBJECTING TO HEAT 



73 



ing fossil resins, such as copal, amber, etc., in manufacturing varnish. 
A schematic outline of what occurs upon subjecting bitumens and 
pyrobitumens to heat is given in the following tabulation : 



TABLE IV 
BEHAVIOR ON SUBJECTING TO HEAT 







Heated 
under 300 C. 


Heated 
300-450 C. 


Heated 
450-700 C. 


Heated 
700-1500 C. 




Non-asphaltic 


Distil and the 


Residues de- 








petroleums 


residues fuse 


polymerize 












slightly 








S e mi- asphalt! c 


Distil and the 


Residues poly- 








and asphaltic 


residues fuse 


merize, form- 








petroleums 




ing asphalt- 












like bodies 


Depolymerize, 




Bitumens 


Mineral waxes 


Small amount 


Depolymerize 


yielding as 








distils with 


and distil 


distillate 








slight decom- 




mostly open- 








position, and 




chain hy- 








the residues 




drocarbons 








fuse 




and a resi- 






Asphalts and 


Fuse 


Distil more or 


due of coke 






Asphaltites 




less 








Asphaltic pyro- 


Infusible and 


Depolymerize 








bitumens 


insoluble 


and become 






Pyrobitumens. . ' 


Non-asphaltic 


Infusible 


more soluble 
Unaffected 


Depolymerize 


Depolymerize, 




pyrobitumens 






slightly and 


yielding as 










distil 


distillate, 












mostly cyclic 












hydrocarbons 












and a residue 












of coke 



F. J. Nellensteyn has proposed the following theory to account 
for the formation of asphalts and the like: 

(/) Formation of Asphalts: 
Hydrocarbons {$$* } = 

Transformed to carbon + Adsorbed protective hydrocarbon bodies 

Asphaltenes 

(//) Behavior of the Asphaltenes: 



Asphaltenes 



extracted 

oxidized 

heated 



74 CHEMISTRY OF BITUMINOUS SUBSTANCES III 

Carbon + Small amount of adsorbed protective hydrocarbon bodies 

Free carbon 

Free carbon { heated } = 

Carbon + Very small amount of adsorbed hydrocarbon bodies 

Retort carbon 

Resulting in a further decomposition of the protective bodies. 

(///) Synthesis of Asphaltenes: 
Retort carbon {electrically atomized in the presence 
of protective hydrocarbon bodies } = 

Carbon + Adsorbed protective hydrocarbons 
Asphaltenes 

(F) REACTIONS WITH GASES 

(a) Oxygenation. On blowing air through bituminous sub- 
stances at fairly high temperatures, hydrogen is removed in the form 
of water, and at the same time the hydrocarbons polymerize, form- 
ing bodies of higher molecular weight and more complex structure. 
The reaction may be roughly represented as follows : 

CxH y + O = CxHy_ 2 + H 2 O 

Analysis shows that little or no oxygen actually combines with 
the asphalt. 17 One theory is that polyhydric compounds acidic in 
character, are formed during the intermediate stage of oxidation, 
which upon further heating change to anhydrides similar to the poly- 
naphthenic acids, with progressive condensation and polymerization. 
Various bituminous substances are affected differently by the blowing 
process. Asphalts present in petroleum are readily converted into, 
tough, rubber-like products having a higher fusing-point and much 
more resistant to temperature changes. Fatty-acid pitch behaves in 
a similar manner. Natural asphalts are affected very much less, 
and pitches derived from coal and wood are scarcely affected at all. 
Even the petroleum asphalts themselves are affected differently, de- 
pending upon their origin and chemical characteristics. This sub- 
ject will be gone into more fully under the heading 44 Petroleum 
Asphalts." 

(b) Hydrogenation. This is carried out by heating bituminous 
substances (e.g., coal, asphalt, paraffin wax, tars, etc.) with hydro- 



Ill (F) REACTIONS WITH GASES 75 

gen in an autoclave at high pressures (100 to 200 atmospheres) at 
400 to 450 C. The process was discovered by Friedrich Bergius, 18 
and has been termed "berginization." The following changes take 
place : 

1 i ) Thermal decomposition, i.e., cracking. 

(2) Hydrogenation, whereby the unsaturated hydrocarbons re- 
sulting from the thermal decomposition, at their moment of forma- 
tion, react with the hydrogen, producing saturated hydrocarbons of 
lower boiling-points. 

The process differs from straight thermal decomposition in the 
following respects: extensive polymerization is avoided and the 
deposition of carbonaceous matter is almost entirely prevented, 
moreover, as the reaction proceeds the pressure in the autoclave 
falls, due to the absorption of hydrogen, whereas in the absence of 
hydrogen, the pressure would increase due to the formation of fixed 
gases. Finally, the end product consists largely of saturated hydro- 
carbons, whereas in the cracking processes, unsaturated bodies will 
predominate. The resulting products are characterized by a higher 
hydrogen content. Any oxygen present in the original material is 
converted into water, and any nitrogen into ammonia. 

In treating petroleum by the Bergius hydrogenation process, hy- 
drogen gas is introduced at a pressure of about 3600 Ibs. per sq. in. 
in the presence of a catalyst. Molybdic anhydride and sulfur 19 
seems to be most favored, although numerous othef catalyzers have 
been proposed, including chromium, tungsten, uranium, manganese, 
cobalt, etc., compounds, also metallic iron or nickel. 20 The catalyst 
should be sulfur-resistant and serve to speed up the reaction and 
eliminate the oxygen from the hydrogenated product. Relatively 
impure hydrogen, containing hydrogen sulfide, is used, produced 
from coal or coke by the water-gas process. 

Asphaltic crudes of all characters (e.g., Venezuelan, Panuco, Co- 
lombian, etc.), likewise residues from refinery crudes, as well as 
cracking-plant tars, may be converted into volatile distillates, free 
from asphalt and low in sulfur, with volumetric yields somewhat in 
excess of 100% (although the specific gravity of the product is 
usually less than the crude stock). Dark asphaltic constituents are 
converted into practically colorless hydrocarbons of the gasoline 
range. In other words, the hydrogen will combine with the colloidal 



76 



CHEMISTRY OF BITUMINOUS SUBSTANCES 



III 



carbon present in the asphalt present. In actual practice, the petro- 
leum is first topped to remove all the gasoline present. From mixed- 
base crudes, highly paraffinic products may be produced, such as 
gas-oils, burning oils and high-grade lubricants. From paraffin 
crudes, so-called aromatic products may be produced, as for example, 
a highly anti-knock gasoline. No coke is produced in the process. 

The charging stock, together with sufficient hydrogen, is pumped 
through heat-exchangers to a coil-furnace, and thence into the reac- 
tion vessel containing the catalyst where it is subjected to the re- 
quired temperature and pressure. Units have been installed capable 
of treating 5000 barrels of crude daily. 21 The final products with 
the gases pass through heat-exchangers and coolers to a high-pres- 
sure separator, where the liquid reaction products are separated 
from the unconsumed hydrogen and other gases, which latter are 
scrubbed with oil under pressure to remove the hydrogen sulfide, 
and the purified gas used over again. 

The following five adaptations of hydrogenation appear to be of 
most importance in petroleum refining: 22 

TABLE V 









APPROXIMATE VOLUMETRIC 












YIELD or 


TOTAL 


GAS 


PROCESS 


CHARGING STOCK 


PRIMARY RESUI-T 










VOLU- 


FORMA- 








Gasoline 


Burn- 
ing Oil 


Gas 
Oil 


Lube 
Oil 


METRIC 
YIELD 


TION 








% 


% 


% 


% 


% 


%byvt. 


z 


High-sulfur, asphalt- 


Asphalt and sulfur elimination 
















ic heavy residue 


with simultaneous conversion 


















entire charge into distillate 


















oils 


30 




71 


. . . 


zoz 


2 to 3 


a 


Low-grade lube dis- 


Production premium lube, par- 
















tillate 


ticularly as regards temper- 


















ature-viscosity relationship, 


















flash, carbon, and gravity 


10 


.... 


29 


6S 


Z04 


0.5 to z,s 


3 


Low-grade burning 


Production of low-sulfur pre- 
















oil distillate 


mium grade burning oil 


3Q 


73 






zo3 


O-S tO 2 


4 


Cracked naphtha 


Desulfurization and gum sta- 












,' 






bilization without deteriora- 


















tion in yield and knock rating 


















characteristic of acid treating 


zoo 


.... 




. . . 


zoo 


0.5 


.5 


Paraffinic gas oil 


Production of low-sulfur, low- 


















gum, good antiknock gasoline 


65 to zoo 








70 to zoo 


S to 35 



If the charging stock is paraffinic in character, it is heated to 
750 F., and if aromatic, to 1000 F. The reaction is exothermic. 23 
It is' advocated that very heavy asphaltic crudes be treated in three 



Ill () REACTIONS WITH ACIDS 77 

stages, at pressures of 1000, 200 and 20 atmospheres, respectively* 04 , 
The residual product obtained from the hydrogenation of residual 
asphalts has characteristics somewhat similar to those of blown pe- 
troleum asphalt. 25 Partial hydrogenation of petroleum stocks at 
900 to 950 F., without using a catalyst, is claimed to result in the 
precipitation of any asphalt present 26 Low-temperature coal-tar 
(topped to 200 C.), when hydrogenated with a mixture of molybdic 
acid and sulfur as catalyst, under an initial pressure of 145 atmos- 
pheres, yielded 99.2% of hydrogenated oil. The reaction started 
at 200 C., which increases to a maximum of 360 C. 27 The prod- 
uct is free from tar acids and pitchy matters. 28 Cdke-oven tar 
showed an increase in volatile products below 300 C. from 31.7 
to 65.5%, and in this case the hydrogen was absorbed by the liquid 
residue as well as by the fixed gases. Paraffin wax was entirely con- 
verted into liquid and gaseous products. Similarly, Alberta san^ 
asphalt has been hydrogenated under a pressure of 1470 Ibs. at 
380 to 410 C. in the presence of ammonium molybdate and alumi- 
num chloride, or NiCOs and Fe2O 8 or CaO (to remove the sulfur), 
being converted into 80 to 90% by weight of oils based on the as-? 
phalt present in the raw material, and involving the absorption of 

by weight of hydrogen. 29 

A modification of the preceding has been devised by Meilach 
Melamid, which consists in atomizing asphaltic petroleum into a 
heated reaction chamber together with hydrogen, so that the two 
are brought in contact with a catalyzer (e.g., tin or bismuth alloys 
melting below 700 F.)- 80 In this process the hydrogenation and 
continuous distillation of the crude oil take place simultaneously. 
In the case of a Panuco (Mexican) crude, the distillate to 320 C. 
was increased from 19 to 26 per cent, and in the case of a brown-* 
coal tar resulting from the Mond gas process, the pitch residue was! 
reduced from 46.8 per cent to o.o per cent, with a corresponding 
increase in the percentages of distillates. 

(G) REACTIONS WITH ACIDS 

(a) Liquid Sulfur Dioxide* This agent has the property of 
dissolving unsaturated hydrocarbons ait low temperatures ( 7 to 
11 F.), whereas the saturated hydrocarbons remain substan- 



78 CHEMISTRY OF BITUMINOUS SUBSTANCES III 

tially insoluble. Advantage is taken of this fact in certain commer- 
cial refining operations, also in the laboratory examination of bitu- 
minous substances. 81 In general, the higher boiling-point paraffins, 
naphthenes and naphthenic acids (i.e., over 175 C.) are insoluble, 
whereas the aromatics and the true unsaturated hydrocarbons (con- 
taining two or more double bonds) are miscible with liquid sulfur 
dioxide in all proportions. Sulfur and its organic combinations, 
nitrogen compounds, resinous and asphaltic substances are also sol- 
uble, though their solubilities decrease with increasing complexity of 
the molecule. 82 

(b) Sulfuric Acid and Sulfur Trioxide. Concentrated sulfuric 
acid, or a mixture of concentrated sulfuric acid with sulfur trioxide 
reacts with bituminous substances in a somewhat complicated man- 
ner, involving both the formation of sulfo derivatives and that of 
simple solution, accompanied by a certain amount of polymeriza- 
tion. In general, it may be stated that the following classes of 
substances are removed by concentrated sulfuric acid: unsaturated 
and aromatic hydrocarbons, asphaltic bodies, saponifiable constitu- 
ents and alkaline bases. This reaction forms the basis of the method 
used commercially for refining petroleum distillates and is likewise 
used in the laboratory under accurately controlled conditions for 
the separation of saturated and unsaturated hydrocarbons. (See 
Test 34.) A process has been described which consists in heating 
residual asphalt with 20 to 25 per cent of concentrated sulfuric 
acid to 120 C. which is then gradually increased to 240 C. The 
addition compounds are separated and the residue (i.e., sludge as- 
phalt) used for molding purposes. 33 

(c) Nitric Acid. Strong nitric acid reacts in two ways, namely 
in the formation of nitro derivatives and in the oxidation of the 
hydrocarbons. Which of these predominates depends upon the 
nature of the hydrocarbons, the strength of the acid, the tempera- 
ture, etc. Although much work has been done in investigating the 
character of end-products, but little commercial use has been made 
of this reaction. 84 Similar products are obtained by heating tars, 
pitches or asphalt with substances containing NOa or NOs radicals. 35 
It has been noted that certain of the nitro addition products are 
soluble in acetone and alcohol, thus differing from the hydrocarbons 
from which they were derived. 



Ill (/) REACTIONS WITH METALLOIDS 71) 

(d) Sulfuric Acid and Formaldehyde. Formaldehyde in the 
presence of concentrated sulfuric acid reacts with unsaturated cyclic 
hydrocarbons and asphaltic constituents with the formation of an 
insoluble formolite, whereas the other classes of bodies remain 
unaffected. This reaction is utilized in the laboratory examination 
of bituminous substances. (See Test 35.) It has also been pro- 
posed to incorporate the formolite with asphalts, pitches, etc., to 
produce molded products, electrical insulation, etc. 86 

(e) Phosphoric Acid. Phosphoric acid has been proposed for 
refining mineral oils, yielding "sludge asphalt" 



37 



(H) REACTION WITH ALKALIES 

Strong alkalies react with the saponifiable constituents present, 
including the following groups of substances : free asphaltous acids, 
asphaltous acid anhydrides, fatty and resinous constituents. The 
saponifiable constituents in commercial bituminous substances vary 
from a trace in the case of bitumens and asphaltic pyrobitumens, 
to as high as 90 per cent and over in the case of rosin pitch and 
fatty-acid pitch. The effects of alkalies will be considered later in 
greater detail. 

(I) REACTIONS WITH METALLOIDS 

(a) Sulfur and Sulfur Bichloride. Under the influence of 
heat, sulfur has the same condensing effect upon bituminous sub- 
stances as oxygen, since it results in the removal of hydrogen, but 
in this instance in the form of gaseous hydrogen sulfide. The reac- 
tion may roughly be represented as follows : 

CxHy + S = CxHy-2 + H 2 S 

A certain amount of polymerization also takes place, and where the 
sulfur is used in excess, it is likely that a certain amount remains in 
combination with the bituminous substances in the form of addition 
products. The process has been termed "vulcanization," and is 
used to improve the stability of bituminous mixtures. This will be 
:onsidered more fully under the description of the respective sub- 
stances in subsequent chapters. 

Sulfur dichloride combines with bituminous substances under 



&) CHEMISTRY Of BITUMINOUS SUBSTANCES III 

moderate heat, with the liberation of hydrochloric acid as a product 
of the reaction, Which may be roughly indicated by the following: 



= GH y _ 6 + 2H*S + 2HC1 



. 38 



This reaction is merely of academic interest 3 

(b) Selenium. Selenium combines with asphalts, etc., at 160 to 
300 C. in a manner analogous to sulfur, with the liberation of 
hydrogen selenide, a proportion of the selenium remaining in com- 
bination with the residue. 30 

(c) Phosphorus. It has been noted that phosphorus, or PgOs 
under the influence of moderate heat, will cause asphalts to polym- 
erize, and in part combine chemically with the asphalt, resulting 
in an increase of hardness, fusing-point and stability. 40 

(d) Halogens. Chlorine and iodine 41 eliminate hydrogen and 
result in the deposition of carbon, in accordance with the following 
reactions : 

C*H y + Cl = CxH y ^ + HC1 

y + Cl = .C.-iH y -i + C + HC1 



Similar reactions take place with iodine, also boron fluoride. 42 
The relation between the "iodine number" of asphalts and their 
structure has also been investigated. 43 

, Halogens seem to destroy the protective colloids that keep the 
colloidal carbon in suspension and result in the deposition of ele- 
mental carbon, if the reaction progresses far enough. Upon treat- 
ing asphalt with chlorine gas in the presence of a trace of iodine at 
200 to 250 C., the fusing-point is increased materially, and a hard, 
glossy product is obtained having a glossy fracture. 44 Similarly, a 
soft coal-tar pitch will have its fusing-point increased from 25 or 
30 F. ,to 120 F,, 45 likewise its adhesiveness increased. 4 * It i$ 
claimed that hexachlorethane will react in a similar manner. 47 A 
process has also been proposed which involves treatment with 
chlorine below 130 C. in the presence of antimony chloride, phos- 
phorus chloride, or iodine; 48 likewise a method of treating with con- 
centrated sulfuric acid, followed by FeCU, AlCls, or PCls. 49 



Ill (/) REACTIONS WITH METALLIC SALTS 81 

(J) REACTIONS WITH METALLIC SALTS 

Bituminous substances act as "dispersoids," in that they have 
the property of dispersing colloidal solids, including certain metal- 
lic salts. Trinidad asphalt is a typical example, in which the asphalt 
acts as a dispersoid for adventitious mineral matter of colloidal 
nature, consisting principally of colloidal clay. That the clay is 
present in a colloidal state is evidenced by the following facts : ( i ) 
a dilute solution of Trinidad asphalt in carbon disulfide, upon stand- 
ing, retains indefinitely the clay in suspension, and moreover it 
cannot be separated upon centrifuging, or upon passing the solution 
through an ultra-filter; and (2) an examination of the solution 
through the ultra-microscope shows the mineral particles to be in a 
characteristic state of active motion, known as Brownian movement 
or "pedesis," which may be made to cease under the influence of an 
electric field ("cataphoresis"). This subject will be discussed fur- 
ther in Chapter XXIV under the heading "Colloidal Particles 
Liberated 'In Situ'." Other metallic salts which will disperse in 
bituminous substances include sulfates and selenates, chlorides, ox- 
ides, acetates and borates. 



CHAPTER IV 

GEOLOGY AND ORIGIN OF BITUMENS AND 
PYROBITUMENS 

GEOLOGY 

Age of the Geological Formations. The earth's crust has been 
divided into natural groups or strata in the order of their antiquity. 
There are five main divisions, which range in sequence as follows : 

1. Quaternary or Post-tertiary, representing the strata now in 
the process of formation. 

2. Tertiary or Caenozoic, embracing the age of recent life. 

3. Secondary or Mesozoic, representing the less recent life. 

4. Primary or Paleozoic, representing the so-called "ancient 
life." 

5. Archaean or Azoic, representing the so-called lifeless strata. 

These divisions are recognized by the distinctive organic re- 
mains, fossils, minerals and other characteristics. They are clas- 
sified into various "systems" as shown in Table VI. 

The systems form a chronological time-chart indicating the rela- 
tive ages of the earth's strata. The systems are further sub-divided 
into groups which differ in different localities, but it will be unneces- 
sary to consider their sub-classification here. 

Petroleum occurs in all of the geological horizons from the Re- 
cent down to the Pre-Cambrian. Certain systems are richer than 
others, especially the Pliocene, Miocene, Oligocene, Eocene, Car- 
boniferous, Upper Devonian and Lower Silurian (Ordovician). 
Asphalts, asphaltites and non-asphaltic pyrobitumens are found in 
all the systems from the Pliocene to the Silurian. Mineral waxes 
are found largely in the Pliocene, Miocene, Oligocene, Eocene and 
Cretaceous. 

The non-asphaltic pyrobitumens do not occur in the older Paleo- 
zoic formations i.e., the Silurian or Cambrian Systems). The 
Carboniferous System contains the most valuable coal deposits; the 
Permian and Triassic Systems contain coals of inferior quality, and 

82 



IV 



CHARACTER OF THE ASSOCIATED MINERALS 



the coals found in the Jurassic, Cretaceous, Eocene and Oligocene 
Series are still more inferior in quality. Lignite occurs in the Oligo- 
cene and Miocene Series, and peat in the Pliocene and Pleistocene. 
The Pre-Cambrian Series consists largely of crystalline, metamor- 
phic rocks of volcanic and igneous origin. The non-asphaltic pyro- 
bitumens, as might be expected, do not occur in rocks of this char- 
acter. Graphite, however, occurs in the Pre-Cambrian rocks, and 
may possibly have been derived from vegetable matter, although no 
signs of associated plant remains have been found in these rocks. 



ERA 

Quaternary or Post- 
tertiary 



Tertiary or Caenozoic. . 



Secondary or Mesozoic. 



TABLE VI 

SYSTEM 

f f Historic ^ 

I Recent or Post-glacial \ Prehistoric 
,.1 I Neolithic 

[ Pleistocene or Glacial 

f Pliocene 
I Miocene 
' ' I Oligocene 
I Eocene 



Cretaceous . . . 


r Upper 
Middle 




Lower 


Jurassic 


Middle 




Lower 


Triassic 




Permian 




Carboniferous < 


Swer 



Primary or Paleozoic. 



Devonian 



Silurian 



Cambrian. . 



f Upper 
| Middle 
[ Lower 

/Upper 

\ Lower (Ordovician) 

f Upper 
| Middle 
[Lower 



Archaean or Azoic Pre-Cambrian 

The particular geological system is of value in enabling us to 
prospect and trace deposits of bitumens and pyrobitumens in any 
given locality. 

Character of the Associated Minerals. Bitumens and pyrobitu- 
mens, with but few exceptions, are found in sedimentary deposits of 
sand, sandstone, limestone and sometimes in shale and clay. Rare 



84 GEOLOGY AND ORIGIN Of BITUMENS AND PYROBITUMENS IV 

occurrences have been reported in igneous 'rocks, but then only in 
very small quantities. 

Modes of Occur .ence. Bitumens and pyrobitumens are found in 
nature in the f oP : wing ways : 

1. Over flews: 

(a) Springs. 

(b) Lakes. 

(c) Seepages. 

2. Impregnating Rocks: 

(a) Subterranean pools or reservoirs. 

(b) Horizontal rock strata. 

(c) Vertical rock strata. 

3. Filling Veins: 

( a ) Caused by vertical cleavage. 

[b ) Caused by upturning. 

c) Caused by sliding. 

d) Formed by sedimentation. 

Springs. Petroleu;n and the liquid forms of asphalt only are 
found in springs (Fig. 25). These emanate from a fissure, crevice, 
or fault which permits the petroleum or liquid asphalt to rise to the 
surface from some depth. Petroleum or asphalt springs have been 
reported in various parts of the world, but are rarely of commercial 
importance. tl 

Lakes. Asphalt only is sometime^ found in lakes, which are in 
reality springs on a very large scale (Fig. 26). Some of the largest 
and most valuable deposits occur in this form, the best known being 
the lakes at Trinidad and Venezuela. It is probable that the as- 
phalt is forced up from below in a liquid or semi-liquid condition 
by the pressure of the o\\ and gas underneath, which causes it to 
flow through a fissure ,or fault and spread over a large area at the 
surface. Lake asphalts are moderately soft where they emanate, 
but harden on exposure to the elements. 

Seepage. These occur in the case of petroleum or liquid 
asphalts, and usually from cliffs or mountains bearing impregnated 
rock. Elmer the pressure of the material itself or the heat of the 
sufi causes ^'certain quantity, Usually not very large, to flow out of 
the rock and rtin towards the lower level (Fig. 27). Seepages are 
ofteft found where d ripidly flowing stream of water cuts its way 



IV 



MODES OF OCCURRENCE 



85 




Spring 
FIG. 25 



FIG. 26 




91 



Miles 

Cap Rock (Shale) 
Oik Oasj 0/'/\ 

\ " -- 




Seepages 
FIG. 27 



Subteranean J?ool or Reservoir 
FIG. 28 




Impregnated^Hprlzontat Strata 
FIG. 29 



Impregnated, Strata in. Thrust, 
FIG. 30 




Fault Filling caused l?y Cleavage 
FIG. 31 



Fault Filling caused by Upturning 
FIG. 32 




Vein Filling caused by Sliding of Strata Veins formect by Sedimentation 
FIG. 33 FIG. 34 





-JL.-1 



Pure Rock Alluvium Sand Sand Limestone Clay Shale Orartift 
Asphalt Asphalt Stone 

1 FIGS. 25-34, 



86 GEOLOGY AND ORIGIN OF BITUMENS AND PYROBITUMENS IV 

through strata of rock impregnated with petroleum or asphalt 
From a commercial standpoint, seepages of asphalt or petroleum 
are of little value. 

Subterranean Pools or Reservoirs. Practically all deposits of 
petroleum of any magnitude occur below the surface of the earth in 
subterranean "pools" or "reservoirs." These consist of porous 
sand, sandstone, limestone (or dolomite) with a more or less imper- 
vious rock cover. The porous bed is exemplified by coarse-grained 
sandstone, conglomerate, or limestone. The limestone may have 
been dense as it existed originally, but rendered porous in the course 
o time by conversion into dolomite, with the consequent production 
of voids due to shrinkage, since dolomite occupies less space than 
the original limestone. The petroleum is carried in the interstices 
of the porous rock and prevented from volatilizing or escaping by 
an impervious cover known as the "cap-rock," usually composed of 
shale or a dense limestone. The main supplies of petroleum have 
been obtained from regions which have been comparatively undis- 
turbed by terrestrial movements. In such cases the accumulation 
of petroleum underneath forms what is known as a "pool" or "res- 
ervoir" (Fig. 28). * 

Impregnated Rock in Strata. Liquid to semi-liquid asphalts 
occur in this manner. Rocks impregnated with asphalt are pro- 
duced in two ways, viz. : 

1 i ) By the gradual evaporation and hardening of an asphaltic 
petroleum due perhaps to the disturbing or removal of the cap-rock, 
leaving the asphalt residue filling the interstices of the stratum car- 
rying it. These are usually found in horizontal strata (Fig. 29). 

(2) By the liquid asphalt being forced upward under pressure, 
or drawn upward by capillarity from underlying strata into a porous 
rock layer above it. These are usually found in the region of a 
"thrust" or upturning of the earth's strata (Fig. 30). 

Filling Feins. The harder asphalts, asphaltites and asphaltic 
pyrobitumens are most commonly found filling fissures in a more or 
less vertical direction, caused by "faulting." In geology, a "fault" 
is a more or less vertical crack in the earth's surface brought about 
by the contraction and uneven settling of the strata. This is occa- 
sioned by a greater movement in the rock on one side of the fault's 
plane than on the other, as illustrated in Fig. 31, or by the upturning 



IV MOVEMENT OF BITUMENS IN THE EARTH'S STRATA 87 

of a section of the earth's crust as shown in Fig. 32. Faults allow 
the liquid or molten asphalt to force its way up from underneath 
and fill the crevice. As will be described later, after the asphalt 
hardens in the fault, it might in time become metamorphosized and 
converted into an asphaltite or asphaltic pyrobitumen. Non-asphal- 
tic pyrobitumens are never found in faults, probably because they 
are incapable of softening or melting under the action of heat, either 
in their original state or afterwards. 

Sometimes we find the harder asphalts, asphaltites and asphaltic 
pyrobitumens filling a more or less horizontal fissure or cleavage 
crack, brought about by the sliding of two strata, one upon the 
other. The opening between the strata becomes filled with the liquid 
or melted asphalt, forced up under pressure through a crevice from 
below, which then hardens, giving rise to a horizontal vein as shown 
in Fig. 33. 

Horizontal veins are sometimes derived from prehistoric asphalt 
"lakes," perhaps similar to our present Trinidad or Venezuela lakes. 
In time, these harden, and become submerged in water, due perhaps 
to a movement in the level of the earth's crust. The water permits 
the sedimentation of mineral matter, so that 'the lake is gradually 
converted into a horizontal vein. If the liquid asphalt again breaks 
through a fault or fissure, it will form a superimposed vein, or per- 
haps a series of such veins between sediments, as shown in Fig. 34. 

In the case of non-asphaltic pyrobitumens, the veins were un- 
questionably formed by a process of sedimentation. The vegetation 
from which these were derived, originally grew in swampy or marshy 
localities, presumably about the mouths of rivers. As the vegetation 
died, it became covered with sediments of sand or clay carried down 
by the water, or by calcium carbonate precipitated from the water, 
which in turn formed soil for subsequent growths. These gave rise 
to the future veins of non-asphaltic pyrobitumens, which are similar 
structurally to the preceding (Fig. 34). 

Movement of Bitumens in the Earth's Strata. It is a singular 
fact that petroleum, mineral waxes, asphalts and asphaltites are not 
always found in the same locality in which they originated. They 
have the power of migrating from place to place, and many deposits 
are still in the process of migration. A "primary deposit" is one in 
which the bituminous material is still associated with the same rocks 



88 GEOLOGY ANf> ORIGIN OF BITUMENS AND PYROSITUMENS IV 

in which it originated, A "secondary deposit'' is one to which the 
material has subsequently migrated. Bitumens usually migrate 
while in a liquid or melted condition, although in certain rare in- 
stances the migration has been induced by the action of flowing 
water while the bitumen is in the solid state. 

The main causes for the movement of native bituminous sub- 
stances in the earth's surface are as follows: 

1 I ) Hydrostatic Pressure, This is largely responsible for the 
accumulation of petroleum in pbols or reservoirs. At some distance 
below the earth's surface there is an accumulation of ground water, 
the level of which wries in different localities and during different 
seasons. The petroleum, being lighter than the water, floats on its 
surface. As the level of the ground water varies, it will move the 
petroleum about through interstices in the rock. The water tends to 
push the oil ahead of it, and this will account for the accumulation 
of the petroleum in the form of pools or reservoirs underneath a 
cap of a dense and non-porous strata through which it cannot per- 
meate. This will also explain why there is often an accumulation 
of petroleum in the ground near the top of a hill or mountain. Oil 
and gas are often encountered under pressure, due to the hydro- 
static head of water. 

Hydrostatic pressure may also cause the migration of solid as- 
phalts, as for example in the case of the Dead Sea, where masses 
become detached from the bottom and are caused to float upward 
by the higher gravity of the water, due to the large percentage of 
salt dissolved in it. 

(2 ) Gas Pressure. It is probable that the action of the heat or 
other forces below the surface of the earth, tend partially to va- 
porize certain bitumens, so that the resulting gas will force them 
into the overlying strata near the surface. In other instances the 
effect of faulting, crumpling, upturning, erosion and other move- 
ments of the earth's strata exposes the oil- or asphalt-bearing forma- 
tions, and enables the gas pressure to force them to the surface. 
Natural gas exists under great pressure in certain localities. Many 
gas wells in the Baku and Pennsylvania fields have registered a pres- 
sure of 600 to 800 lb., and even as high as 1000 Ib. per square inch. 
This may be accounted for by the fact that as the gas is constantly 
being generated, it accumulates inside of the earth's surface and 
has no access to escape owing to the density of the strata above. 

(3) Capillary. This force takes place m dry porous rocks 
and acts on permanently liquid bitumens, of bitumens solid at ordi- 
nary temperatures but transformed to the melted state by the action 
of heat. Under these conditions the bitumen will' soak into the 



IV ORIGIN AND METAMORPHOSIS OF BITUMENS, ETC, 89 

pores of the rock or sand and gradually fill the interstices. Capil- 
larity is a very much stronger force than gravity, although other 
forces, such as the action of heat (see under 5) may be partly re- 
sponsible. The finer the pores in the rock, the greater will be the 
capillary force. Rocks saturated with moisture tend to resist the 
action of capillarity, w r hich is most effective in the dry state. 

(4) Gravitation. The natural weight of the overlying strata 
caused by gravitation sets up a pressure where there are accumula- 
tions pf petroleum or other forms of liquid bitumen underneath^ 
and if a fissure or fault occurs in the earth's crust, the bitumen, 
being softer than the surrounding rock, will be forced to the sur- 
face. Gravitation is therefore selective in its action and by exerting 
a greater pull on the heavier bodies will tend to force the lighter 
ones upward. Under other circumstances, where the substances 
are not confined, the result of gravitation is^ to cause the petroleum 
or liquid asphalt to ooze from the overlying rock matrix in the 
form of "seepages." 

(5 ) Effect of Heat. Heat is also a large factor in causing the 
migration of bituminous substances. Its effect is variable. Undter 
certain circumstances it will convert the solid bitumens into a liquid 
state and thus enable them to be acted upon by the various forces 
considered previously. Under other conditions, heat in the interior 
of the earth will vaporize the bitumens such as petroleum and force 
them upward. Again, if the heat is sufficiently intense, it is apt to 
cause the bitumens to undergo destructive distillation, the distillate 
condensing in the upper and cooler layers. 

ORIGIN AND METAMORPHOSIS OF BITUMENS AND ASPHALTIC 

PYROBITUMENS 

Probable Origin of Bitumens and Asphaltic Pyrobitumens. Al- 
though much has been written on this subject, no generally accept- 
able conclusions have been reached. The discussion has in the main 
centered about the origin of petroleum, as this is conceded to be the 
mother substance, from which the other bitumens and pyrobitumens 
are supposed to have been produced by a* process of metamorphosis. 
The theories have been divided into two classes, namely, the inor- 
ganic and the organic. We will consider these in greater detail. 

Inorganic Theories. It is contended that the interior of the 
earth contains free alkaline metals, presumably in a melted condi- 
tion. These at high temperatures would react with carbon dioxide, 
forming acetylides which in turn produce hydrocarbons of the acety- 
lene series upon coming in contact with water* The acetylenes being 



90 GEOLOGY AND ORIGIN OF BITUMENS AND PYROBITUMENS IV 

unsaturated would have a tendency to combine with free hydrogen 
and give rise to the olefine and paraffin series. 

Still another theory based on similar lines assumes the presence 
of metal carbides, including iron carbide, some distance below the 
surface of the earth. These are supposed to decompose on coming 
in contact with water and produce hydrocarbons, which upon con- 
densing in the cooler upper strata give rise to petroleum. This, 
however, is mere speculation, for no iron carbide has ever been 
found. The occurrence of hydrocarbon gases in volcanic emana- 
tions has been cited to substantiate this theory. 

The cosmical hypothesis is based upon the assumption that hy- 
drocarbons were present in the atmosphere which originally sur- 
rounded the earth, after it had been thrown off by the sun. These 
hydrocarbons are claimed to have been formed by a direct combina- 
tion of the elements carbon and hydrogen in the cosmic mass. As 
the earth cooled, the hydrocarbons condensed in the earth's crust, 
giving rise to deposits similar to those existing to-day. This theory 
has also been connected with the carbide theories, upon the assump- 
tion that at the high temperatures to which the gases must have 
been subjected at the time they were thrown off by the sun, and 
before they condensed, the first compounds formed were carbides, 
silicides, nitrides, and the like. As oxidation would not commence 
until some time later, it is assumed that these carbides would remain 
locked up in the interior of the earth for geologic ages, and then 
gradually give rise to hydrocarbons upon being decomposed through 
the agency of water. 

Vegetable Theories. It has long been known that certain hydro- 
carbons result during the decay of vegetation. The hydrocarbon 
methane (CH 4 ), otherwise known as "marsh gas" is produced in 
this manner, but only in comparatively small amounts. Similarly, 
methane has been detected in the gases resulting during the decay 
of seaweed. 

It has been shown by others that under certain conditions hydro- 
carbons may be produced artificially by the fermentation and decay 
of certain forms, of cellulose, including woody fiber. Still other 
scientists maintain that petroleum is produced by microscopic plants 
known as diatoms, which occur abundantly in peat beds, and certain 
bogs. These organisms are found to contain minute globules of 



IV ORIGIN AND METAMORPHOSIS OF BITUMENS, ETC. 91 

oily matter distributed in the plasma, and moreover, a waxy sub- 
stance resembling ozokerite may be extracted by solvents from the 
diatomaceous peat. It is contended that this oil will in time and 
under pressure become converted into liquid petroleum, and at 
higher temperatures and pressures possibly into asphalt. In sup- 
port of this hypothesis a bed of peat has been described near Stettin, 
Germany, consisting largely of diatoms and from which hydro- 
carbons have been extracted in quantities up to 4 per cent. 

Another theory based on similar lines infers that petroleum is 
derived from a slimy substance rich in organic matter known as 
"sapropel," composed largely of algae, which accumulates at the 
bottom of stagnant waters. This slime becomes covered with sedi- 
ments which through the agency of moisture, time and pressure, is 
assumed to give rise to petroleum, and under certain conditions, to 
asphalt It is of interest to note that petroleum and asphalt have 
been produced in the laboratory by the hydrolysis of algae in acid 
solutions. 1 

In a similar manner, bitumens are claimed to have been formed 
from deposits of vegetable matter, including various marine plants, 
seaweeds, etc., which accumulate at the bottom of the ocean. Just 
as the non-asphaltic pyrobitumens (e.g., coal) are produced by the 
decomposition of terrestrial vegetation, it is contended that bitumens 
have arisen from the decay of marine plants. This theory has a 
number of adherents. The optical activity of certain petroleums h^s 
been cited to substantiate the contention, since oils derived from 
organic matter can only possess this property. It has been proven 
that hydrocarbons produced from inorganic substances, such as 
metal carbides, do not exhibit optical activity. 

Still another theory, advocating the vegetable origin of petro- 
leum, assumes its derivation from peat, lignite or coal, which have 
been subjected to a sufficiently high temperature to undergo a prqc- 
ess of destructive distillation, resulting in the production of liquid 
and gaseous hydrocarbons. This is supposed to have occurred at 
great depths below the earth's surface and the hydrocarbons con- 
densed in upper layers. 

The asphaltic pyrobituminous shales are similarly claimed to 
have generated petroleum under the action of heat, based on the 
well-known fact that when these shales are distilled commercially, 



92 GEOLOGY AND ORIGIN OF BITUMENS AND PYROBITVMENS W 

petroleum-like oils are produced. It is contended that the shales 
themselves were derived from gelatinous algae whose remains are 
still recognizable in certain of them with the aid of a microscope. 

Animal Theories. In a similar manner, petroleum and asphalt 
are supposed to have been produced from the accumulation of ani- 
mal matter at the bottom of the ocean, which in time decomposed 
into hydrocarbons. The presence of nitrogen in all forms of bitu- 
men is cited in substantiation of its production from albuminoid 
matter. The remains of molluscs and fish are present in certain 
asphaltic pyrobituminous shales, including the Albert series of New 
Brunswick, and in many rocks carrying petroleum and asphalt. 
Deposits of the latter have been reported in Galicia, Wyoming, and 
are particularly noticeable in the case of oil and asphalt deposits in 
Uvalde County, Texas, and southeastern California. In Egypt, 
shells are also found filled with bitumen. Others contend that the 
living cells are in some manner absorbed into the pores of coral 
reefs, and that these in time result in the formation of bituminous 
limestone. 

Substances closely resembling petroleum or bitumens have been 
produced artificially by subjecting fish albumin to heat, under pres- 
sure. Asphalt-like substances have been produced by heating gela- 
tine, casein, calcium carbonate and magnesium carbonate in an at- 
mosphere of hydrogen at 240 C under pressure of 33 atm. The 
solution of the resultant product in carbon disuifide exhibited 
Brownian movement and the particles were flocculated by ether. 2 
Animal fats have similarly been converted into hydrocarbons boil- 
ing below 300 C. The conversion of fats and albuminous sub- 
stances into petroleum is said to depend upon three factors, namely, 
pressure, temperature and time. The variations in the composition 
of petroleum found in different localities, are accounted for by varia- 
tions in one or more of these factors. 

In conclusion it might be stated that probably all three theories 
embody certain elements of truth. The cosmical hypothesis is sus- 
tained by the fact that hydrocarbons have often been found in me- 
teorites, although this supposition has been refuted. 3 The inorganic 
theory/is f boi-ne out by the fact that hydrocarbons occur in volcanic 
emanations.: The vegetable and animal theories in turn are sup- 
ported by the presence of bitumens and pyrobitumens in rocks of 



IV METAMORPHOSIS OF MINERAL WAXES, ETC. 93 

sedirheritary character, often carrying vegetable and animal fossil 
remains. Mabery contends that the presence of nitrogen in petro- 
leum derived from all the principal oil fields, exists in the form of 
tombinations which could only have had their origin in vegetable 
or animal remains. 4 

It is highly probable, therefore, that bitumens owe their origin 
to two or more of the theories which have been discussed, and which 
would account for their varying chemical composition and physical 
characteristics. 

Metamorphosis of Mineral Waxes, Asphalts, Asphaltites and 
Asphaltic-Pyrobitumens from Petroleum. Although there seems 
to be a wide difference of opinion regarding the origin of petroleum 
authorities are pretty well agreed that petroleum when once formed, 
is gradually converted into the other types of bitumen and pyro- 
bitumens, under the influence of time, heat and pressure. This 
process of transformation is known as "metamorphosis." 

Several chemical processes are involved, e.g., oxidation, sulfuri- 
zation, polymerization (i.e., the combination of like molecules) and 
condensation (i.e., the combination of unlike molecules). Some 
natural asphalts are derived through the slow evaporation of lower 
boiling-point fractions from the original petroleum; others indicate 
conversion by heat and pressure; still others show evidence of slow 
oxidation. It is likely that a combination of these three processes 
occur simultaneously. Asphalt associated with tar sands has under- 
gone little change other than the loss of volatile fractions; on the 
other hand, gilsonite, glance pitch and grahamite appear to be prod- 
ucts of reaction and conversion, rather than products of evaporation. 

It is contended that mineral matter in a finely divided form, as 
for example "colloidal" clay, hastens the transformation of natural 
gas or petroleum, by acting as a catalyzer. This theory is advanced 
by Clifford Richardson. 5 In studying the well-known Trinidad 
asphalt lake, Richardson concludes that an asphaltic petroleum 
existing at a considerable depth is converted into a more solid form 
of bitumen, namely asphalt, upon being thoroughly emulsified with 
colloidal clay, sand and water through the medium of natural gas 
at a high pressure. During the metamorphosis, hydrogen is gradu- 
ally eliminated, the hydrocarbons becoming enriched in carbon, and 
from a chemical standpoint more complex structurally. The changes 



94 GEOLOGY AND ORIGIN OF BITUMENS AND PYROBITUMENS IV 

brought about during this process may be regarded as a form of 
polymerization, in which the hydrocarbon molecules become rear- 
ranged into more complex molecules of higher molecular weight 

The simplest hydrocarbons are present in petroleum. Those in 
mineral waxes are somewhat more complex, and both the structural 
complexity and the molecular weight increase in the case of asphalts 
and the asphaltic pyrobitumens. There are no sharp lines of de- 
marcation between the various types of bitumens or asphaltic pyro- 
bitumens. Each class gradually merges into another, and specimens 
will often be found on the border line, so that it is difficult to decide 
to which class they actually belong. 

From this viewpoint we may regard petroleums as passing in 
gradual stages, uftder the influence of time, heat, pressure and cata- 
lyzers into the soft native asphalts, which in turn pass into harder 
native asphalts, and then into asphaltites and finally into the asphal- 
tic pyrobitumens and asphaltic pyrobituminous shales. 6 

TABLE VII 

PETROLEUM (Crude Oil) 



/ \ 

Non-asphaltic Petroleum Semi' Asphaltic and Asphaltic Petroleums 

I I 

Mineral "Waxes Native Asphalts 

( Ozokerite ) / * \ 

Pure and Impure 

Fairly Pure Asphalts (Rock Asphalts) 

J I 

Asphaltites (Impure Asphaltites) 

I I 

Asphaltic Pyrobitumens Asphaltic Pyrobituminous Shales 

CELLULOSE (Woody Fiber) 



Vegetable Growths (Sphagnum) in Bogs, Swamps, etc. Trees, etc* 

Jr 

Peat 
Impure (Associated with Mineral Matter) Pure 

Lignite Shales Lignite 

I I 

Coal Shales Bituminous Coal 

Anthracite Coal 
Graphite 



IV ORIGIN OF NON-ASPHALTIC PYROBITUMENS 95 

It is highly probable that all deposits of asphalt are produced 
by metamorphosis from asphaltic petroleum. Similarly it seems 
likely that all deposits of mineral wax, such as ozokerite, etc., result 
from the metamorphosis of paraffinaceous petroleum. 

Elaterite, wurtzilite, albertite, impsonite and the asphaltic pyro- 
bituminous shales represent the final stages in the metamorphosis 
of petroleum. The first four are comparatively free from mineral 
matter. If the latter predominates, the product is known as an 
asphaltic pyrobituminous shale. The non-mineral matter contained 
in these shales has the same general characteristics as elaterite, 
wurtzilite, albertite or impsonite, depending upon how far the meta- 
morphosis has progressed. 

Table VII gives an approximate idea of the natural metamor- 
phosis of bitumens and pyrobitumens, one from another. 7 

ORIGIN AND METAMORPHOSIS OF NON-ASPHALTIC 
PYROBITUMENS 

The origin of non-asphaltic pyrobitumens has been definitely 
established. The associated fossil remains clearly prove that these 
have been derived from vegetable matter containing cellulose, a 
carbohydrate having the empirical formula (CeHioOs)^ 

The decomposition of cellulose when the air is partly or wholly 
excluded, as would be the case when buried in the ground, results in 
the loss of carbon dioxide, methane, and water. In this manner, 
cellulose ultimately yields a series of products grouped under the 
heading of non-asphaltic pyrobitumens. The conditions favorable 
to their production seem to be the growth of vegetable substances 
about the mouths of rivers, combined with a change in water-level. 
The sediment carried down by the river, formed beds of sand or 
clay which sealed the vegetation in between the strata. In this man- 
ner the vegetable matter was protected from atmospheric oxidation 
and at the same time probably subjected to fermentative heat, also 
to a gradually increasing pressure, as successive layers accumulated. 
The vegetation doubtlessly embraced many different kinds, including 
trees, ferns, grasses, mosses, and the like. Fossil ferns are still 
clearly evident in coal beds. In other cases carbonized trees, roots 
and fibrous tissue are recognizable, and in still others, the resins 
originally present in the wood are found intact. Amber and fossil 



36 GEOLOGY AND ORIGIN OF BITUMENS AND PYROBITUMENS IV 

copal often occur in peat, and large masses of vegetable resin have 
been identified in beds of lignite and bituminous coal 

Peat represents the first stage in the metamorphosis of coal from 
vegetable matter, and occurs in bogs or other swampy places. Very 
often on the surface of a bog or swamp we see the still living and 
growing plants. A little below, we find their decayed remains, and 
still deeper, a black glutinous substance saturated with moisture, 
known as "peat" 8 

The exact nature of the changes which take place in the trans- 
formation of vegetable matter into peat is not clearly understood. 
The ultimate analysis shows that the percentages of hydrogen and 
oxygen have diminished, and carbon correspondingly increased. In 
the most recent deposits, peat is loosely compacted, but as it accumu- 
lates under the sediments, it becomes compressed. A bed which 
was possibly once a foot thick might shrink to several inches. In 
all probability the pressure developed by the superimposed layers, 
aids in the transformation of peat into coal. 

Lignite 9 or browncoal is intermediate between peat and bitumi- 
nous coal. The most recent deposits approach peat in composition, 
and the oldest merge into bituminous coal. Lignite contains a larger 
percentage of carbon and smaller percentages of hydrogen and oxy- 
gen than peat It is often associated with mineral resins or wax-like 
hydrocarbons * which may be extracted by means of solvents, 

Jet, gagate, azabache and "black amber" are species of lignite. 

Cannel coal 10 and bog-head coal and torbanite are in reality a 
sub-class of bituminous coal, rich in volatile matter. The former 
are supposed to have been derived from spores, spore cases, and 
resinous or waxy products of plants (e.g., sapropel). The absence 
of woody material gives cannel coal a uniform texture and grain 
not present in other coajs, so that it breaks with a conchoidal frac- 
ture, and a splinter ignites in contact with a lighted match, burning 
like a candle, whence it derives its name. 

*The associated resins or waxes, or asphalts, as they are termed by some, have been 
described under various names, including: Anthracoxenite, Bombiccite, Branchite, Bu- 
tyrellite, Dinite, Dopplerite, Duxite, Dysodile, Euosmite, Fichtelite, Geomyficite, Hartine, 
Hartite, Hofmannite, lonite, Koflachite, Leucopetrin, Leucopetrite, Melanchyme, Mellite, 
Middletonite, Muckite, Neudorfite, Neft-Gil, Phytocollite, Pianzke, Pyronetin, Refikite, 
Retinasphaltum, Retinite, Rochlederite, Schleretinite, Sieburgite, Trinkerite, \Valchowite, 
Wheelerite, etc. ; - , 



IV ORIGIN OF NON-ASPHALTIC PYROBITUMENS 97 

Bituminous coal falls between lignite and anthracite coal. It is 
often a matter of difficulty to determine where the lignites stop and 
the bituminous coals begin; similarly, the line of demarcation be- 
tween bituminous and anthracite coals is not very distinct. Bitu- 
minous coals contain a larger percentage of carbon and smaller 
percentages of hydrogen and oxygen than lignite. The name "bi- 
tuminous coal" is derived from the fact that this coal apparently 
softens and undergoes fusion at a temperature somewhat below that 
of actual combustion. The term, however, is a misnomer. The 
softening which takes place marks the point at which destructive 
distillation commences, accompanied by the formation of gaseous 
hydrocarbons. "Bitumen" does not actually exist in bituminous 
coal. That portion which dissolves in solvents (e.g., xylol, phenol, 
tetralin, etc.) has been termed "bituminic substance," since it re- 
sembles bitumens. The insoluble portion has been termed the "lig- 
nitic residue," since it resembles lignite. Bituminous coals contain 
a substantial portion of volatile matter, which causes them to burn 
more rapidly than anthracite, and with a larger amount of flame. 
The so-called "coking coal" is a class of bituminous coal, used in 
the manufacture of coke. The relationship between bitumens and 
coal has also been traced by the similarity of the substances sepa- 
rated by the selective action of certain solvents, in their deportment 
under heat, vacuum distillation, behavior towards chemical agents, 
etc. 11 

Anthracite coal represents the final stage in the transformation 
of vegetable matter into a non-crystalline form. It contains definite 
proportions of hydrogen and oxygen. Certain forms of anthracite 
approach graphite in their composition. Graphite on the other hand 
is a crystallized mineral composed entirely of carbon, and which is 
supposed to represent the final stage in the metamorphosis of coal. 
The mode of occurrence and microscopic structure of graphite de- 
posits corresponds closely with those of coal, giving rise to the belief 
that both were derived from a common source. 



CHAPTER V 

ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES 
AND THEIR MANUFACTURED PRODUCTS 

PRODUCTION OF ASPHALTS, ASPHALTITES AND ASPHALTIC 

PYROBITUMENS 

World Production. Deposits of natural asphalts have been dis- 
covered in all parts of the world. Table VIII, compiled from data 
furnished by the Department of Interior of the U. S. Geological 
Survey, shows the total production of all forms of native asphalts 
(including pure and rock asphalts), asphaltites and asphaltic pyro- 
bitumens, from 1906 to 1931 inclusive, as far as reliable statistics 
are available. 1 

In 1931, the United States produced the largest quantity of 
native asphalts, having assumed the lead since 1920. Italy ranks 
second, followed by Trinidad, Germany, France and Venezuela, in 
the sequence stated. 

Production in the United States. Table IX gives the total 
production by states in the United States of natural asphalts, as- 
phaltites and asphaltic pyrobitumens for the years 1911 to 1935 
inclusive, and Table X gives the production by varieties of natural 
asphalts, asphaltites, asphaltic pyrobitumens and petroleum asphalts 
from 1900 to 1935 inclusive. 

No appreciable tonnage of asphalt was produced in the United 
States until 1883, when about 35,000 tons was imported mainly from 
Trinidad, which found its way into pavements. Prior to this, rela- 
tively small quantities of Trinidad was used, whereas European 
rock asphalts were imported for this purpose. In 1892 Trinidad 
asphalt had displaced most of the European products, and in that 
same year Bermudez asphalt made its appearance and gradually 
increased until 1919, when its tonnage approximated that of Trini- 
dad asphalt. 



V PRODUCTION OF PETROLEUM ASPHALTS 99 

The petroleum first known in the United States was derived 
from the Pennsylvania, Ohio and Indiana fields. This was of the 
paraffin type, and when distilled it left a viscous residue, more or 
less asphaltic in character, which was used principally to flux the 
harder native asphalts. This flux could not be distilled to a solid 
without decomposition and the formation of coke. In 1894 Byerley 
was granted a patent for converting these fluxes into semi-solid resi- 
dues by blowing air through them at high temperatures, thus per- 
mitting them to be used without admixture for most purposes, 
although they never met with much favor in the paving industry. 
Upon the discovery of petroleum in California it was possible to 
obtain semi-solid to solid residual asphalts, closely resembling the 
native asphalts, and suitable for use in the construction of pave- 
ments. In 1902, petroleum asphalts found their way on the market 
in appreciable quantities, about 20,000 tons having been produced 
in that year. By 1911, the tonnage of domestic petroleum asphalts 
exceeded the importations of Trinidad and Bermudez asphalts com- 
bined, and from that time on the production of petroleum asphalts 
rapidly increased. In 1913 large quantities of Mexican petroleum 
asphalt found their way into the United States and rapidly increased 
until in 1918 it exceeded the domestic production. Since 1922, 
asphalt produced from Venezuela petroleum has been produced in 
rapidly increasing quantities, followed in 1925 by asphalt derived 
from Colombian petroleum. 

At the present time petroleum asphalt far outranks other as- 
phalts in importance. In 1935 the total tonnage of petroleum 
asphalt was almost ten times that of native asphalts and related 
substances. Of the total production, approximately 60 per cent 
was reported as having been derived from domestic crude petro- 
leum, and 40 per cent from foreign crudes, including Venezuelan, 
Mexican and Colombian petroleum. 

Table XI shows the production of petroleum asphalts by va- 
rieties in the United States in 1935, divided into two classes solid 
and semi-solid products of less than 200 penetration and semi-solid 
and liquid products of more than 200 penetration. The major por- 
tion of the latter class is known by the general term "flux," which 
as the name implies, is used mainly as a blending material for the 
harder grades and also for blowing purposes. 



100 



ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES 



1 



co 'C 

< 



^ A 
M ^""^ 

a. 



I 

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3 

I 
I 



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H 

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Hi 



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f : ' : I .8 : . 

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WORLD PRODUCTION 



101 



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8 



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S 

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vofOVO t^OO 



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102 



ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES 



M 



I 

H 

I 



< 
!f 

5U 

3 I 

H B 



S 



I 



D 

14 

B 

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- 



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3 S3SS 



PRODUCTION IN THE UNITED STATES 



103 



TABLE X 

PRODUCTION BY VARIETIES IN THE UNITED STATES OF NATURAL ASPHALTS, ASPHALTITES, 
ASPHALTIC PYROBITUMENS AND PETROLEUM ASPHALT (1900-1935) 

(In Short Tons of 2000 Ib.) 



Year 


Natural 
Asphalts 


Asphaltites 


Asphaltic 
Pyro- 
bitumens 


Total 
Natural 
Asphalts, 
Asphalt- 
ites and 
Asphaltic 
Pyro- 
bitumens 


Petroleum Asphalts 


Gilsonite 


Grahamite 


Wurtzilite 


From 
Domestic 
Petro- 
leum 


From 
Foreign 
Petroleum 


Total Do- 
mestic and 
Foreign 


1900 
1901 
1902 
1903 
1904 
1905 
1906 
1907 
1908 
1909 










54,389 
63,134 
84,632 
55,o68 
64,167 
62,898 
73,o62 
85,913 
78,565 
99,o6i 






























20,826 
46,187 
44,405 
52,369 
64,997 
137,948 
119,817 

J 29,594 




20,826 
46,187 
44,405 
52,369 
64,997 
137,948 
119,817 

129,594 












59,639 
49,982 
58,163 
64,240 
57,296 
66,278 


2,978 
10,916 

12,447 
20,285 

18,533 
28,669 


1,000 
1,500 

I)9 H 

966 
2,286 
3,894 


550 
500 
500 
422 
450 

220 
















1910 
1911 
1912 

1913 
1914 
1915 
1916 
1917 
1918 
1919 


70,061 
51,228 
55,236 
57,549 
51,071 
44,329 
63,172 

4i,9i9 
25,346 
53,589 


25,432(*) 
30,236 
31,478 
28,000(0) 
1 8,548(0) 
19,909(0) 
24,5H(*) 
33,549(*) 
30,848 
29,192(0) 


4,000 (a) 
5,000 
7,700 (a) 
6,500 (a) 
9,669 
10,863 

8,431 
4,618 

3,803 W 

5,ooo (a) 


400 (a) 
610 
750 (a) 
700(0) 
600 (0) 
650 (0) 
2,360 (0) 
1,51 8 (ac) 

37 W 

5oo (0) 


98,893 
87,074 
95,166 
92,604 
79,888 
75,751 
98,477 
81,604 
60,034 
88,281 


161,187 

277,192 

354,344 
436,586 
360,683 
664,503 
688,334 
701,809 
604,723 
614,692 




161,187 
277,192 
354,344 
551,023 
674,470 
1,052,821 
1,260,721 
1,347,422 
1,202,420 
1,289,568 






i M,437 
313,787 
388,318 

572,387 
645,613 
597,697 
674,876 


1920 
1921 
1922 
1923 
1924 
1925 
1926 
1927 
1928 
1929 


132,353 
284,037 
298,047 
365,601 

525,831 
545,o6o 
672,750 
796,100 
760,497 
748,550 


56,204 
10,066 
29,693 
34,425 
35,907 
39,520 
42,190 
42,580 
47,023 
54,987 


9,940 (b) 
2,004 
41 




198,497 
296,412 
327,792 
400,236 
562,367 
584,850 
715,180 
839,040 
807,860 
804,027 


700,496 
624,220 
805,145 
995,654 
,158,456 
,206,700 
,245,160 
,525,420 
,930,536 
2,332,973 


1,045,779 
908,093 
1,242,163 
1,378,722 
1,920,915 
1,971,670 
2,213,310 
2,426,030 
2,298,848 
2,355,498 


1,746,275 

1,532,313 
2,047,308 
2,374,376 
3,079,371 
3,178,370 
3,458,470 
3,951,450 
4,229,384 
4,688,471 


305 
II 
210 (e) 

569 w 

270 
240 

360 Or) 

340 tt) 
490 (l) 


60 












1930 

1931 
1932 

1933 
1934 
1935 


664,871 
470,491 

3H,039 
285,070 

410,453 
3H,i09 


37,684 
32,763 
25,955 
28,029 

30,355 
33,227 




222 

129 

2 I 
36 

ft 


702,777 

503,383 
340,019 

313,135 
440,808 

347,336 


1,403,552 

1,274,744 

i," 5,547 
1,237,386 
1,444,846 
1,801,778 


1,824,089 
1,700,946 
1,359,372 
1,218,665 
1,395,650 
1,485,225 


3,227,641 

2,975,690 
2,47^,919 
2,456,051 
2,840,496 
3,287,003 















(a) Estimated. 

(b) Including wurtzilite. 

(c) Including 18 tons ozokerite. 
(<f) Including 37 tons ozokerite. 
(c) Including 10 tons ozokerite. 



(/) Including 300 tons ozokerite, 
(f ) Including 80 tons ozokerite. 
(k) Including 150 tons ozokerite, 
(i ) Including 290 tons ozokerite. 



104 



ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES 



TABLE XI 

ASPHALT AND ASPHALTIC MATERIAL (EXCLUSIVE OF ROAD OIL) SOLD AT PETROLEUM 
REFINERIES IN THE UNITED STATES, IN 1935, BY VARIETIES 

[Value f. o. b. refinery] 





From Domestic 
Petroleum 


From Foreign 
Petroleum 


Total 


Short 
Tons 


Value 


Short 
Tons 


Value 


Short 
Tons 


Value 


Solid and semisolid products of less 
than 200 penetration: * 
Asphalt for: 
Paving 


4i9,77i 
303,234 
83,294 
3,i87 
37,674 
192 

6,212 
6,856 

47,749 


13,994,713 
3,170,647 
917,623 
40,663 
416,870 
1,718 
"3,3" 
75,9H 
500,746 


457,695 
328,138 
65,821 
",944 
3,271 
2,310 
1,728 
7,814 
56,836 


$4,805,877 
3,585,501 
703,7" 
136,081 
39,305 
25,393 
16,963 
85,016 
639,325 


877,466 
631,372 
i49,"5 
15,131 
40,945 
2,502 
7,940 
14,670 
104,585 


$8,800,590 
6,756,148 
1,621,334 
176,744 
456,175 
27,111 
130,274 
160,930 
1,140,071 


Roofing 


Waterproofing 


Blending with rubber 


Briquetting 


Mastic and mastic cake 


Pipe coatings 


Molding compounds 


Miscellaneous uses 


Total 


908,169 

67,393 
225.I9S 
3,736 


$9,232,205 


935,557 

45,673 
54,649 
24,074 
32 
329,899 
17,449 
8,528 
17,624 


$10,037,172 


1,843,726 


$19,269,377 


Semisolid and liquid products of 
more than 200 penetration: * 
Flux for 
Paving \ 


$581,032 
1,540,995 
58,480 


$432,539 
616,485 
299,767 
320 
3,481,445 
119,861 

83,321 
142,605 


113,066 
279,844 
27,810 
32 
707,953 
39,861 
20,744 
109,566 


$1,013,57! 
2,157,480 
358,247 
320 
7,409,279 
359,650 
245,941 
540,813 


Roofing 


Waterproofing 


Mastic 


Cut-back asphalts 


378,054 
22,412 
12,216 
9i,942 


3,927,834 
239,789 
162,620 
398,208 


Emulsified asphalts and fluxes 


Paints, enamels, japans, and lacquers 
Other liquid products 

Total 


800,948 


$6,908,958 


497,928 


$5,176,343 


1,298,876 


$12,085,301 


Grand total, 1935 


i,709,H7 
1,353,639 


$16,141,163 
$13,973,765 


1,433,485 
1,373,602 


$15,213,515 
$15,921,674 


3,142,60^ 
2,727,241 


$31,354,678 
$29,895,439 


Total, 1934 





* DEFINITIONS 

Paving asphalt.*- Refined asphalt and asphaltic cement, fluxed and unfluxed, produced for direct use in the con- 
struction of sheet asphalt, asphaltic concrete, asphalt macadam, and asphalt block pavements, and also for use 
as joint filler, in brick, block, and monolithic pavements. 

Roofing a^>Aofc. Asphalt and asphaltic cement used in saturating, coating, and cementing felt or other fabric 
in the manufacture of asphalt shingles. 

Waterproofing asfhalt. Asphalt and asphaltic cement used to waterproof and dampproof tunnels, foundations of 
buildings, retaining walls, bridges, culverts, etc., and for constructing built-up roofs, 

Briquetting asphalt, Asphalt and asphaltic cement used to bind coal dust or coke breeze into briquets. 

Mastic and mastic cake. Asphalt and asphaltic cement for laying foot pavements and floors, waterproofing bridges, 
lining reservoirs and tanks, capable of being poured and smoothed by hand troweling. 

Pipe coatings. Asphalt and asphaltic cement used to protect metal pipes from corrosion. 

Molding compounds. -AsphsAte used in the preparation of molded composition, such as battery boxes, electrical 
fittings, push buttons, knobs, handles, etc. 

Miscellaneous uses. Asphalt and asphaltic cement used as dips, and in the manufacture of acid-resisting com- 
pounds, putty, saturated building paper, fiber board and floor coverings, and not included in the preceding 
definitions. 

F/w*. Liquid asphaltic material used in softening native asphalt or solid petroleum asphalt for paving, roofing, 
waterproofing, and other purposes. 

Cut-back asphalts. Asphalts softened or liquefied by mixing them with petroleum distillates. 

Emulsified asphalt and ftuxes.~- Asphalts and fluxes emulsified with water for cold-patching, road laying, and 
other purposes. 

Other liquid Products. ^?etTo\e\w asphalt, exclusive of fuel oil used for heating purposes, not included in the pre- 
ceding definitions, 



PRODUCTION OF ROAD OIL IN THE UNITED STATES 



105 



ROAD OIL SOLD BY PETROLEUM REFINERIES IN THE UNITED STATES, 1934-35, 

BY DISTRICTS 



District 


I 


934 


19 


35 




Barrels 


Value 


Barrels 


Value 


_, 


938,053 


$1,392,665 


1,001,845 


$1,614,179 




88,195 


186,298 


34,035 


64,437 




1,984,414 


2,390,175 


1,957,569 


2,439,100 


Oklahoma-Kansas-Missouri 


942,072 


1,071,260 


597,450 


547,789 


Texas: 
Gulf coast * 


204,888 


$274,188 


99,969 


$153,069 


Rest of State 


79,969 


79,963 


22,772 


35,775 


Total Texas 


284,857 


$354,iSi 


122,741 


$188,844 


Louisiana- Arkansas : 


52,464 


$ 9S,o89 


68,203 


$103,334 




157,992 


158,104 


384,769 


357,745 












Total Louisiana and Arkansas 


210,456 


$253,193 


452,972 


$461,079 




1,023,434 


$1,431,920 


644,485 


$1,032,907 


California 


2,231,272 


3,662,336 


1,987,835 


2,194,621 


Grand total 


7,702,753 


$10,741,998 


6,798,932 


$8,542,956 













106 



ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES 



PRODUCTION OF TARS AND PITCHES 

Tars Derived from Coal. By far the most important source of 
tar produced in the United States is derived from bituminous coal. 
The following represents the production in United States gallons : 2 



TABLE XII 





Gas Works 
(Horizontal, Vertical 
and Inclined) 


Coke Ovens 
(All Types) 


Water and 
Oil Gas 


1904 


42 million 


28 million 




9 million 


1908 


58 


43 




9 


1912 


4i 


94 




34 


1916 


50 


1 80 




55 


1918 


53 


263 




IOI 


1919 


53 


289 




105 


1920 


5i 


361 




116 


1921 


50 


^53 




109 


1922 


48 


328 




104 


1923 


48 


441 






1924 


48 


422 




108 


1925 


49 


480 






1926 


50 


529 




105 


1927 


51 


547 






1928 


5* 


632 




no 


1929 


47 


681 




117 


1930 




602 






1931 




45i 






1932 


50 to 40 (est'd) 


304 




1 10 to 80 (est'd) 


1933 




363 






1934 




409 






1935 


40 (est'd) 


468 (est'd) 




85 (est'd) 



No statistics are available giving the production of the corre- 
sponding types of pitch. 

Tars and Pitches Derived from Wood. The following figures 
have been reported by the U. S. Department of Commerce : 8 





Wood Tar 
(gallons) 


Wood-tar Pitch 
(tons) 


ion 


5, <oo,ooo 




iqa< 


9,000,000 


13,500 


TQ27 


8,500,000 


10,000 


IQ2Q 


10,500,000 


4,500 









PRODUCTION OF MANUFACTURED PRODUCTS 



107 



Other Tars and Pitches. There are no published figures giving 
the annual production of other tars and pitches in the United States. 
The following estimates have been compiled by the author as a mere 
approximation of what he believes to be their present relative 
standing. 

Tons Annually 

Rosin pitch 20,000 to 30,000 

Fatty-acid pitch 15,000 to 20,000 

Blast-furnace tar and pitch 5,ooo to 10,000 

Bone tar and bone-tar pitch 2,000 to 5,000 

Shale and lignite tars and pitches 250 to 500 



MANUFACTURED PRODUCTS 

Bituminous Paving Materials. The total tonnage of all types 
of asphalt, including asphalt cements, fluxes, cut-back asphalts, emul- 
sified asphalts and liquid residual asphaltic products used for high- 
way purposes in the United States have been reported as follows : 4 

Year Tons 

1925 1,764,700 

1926 1,800,180 

1927 2,179,100 

19^8 2,487,642 

'9*9 , 2,655,989 

J 930 2,693,552 

I9JI 2,901,851 

J 932 2,838,344 

1933 2,500,110 

J 934 2,977,990 

1 935 3,225,000 

The mileage of improved roads completed and under construc- 
tion as of January ist of the current year has been estimated to be 
as follows : 5 



/ 


1935 
Miles 


1936 

Miles 


1937 

Miles 


Sand-clay treated 


A O7O 


7CO2 


c 60 


Gravel treated 


T-jW" 

22 8ol 


OVA 
0*7 72 C 


ji uw j 

A 7 IQA 


Macadam treated 


*-*,yj 

11 66d. 


* /,/^J 
2A 6l C 


^J, 1 ^ 
17 7C6 


Low-cost bituminous mixture 


) * y j ^'*r 
11.I2O 


*4, U J3 
on 8*72 


* hi O v 

AC fff 


Bituminous macadam 


I6.CQ7 


jy," /* 
16,466 


*TJ9JJJ 

i6.c<< 


Bituminous concrete 


IQ.7I7 


II C72 


ii <8^ 




* w > / * / 


1 *O /* 


* *O W > 



108 



ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES 



Bituminous Roofing Products. Table XIII compiled from sta- 
tistics furnished by the Asphalt Shingle and Roofing Institute, New 
York City, and the U. S. Department of Commerce, Washington, 
D. C, show the sales of asphalt roll-roofings and asphalt shingles 
in the United States from 1917 to 1936. 

TABLE XIII 
SHIPMENTS IN " SALES" SQUARES TOTAL INDUSTRY U. S. A. 



Year 


Smooth-roll 
Roofings 


Slate-roll 
Roofings 


Strip 
Shingles 


Individual 
Shingles 


Total 
All Types 


1917 


21,252,000 


4,134,000 


1,266,600 


1,625,000 


28,277,000 


1918 


19,250,000 


4,312,000 


1,017,000 


1,149,000 


25,728,000 


1919 


16,930,000 


6,428,000 


2,311,600 


2,183,000 


27,952,600 


1926 


I7,579,ooo 


6,624,000 


2,253,900 


1,866,000 


28,322,000 


1921 


13,992,000 


7,670,000 


2,865,230 


1,632,000 


26,159,230 


1922 


14,604,000 


9,252,000 


4,243,630 


2,395,ooo 


30,494,630 


1923 


12,558,000 


9,847,000 


5,602,150 


2,492,000 


30,499,150 


19214. 


11,951,450 


10,608,100 


6,707,950 


3,103,000 


32,570,506 


1925 


11,990,709 


10,529,521 


7,803,202 


3,406,975 


33,730,4H 


1926 


13,502,977 


11,061,229 


8,529,382 


3,209,728 


36,303,316 


1927 


14,783,909 


10,798,454 


9,810,918 


2,582,031 


37,975,312 


1928 


16,074,654 


9,608,380 


9,002,297 


1,854,393 


36,539,724 


1929 


17,896,549 


9,989,787 


9,959,382 


2,015,781 


39,861,499 


1930 


I2,359,4H 


7,147,670 


6,820,775 


1,546,238 


27,874,097 


i93i 


10,794,478 


5,563,338 


4,887,134 


i,3i9,752 


22,564,702 


1932 


",996,723 


5,493,513 


4ii43ii33 


1,130,522 


22,763,891 


1933 


13,837,632 


5,684,905 


4,223,069 


991,547 


24,737,153 


1934 


12,837,702 


5,489,467 


4,422,486 


1,255,346 


24,005,001 


*935 


12,485,950 


6,426,369 


5,350,006 


1,787,826 


26,050,151 


1936 


15,251,646 


8,005,678 


6,851,860 


2,118,724 


32,227,908 



PRODUCTION OF MANUFACTURED PRODUCTS 



109 



The statistics in Table XIV have been compiled by the U. S. 
Department of Commerce, Washington, D. C. : 6 

TABLE XIV 
PRODUCTS, BY KIND, QUANTITY AND VALUE, 1929, 1931 AND 1935 



Kind 


1935 


1931 


1929 


Roofing, built-up and roll; asphalt shingles; roof coatings 
other than paint, all products 


$76,172,740 


$58,962,919 


$ J 03, 506,090 


Roofing 


70,589,616 


4945335 2 




Other products (not normally belonging to the industry) . . 
Receipts for contract and custom work 


5,517,081 
66,043 


9,509,567 


8,914,512 


Roofing, built-up and roll, asphalt shingles, and roof coat- 
ings other than paint, made as secondary products in 
other industries 


3,434,376 


6,143,744 




Asphalt roll roofing: 
Total roofing squares 


22,331,481 


17 I ?2 I \ 143 




Total value 


$24,768,468 


$20,272,517 


$36,109,653 


Smooth-surfaced : 
Roofing squares 


14,373,813 


II 659 193 




Value 


$13,710,544 


$11 213,050 




Grit-surfaced: 
Roofing squares 


7,957,668 






Value 


$11,057,924 


<tg' O cg' 467 


? ' Z 2 


Asphalt shingles: 
Total roofing aquares 


7,731,034 


655852 4 




Total value 


$26,801,952 


$22,566,749 


$42,291,343 


Strip: 
Roofing squares 


6,048,383 


S2o6 2 ?Q 




Value 


$21,897,294 


$18 328 528 


9,692,774 


Individual : 
Roofing squares 


1,682,651 


I 352 265 


33,707,3 4 


Value 


$4,904,658 


&A 238 221 


88 


Saturated felt: 
Total tons 


298,219 


143. CT2 


3, 5 


Total value 


$8,042,840 


$6,025,401 


2O5j5 2 5 
$9,803,629 


Asphalt-saturated felt: 
Tons 


271,241 


IIO 727 




Value 


$6,237,267 


$4 68< 83^ 


A/- * S 


Tar-saturated felt: 
Tons 


26,978 


32 785 


f& A(\C\ 


Value 


$1,805,573 


$i 339 566 


00,499 


Waterproofing fabrics, value 


$400,417 


(a) 


v3 7 * 


Roof-coatings and cements, total value 


NP*frV/v,,<t / 

$6,374,359 


$4,298,946 


$6,311,449 


Asphalt roof cement (solid) : 
Tons 


106,790 


16 630 




Value 


$1,420,651 


$333 7 CO 


eo 


Coal-tar roofing pitch: 
Tons 




1 




Value 


$808,808 


I (&) 


(a) 


Fibrous plastic roof-cement: 


31 460 O42 


29,488,86l 




Value 


$1,176,998 


$1,347,599 


$2 336 III 


Fibrous liquid roof-coating: 
Gallons . . 


4,88l,023 


4,979,oi3 


4 O4I ^63 


Value 


$1,928,595 


$2,040,783 


$2 II 1 ? *!78 


Nonfibrous liquid roof-coating: 




1,420,622 


I O3I 260 


Value 


$040.217 


$1-76.814 


$1 OI7 34O 


Other roofing materials value 


S6.383. 41 7 


$2.433 483 


$6 168 787 


Asphalt brick siding: 


m_7O 


1 t \ 




Value 


"^ 
$1,243,539 


} (a) 


(a) 











(a) No data. 



110 



ANNUAL PRODUCTION OF BITUMINOUS SUBSTANCES 



TABLE XIV Continued 
PRODUCTS, BY KIND, QUANTITY AND VALUE, 1929, 1931, 1933 AND 1935 



Kind 


Year 


Quantity 


Value 




1935 


Squares 
1,171,095 


$5,234,727 




J933 
1931 
1929 

J 93S 


408,256 
565,997 
894,164 
890,854 


1,826,279 
3,266,054 
5,277,308 

C67.QII 


Asphalt roll roofing (c) 


1935 


22,331,481 


24,768,468 


Asphalt shingles (d) 


1933 
I93i 
1929 

1935 


12,333,342 
17,525,143 
28,437,076 

7,731,034 


12,763,519 
20,272,517 
36,109,653 

26,801,952 


Asphalt and tar saturated felt (d) 


1933 
i93i 
1929 

1935 


4,008,811 

6 >558,524 
11,676,636 
Tons (2000 Ibs.) 
298,219 


11,994,618 

22,566,749 
42,291,343 

$8,042,840 


Clay roofing tile (e) 


1933 
i93i 
1929 

1935 


75,623 
143,5" 

205,525 
Squares 
253,951 


2,778,308 

6,025,401 
9,803,629 

1,145,434 


Concrete roofing tile (f) 


1933 
i93i 
1929 

1935 


103,257 
285,253 

370,771 
Tons (2000 Ibs.) 
(g) 


810,647 

3,125,175 
3,943,847 

(g) 


Steel sheets, corrugated and crimped (h): 
Galvanized 


1933 
i93i 
1929 

IO^S 


11,971 
31,860 
137,052 
Tons (2240 Ibs.) 

e8. S74. 


338,809 
862,197 
2,869,092 

27 611 766 


Not galvanized 


1933 
1931 
1929 
1935 


243,542 
262,307 
306,423 
6,506 


15,922,000 
18,381,000 
26,363,000 

ex.2 O8l 


Wood shingles (*) 


1933 
1931 
1929 

TQ7 e 


2,338 
3,O26 
5,285 

Thousands 
3^26 ^18 


140,000 
175,000 
380,000 

10 ^^8 ^60 


Asphalt roof-cement (solid) (c) 


1933 
1931 
1929 

IQ*< 


2,929,800 
2,713,972 
6,110,672 
Tons (2000 Ibs.) 
106.700 


6,958,275 
4,993,708 
18,026,482 

I A2O 6?I 


Fibrous plastic roof-cement (c) 


1933 
1931 
1929 

1935 


io,373 
16,630 
35,i6i 
Pounds 

sj 4.60.04.2 


255,471 

333,750 
842,420 

1.176.008 


Fibrous liquid roof-coating (c) 


1933 
1931 
1929 

IO"*{ 


13,968,939 
29,488,861 

52,753,395 

Gallons 
A 881 02 * 


**/w,yyo 
661,044 

1,347,599 

2,336,111 

i 028 <co< 


Nonfibrous liquid roof-coating (c) 


1933 
I93i 
1929 

1935 


3,003,734 
4,979,oi3 
4,941,563 

3,424,671 


1,011,323 
2,040,783 
2,115*578 

O4.O.2I7 




1933 
1931 
1929 


799,844 
1,420,622 
1,931,269 


183,729 
576,814 
1,017,340 



(a) Made in the Asbestos Products industry, (b) No figures available for earlier years, (c) Made principally 
in the Roofing Materials industry, (d) Made in the Roofing Materials industry, (c) Made in the Clay Products 
industry, (f) Made in the Concrete Products industry, (g) Not yet available. (A) Made principally in the 
Steel Works and Rolling Mills industry, (h) Made in the Lumber and Timber Products industry. 



PRODUCTION OF MANUFACTURED PRODUCTS 



111 



Asphalted Felt-base Floor Coverings. The data in Table XV 
have been compiled by the U. S. Department of Commerce, Wash- 
ington, D. C. : 7 

TABLE XV 

ASPHALTED FELT-BASE FLOOR COVERING PRODUCTS, BY KIND, QUANTITY AND VALUE 





1935 


1931 


I 9 2 9 


Total square yards 


128,041,256 


87,575,642 


117 060 72 C 


Total value 


t3 I >*S9>943 


$21,628,899 


$36,943,057 


Piece goods: 
Total square yards 


66,610,504 


48,401,10 


57.O26 l6o 


Total value 


$ 1 4,46 1, 266 


$11,341,150 


$I4,68O,OI7 


12/4 an d wider: 
Total square yards 


2O.7O4.420 


5.2IO.5QO 


6 060 cci 


Total value 


$4,412,620 


$1,227,276 


u >y v - n -'o$j 
$2,032,865 


Made on less than .050-! nch-gauge felt: 
Square yards 


1 2. 11O.OO 5 


2.444.084 


2 1 60 III 


Value 


$2,448,780 


$5O2.Q1O 


^,iuy,i 1 1 
$ Coo 821 


Made on .O5o-inch-gauge felt or thicker: 
Square yards.' 


8,374,424 


2,76C,6o6 


f jvy^ojii. 
4.7QI.442 


Value 


$I.Q6l.8lI 


$724.146 


$1 C21 OA.A. 


8/4: 
Total square yards 


4.1.766.061 


l8,886,OQ6 


' A >J < *J> W T^ 

44 4OO 278 


Total value 


19,53!, 5^4 


$9,110,304 


$11,621,078 


Made on less than .050-1 nch-gauge felt: 
Square yards 


24,644,42 5 


22,824,070 


2 1.8OO.2O1 


Value 


$5,124,065 


$4.<84.784 


$C~d.7O 6l2 


Made on .O5o-i nch-gauge felt or thicker: 
Square yards 


10,121,618 


l6,o6l,II7 


fjrr/^yJjA 
2O COO 08 C 


Value 


$4.4O7.45Q 


$4,525,520 


' t '^'9jy^ J )y Q j 
$6 I CO*AA6 


Narrower than 8/4: 
Total square yards 


2,l6o,IO2 


4.1O4.47I 


f>V/,l^W^J.^.V 

C 66 C C2O 


Total value 


$517,122 


$1,003,570 


$1,026,074 


Made on less than .O5o-inch-gauge felt: 
Square yards 


1,224,071 


1,658,007 


C.4Q4 6 CO 


Value 


$285.804 


$807 1 06 


$06 c 87^1 


Made on .050-! nch-gauge felt or thicker: 
Square yards 


Ol6 O2Q 


645 474 


ry u j>/4 
I7O 87O 


Value 


$231,228 


4 1 06 464 


1 /U,O /U 

26o 2OO 


Rugs: 
Total square yards 


6l,4l2,662 


10. 1 74 48C 


J>UV)4VAJ 

60 QAl l6c 


Total value 


$16,798,677 


$10,287,749 


uw >y4J,J u J 
$22,263,040 


Made on less than .050-1 nch-gauge felt: 
Square yards 


11 741.412 


2 C.148 .060 


27 2QO.1O1 


Value 


28.142.774 


$5,76o,542 


^/j^^y >o w j 
$7.758,888 


Made on .050-1 nch-gauge felt or thicker: 
Square yards . 


27.671 .2 CO 


11.826,425 


11.644.062 


Value 


$8,455,QO1 


$4.527.207 


$14,504.152 











PART II 

SEMI-SOLID AND SOLID BITUMENS AND 
PYROBITUMENS 



CHAPTER VI 
METHODS OF MINING, TRANSPORTING AND REFINING 

MINING METHODS 

Three general methods are followed in mining semi-solid and 
solid bituminous substances, depending upon the nature of the 
deposit. 

Open-cut Quarrying. Deposits at or near the surface are mined 
by simple quarrying methods. If exposed on hillsides, the rock 
asphalt is blasted loose and loaded on railroad cars by means of 
steam shovels or buckets running on a cable way. Deposits located 
beneath flat terrain are mined by open cuts, after first removing the 
overburden, as illustrated in Figs. 46 and 49. The asphalt may be 
hauled from the cut by means of buckets suspended from an over- 
head cable way, or by dump-cars pulled up inclined tracks on cables. 

Tunnelling. Veins situated a distance beneath the surface are 
mined by tunnelling methods, which also adapt themselves to 
handling veins filling hillside faults or fissures. Typical tunnelling 
methods are illustrated in Figs. 64 and 69. Horizontal veins may 
be handled by pit-and-stall methods if the overlying stratum is solid 
enough to resist caving in, otherwise the roof and possibly also the 
sides of the tunnel must be timbered, which of course adds to the 
cost of mining, Asphaltites are generally mined in this manner. 

Special Methods. Asphalts deposits occurring in the form of 
so-called lakes, as for example at Trinidad and Bermudez, are mined 
by comparatively crude methods, involving the use of the pick and 

shovel, as illustrated in Figs. 43 and 59. The asphalt is dumped 

112 



VI 



METHODS OF SHIPMENT AND TRANSPORTATION 



H3 



by hand in small cars on a movable track, whence it is transported 
to the main railroad line or to steamers, if near the seacoast. 

METHODS OF SHIPMENT AND TRANSPORTATION 

Hard rock asphalts and asphaltites are shipped in fragments, 
either in bulk the same as coal, or if the material is of sufficient 
intrinsic value to warrant the expense, it may be shipped in sacks 
weighing 150 to 200 Ib. each. Where intended for constructing 
asphalt mastic pavements or floors, the rock asphalt is cast in the 













Courtesy Atlantic Refining Co. 
FIG. 35. Tank-cars Used for Transporting Asphalt. 

form of flat cakes weighing between 50 and 75 Ib. for the con- 
venience of handling. 

If the asphalt is comparatively free from mineral matter, and 
this applies also to petroleum asphalt, it may be shipped in six 
types of containers, as follows: 1 

(i) In tank cars having capacities of 6500, 8000 and 10,000 
gal. as illustrated in Fig. 35. These are provided with steam coils 
for remelting the asphalt upon arrival at destination, and are prefer- 
ably insulated, so that they may be transported in a melted state 
with the minimum loss of heat. 



114 METHODS OF MINING, TRANSPORTING AND REFINING VI 

(2) Tank trucks equipped with heating flues in which a fire is 
maintained by an oil burner during transit. These are generally 
used for transporting asphalts for road and paving purposes. 

(3) Light metal drums with a metal top having a 6-in. hole in 
the center for convenience in filling. These usually weigh 475 to 
525 lb., holding 50 to 55 gal. 

(4) Wooden barrels of about the same capacity as stated in 
(3). These are generally used for transporting liquid to semi- 
liquid materials, and are filled at the lowest temperature to prevent 
excessive contraction taking place upon cooling. 

(5) Fiber barrels and other containers, 2 which should be filled 
at temperatures lower than 300 F. It is recommended that these 
be lined with clay to prevent adhesion of the asphalt 3 and thus 
facilitate stripping off the container when used. Other products 
recommended for this purpose include alkaline sludge obtained as 
a by-product in refining petroleum products, 4 glycerol foots, 5 an 
aqueous solution of oxalic acid or sodium-hydrogen phosphate con- 
taining glycerol, 6 etc, 

(6) Molds for the shipment of high melting-point asphalts, 
which may be of the same form as barrels. These are filled in the 
same manner as drums, and when the asphalt has cooled, they are 
opened up and the block removed and shipped as such. 7 The 
cakes may also be coated with a high fusing-point asphalt or as- 
phaltite (e.g., gilsonite). 8 This method eliminates the payment of 
freight on the container, but only adapts itself to materials which 
are sufficiently rigid and tough to withstand shipment. 



METHODS OF REFINING 

Dehydration. Most native asphalts contain more or less mois- 
ture, which may be present either accidentally as hydroscopic 
moisture, or in the form of an emulsion. Trinidad asphalt is an 
'example of the latter, in which about 29 per cent of water is emul- 
sified with the asphalt and clay. 

Before the asphalt can be used commercially, this water or 
moisture must be removed. The process by which this is accom- 
plished is known as "dehydration." The expulsion of water is 
brought about by heating the asphalt in a suitable open container 
constructed of iron or steel, which is built in two types, viz. : 

(1) Semi-cylindrical. 

(2) Rectangular. 



METHODS OF REFINING 



115 



In either case the top is left open so that the water may be 
expelled readily. In modern plants, the heating tanks are built to 
contain between 10 and 30 tons of the crude asphalt. 

The heating is effected by various means: 

( i ) By direct fire heat, in the form of a combustion chamber 
underneath the tank, enclosed in fire bricks. Three kinds of fuel are 
used for this purpose, depending upon which is most readily ob- 
tained in the locality where the asphalt is to be refined; namely, 
coal or coke, oil, or gas. Coal is burnt on a grate ; oil is usually 




FIG. 36. Showing Arrangement of Refining Stills for Natural Asphalt. 

sprayed into the combustion chamber by compressed air or steam ; 
and natural or producer gas is introduced through a suitable type 
of burner. 9 In any case, the best practice consists in protecting 
the bottom of the melting-tank by a fire-brick arch work, so that 
the hot gases are compelled to circulate back and forth. 10 This 
subjects the bottom of the tank to a more uniform temperature, and 
tends to prolong its life. At the same time, it economizes fuel by 
more thoroughly extracting the heat from the hat gases, due to the 
increased area of contact with the bottom of the tank. Some recom- 
mend the use of a perforated brick arch to distribute the hot gases 
uniformly and prevent the bottom of the tank from being^ over- 
heated locally. Fire melting-tanks are usually semi-cylindrical in 
form, although sometimes they may be rectangular at the top, with 
a semi-cylindrical bottom. 



116 METHODS OF MINING, TRANSPORTING AND REFINING VI 

(2) By means of steam. In this case the heating is effected by 
coils of steam pipes contained in the tank. One and one-quarter to 
i^-in. pipes are generally used for this purpose. According to the 
best practice, these are bent in coils composed of a continuous 
length of pipe without unions or joints, as illustrated in Fig. 36. X1 
Another method consists in using cast-iron headers with straight 
lengths of 1^4 or i ^-in. pipes fastened in between. Steam is used 
at pressures between 125 and 150 Ib. This will raise the tempera- 
ture of the asphalt to 300 or 400 F. Steam has the advantage 
over fire heat in not coking the asphalt, which would tend to insu- 
late the bottom, induce local overheating, and burn out the tank in 
a comparatively short time. 




Courtesy of Parks Cramer Co. 
p IG . 37 . Hot Oil Circulation Method for Heating Asphalts. 

(3) Electrical Immersion Heaters. 12 Electric heating units 
contained in a series of ic-in. pipes (closed at both ends) are placed 
at the bottom of the tank. Each unit has a capacity of 54 k.W. 
and serves to heat the air in the pipe, which in turn imparts its 
heat to the surrounding asphalt. This same device has been uti- 
lized for saturating roofing felt, in which case the asphalt is main- 
tained at 440 F. while the felt is being treated at the rate of I ton 
per hour, which corresponds to a heat consumption of about 10,000 
B.t.u. per hour per ton of asphalt. 

(4) By contact with molten metals or alloys. Another pro- 
cedure consists in promoting the rapid heating of the asphalt by a 
bath of molten lead, tin, zinc, or various alloys of low fusing- 
point. 18 



VI METHODS OF REFINING 117 

(5 ) By hot oil circulation. This is accomplished by circulating 
heated mineral oil of a high flash-point through a closed system of 
pipes, including a heating coil in the asphalt melting tank and a 
second coil located in a furnace situated a short distance away from 
the tank. The second coil is heated by means of an oil or gas 
burner, which by means of a thermostatic control serves to heat the 
oil to a predetermined temperature, usually at 550 to 600 F. Fig. 
37 illustrates the oil heater and circulating pump. 14 

(6) By means of diphenyl vapor. Dbhenyl is a white solid, 
melting at 156.6 F. and boiling at 491.5 F. under a pressure of I 
atmosphere. At 491.5 F. it has a pressure of 14.7 Ib. absolute 
and at 600 F. it has a pressure of only 47 Ib. In view of these 
properties, its use has been promoted for heating asphalts, etc. 15 A 
mixture of diphenyl and diphenyl oxide has also been proposed, 16 
likewise naphthalene. 

(7) By circulating the asphalt itself. 17 This is a modification of 
the preceding method, in which the mineral oil is replaced by the 
asphalt which is to be heated. In this case the heating coil in the 
asphalt melting tank is omitted, and the asphalt is pumped directly 
from the bottom of the tank through a heating coil in the outside 
furnace, and then back again into the melting tank. The heating 
coil is brought to the proper temperature (which may be controlled 
thermostatically) by oil or gas combustion. This procedure^ is 
simple and efficient, but adapts itself only to asphalts having a high 
flash-point and which are substantially free from mineral matter or 
other ingredients which will settle in the coils and induce carboniza- 
tion. The asphalt must also be free from water and capable of 
being heated rapidly without frothing. 

The time of heating can be reduced materially by agitating the 
asphalt mechanically, since the transfer of heat through a mass of 
asphalt is very slow. The agitation may be Accomplished: 

(a) By jets of dry steam which should be introduced after the 
temperature of the asphalt becomes sufficiently high to prevent con- 
densation, and thus avoid excessive foaming. 18 

(b) By jets of air. 

(c) By mechanical agitators. 

During the process of dehydration, the mass is apt to froth when 
the temperature is raised beyond the boiling-point of water. For 
this reason, it is well to build the tanks large enough to accommo- 
date the foam without danger of overflowing. Shallow tanks are 
preferable to deep tanks. 



118 METHODS OF MINING, TRANSPORTING AND REFINING VI 

Certain types of asphalt are most difficult to dehydrate, as they 
foam very badly. Numerous devices have been used to keep down 
the foam, the simplest and most successful consisting in directing a 
current of hot air against the surface of the asphalt while it is being 
melted. 

The use of steam accelerates the evaporation of the more vola- 
tile constituents in the asphalt, and is therefore apt to cause a 
greater shrinkage during the dehydration than when air or mechani- 
cal mixing is used. 19 On the other hand, air is apt to "oxidize" the 
asphalt and increase its fusing-point, especially if its use is con- 
tinued for long periods of time. 

Sometimes the asphalt is subjected to a process of partial distilla- 
tion in a closed retort to remove the volatile constituents and raise 
its fusing-point, which, 'however, is stopped before the formation of 
carbonaceous matter. 20 A modification consists in adding a propor- 
tion of vegetable oil during the refining process for the purpose of 
absorbing the sulfur derivatives loosely combined with the asphalt; 21 

Any impurities such as vegetable matter, chips of wood, etc., 
which rise to the surface when the asphalt is melted should be 
skimmed off. When the asphalt is thoroughly melted and the foam- 
ing ceases, the dehydration is complete. It is usually unnecessary to 
raise the temperature of the asphalt higher than 350 F. The de- 
hydrated asphalt may be discharged : 

1 i ) By a valve at the bottom of the tank, permitting the asphalt 
to flow out by gravity. 

(2) By a rotary pump which may either be steam-jacketed 22 
or surrounded by a steam coil in close contact with the pump, the 
entire installation being well insulated. The rotary pump is usually 
installed above the level of the asphalt, and the intake pipe extended 
almost to the bottom of the heating-tank. 

(3) By means of a pneumatic lift installed below the bottom of 
the tank. The asphalt is allowed to flow by gravity into the pneu- 
matic lift, which, by a suitable mechanism, automatically shuts off 
the flow when it is filled, and then admits compressed air, forcing 
the asphalt upward through the discharge pipe. The pneumatic lift 
may either be steam-jacketed or heated with a steam coil as de- 
scribed. 

(4) By means of an Archimede's screw, which serves to extrude 
asphalt compositions in the plastic state. 23 



VI 



METHODS OF REFINING 



119 



A device for discharging the melted asphalt into light metal 
drums, in which nine are filled simultaneously, is illustrated in 
Fig. 38. 

Asphalt may be pumped through pipe lines for distances of 500 
feet or more. To effect this it must be maintained in a melted 
state. This is accomplished by running a steam pipe of small 




Courtesy Atlantic Refining Co. 
FIG. 38. Discharging Melted Asphalt into Drums. 

diameter inside the pipe carrying the asphalt. 24 The outer pipe 

should be well insulated. 

Hard asphalts are first pulverized and then dried in air. 25 
Distillation. Attempts have also been made to utilize rock 

asphalts associated with a small percentage of bituminous matter, 

and which cannot be utilized for other purposes, by subjecting them 



120 METHODS OF MINING, TRANSPORTING AND REFINING VI 

to a process of destructive distillation 26 and recovering the volatile 
products, including the lubricating oil fraction, 27 which correspond 
closely with those obtained upon distilling pyrobituminous shales. 




FIG. 39. Jaw Crusher. 

However, the low market price of petroleum has been an obstacle 
to the success of such operations. 

Rock asphalts may be distilled to harden same for use in paving 




FIG. 40. Toothed-Roller Crusher. 



impositions. 28 If coarse or undesirable mineral aggregate is pres- 
mt, it may be screened to the desired mesh while in a melted state, 
ind electrically heated screens have been proposed for this purpose. 



20 



VI 



METHODS OF REFINING 



121 



Comminution. Natural rock asphalts and asphaltites may be 
comminuted 30 in three different types of apparatus, including jaw- 
crushers illustrated in Fig. 39, toothed rollers as illustrated in Fig. 







FIG. 4IA. Disintegrator (Showing Wheels Separated). 



40, and a disintegrator as illustrated in Figs. 41 (A) (showing the 
machine taken apart) and 41(6) (showing the machine assembled). 
After being crushed and ground, the product is screened to the re- 




FiG. 4iB. Disintegrator (Showing Machine Assembled). 

quired mesh, and finally heated in a revolving, fire-heated cylinder to 
expel the associated moisture, usually at a temperature of 260 to 
300 F. The asphalt content of the comminuted material can be 



122 METHODS OF MINING, TRANSPORTING AND REFINING VI 

adjusted by grinding together rock taken from the rich veins with 
material mined from the poorer strata. When used for paving 
purposes, the product is usually transported directly to the job 
while it is still hot. 31 

Sedimentation. This process is used to separate the water where 
it is present in substantial quantities, as well as any coarse particles 
or lumps of mineral matter. It can only be used successfully with 
asphalts or other forms of bitumen melting below the boiling-point 
of water (212 F.), and not carrying the water in an emulsified 
state. The asphalt is maintained at a temperature not exceeding 
200 F. by any of the devices described under "Dehydration," and 
allowed to undergo a process of sedimentation, whereby the en- 
trained water and coarse mineral matter settle to the bottom, leav- 
ing the purified asphalt on top. The latter is then carefully drawn 
off. 32 Steam heating is most satisfactory for this purpose. 

In some cases only a portion of the water separates by sedimen- 
tation, whereupon the process is supplemented by one of dehydra- 
tion. The sedimentation will remove most of the water and has 
the advantage of materially shortening the dehydration process. 
A combination of the two processes will thus prove more effective 
than the use of either one alone. 

Since water usually has a higher specific gravity than melted 
asphalt, it tends to settle to the bottom of the vessel containing it. 
This invariably proves to be the case with the softer forms of na- 
tive asphalt. 

Extraction. Two media have been used for this purpose, namely 
water and volatile solvents. As the methods are entirely different, 
they will be considered separately. 

Extraction by Means of Water. This method has been used 
with more or less success for extracting asphalt from asphaltic sands, 
sandstone and limestone. It is based on the principle that water 
has a higher specific gravity than the melted asphalt, and a lower 
gravity than the accompanying mineral matter, so that when boiled 
together, the melted asphalt will rise to the surface and the mineral 
constituents settle to the bottom. 33 Calcium chloride, 84 sodium car- 
bonate 85 and salt ae have been proposed to be added to the water 
to increase its gravity and thereby effect a more thorough separa- 



VI METHODS OF REFINING 123 



tion of the asphalt. Rock asphalts after weathering yield more 
difficultly to the water-separation process. 87 

To yield successfully to this method, the rock asphalt must pos- 
sess the following characteristics: 

1 i ) The asphalt present in the rock should have a fusing-point 
of not exceeding 90 F. (Test 150.) 

(2) The particles of mineral matter should be unconsolidated. 

3 C rr\t f f t ., 1 111 _ 1 ._ ,_ 



(3) The grains of mineral matter should be fairly coarse to 
enable them to settle rapidly. 

Experience has shown that when the fusing-point of the asphalt 
contained in the rock is higher than 90 F., boiling water will not 
effect a thorough separation. 

A specimen of asphaltic sand obtained near Woodford, Okla., 
carrying approximately 12 per cent of asphalt and 88 per cent of 
sand in the form of loose, rounded grains between 40- and 8o-mesh, 
separated fairly completely on boiling with water. The pure asphalt 
showed a fusing-point between 65 and 70 F. 

Another asphaltic sand obtained near Fort McMurray, in 
northern Alberta, carrying approximately 15 per cent of asphalt 
and 85 per cent of non-compact sand, between 40- and loo-mesh, 
likewise largely separated on boiling with water. The fusing-point 
of the pure asphalt was 50 F. 

The same was true with an asphaltic sand carrying 1 7 per cent 
of asphalt obtained from a deposit 46 miles northwest of Edmon- 
ton, and 12 miles north of Onoway. In this case the pure asphalt 
fused at 62 F. 

A Mexican asphaltic sand carrying 16 per cent of asphalt also 
separated completely on boiling with water, the fusing-point of the 
pure asphalt being 78 F. 

On the other hand, certain asphaltic sands obtained from various 
localities of Oklahoma, carrying between 10 and 15 per cent of 
asphalt, refused to separate on boiling with water. The fusing- 
points of the pure asphalts were found to be 113 F., 118 F., and 
127 F., respectively. The particles of the sand were substantially 
similar to the preceding, ranging between 40- and loo-mesh. 

Plants for the water-extraction of asphalt from rock asphalt 
have been in operation in Oklahoma (sand asphalt) ; Texas (as- 
phaltic limestone) ; Alberta, Canada (sand asphalt) ; Pechelbronn, 



124 



METHODS OF MINING, TRANSPORTING AND REFINING 



VI 



Alsace-Lorraine (asphaltic limestone); Seyssel and Bastennes, 
France (asphaltic limestone) ; San Valentino, Italy (asphaltic lime- 
stone) ; Tataros, Austria (asphaltic limestone) ; also in Russia 
(sand asphalt). 

A cross-sectional diagram of an apparatus which gives fairly 
successful results is shown in Fig. 42. The separated asphalt must 
be treated in accordance with the methods described under the 
heading "Dehydration/* to separate the water which is mechanically 
carried along with it If the process has been performed properly, 
the purified asphalt will not contain more than 5 to 7 per cent of 
mineral matter. The water-extraction process also is used for puri- 



Perforateef Metal Plat* 
TO allow Wafer to dram off 
separated Asphalt 



iStirring Dev 

\ Cham with diodes 
\to carry oft separated 
asphalt 



Pure Asphalt Floats on 
Surface o 




Vo/res to draw off'' 
Mtneral Matter ; 



Serrf/ngr Chamber for 
Mtneral Matter 



FIG. 43. Apparatus for Separating Soft Asphalt from Sand by Means of Water. 

fying ozokerite and to remove water-soluble constituents (e.g., salt) 
from certain native asphalts, and thereby improve their weather- 
resisting properties. 38 

A flotation process has been proposed, which consists in agitating 
the sand asphalt at 60 to 80 C. with a o.i per cent solution of a 
froth former, e.g., soda ash, alkaline soap, turkey-red oil, saponin, 
glue, etc.; the aqueous solution being then separated by decantation 
and the mineral matter removed by lixiviation. 80 The use of ben- 
tonite 40 alkali (e.g., NaOH or Na 2 CO 3 ), 41 sodium phosphate, 42 so- 
dium silicate, 48 sodium silicate in combination with calcium chloride 
or salt, 44 sulfonated mineral oils, 45 etc., have also been suggested 
for this purpose. 



VI METHODS OF REFINING 125 

Extraction or Precipitation with Solvents. Carbon disulfide, 
petroleum distillates and benzol have been used for this purpose. 
This method has not proven successful commercially, on account of 
its expense. Several plants have been constructed in the United 
States for extracting asphalts from asphaltic sands and sandstone. 
The Alcatraz Asphalt Co. of Alcatraz, Cal. (18961899), erected 
an elaborate plant for treating rock carrying 10 to 16 per cent of 
asphalt. The venture, however, proved a failure through losses in 
solvent (a light distillate of petroleum), which made the cost of 
treatment prohibitive. The loss was due in part to unavoidable 
evaporation during the extraction process, also ,to the impossibility 
of fully recovering the solvent from the extracted residue. 

Solvents may be used either to extract solid bituminous sub- 
stances (e.g., rock asphalts, sand asphalts, certain pitches, etc.), or 
to precipitate components from fluid bituminous substances (e.g., 
petroleum, tars, etc.) or solutions of solid bituminous substances in 
various menstra. The following classes of solvents have been pro- 
posed for these purposes : 46 

(a) Solvents derived from petroleum: 

Crude petroleum; 47 liquid ethane, pentane, propane or bu- 
tane; 48 light petroleum distillates (e.g., petroleum ether, gasoline, 
or petroleum naphtha) ; 49 kerosene; 50 heavy mineral oils; 51 etc. 

(b) Solvents derived from coal tar: 

Benzol; 52 toluol; 58 xylol (solvent naphtha); 54 heavy oils; 55 
naphthalene ; 56 tetrahydronaphthalene ( "tetralin" ) ; 57 nitroben- 
zene; 58 benzonitrile ; 59 phenol; 60 phenyl nitrile; 61 aniline; 62 pyri- 
dine or quinoline. 

(c) Solvents derived from wood: 

Turpentine; 63 methyl or ethyl alcohol; 64 higher alcohols (e.g., 
butyl, isobutyl, propyl, iso-propyl, amyl, fusel oils, benzyl, etc.) ; 65 
acetone ; 6e acetone oils ; 67 wood oils ; 68 furfural or methyl furfural 
("furfural process"); 69 glacial acetic acid; 70 methyl or ethyl ace- 
tate; 71 amyl acetate; crpton aldehyde ("Foster- Wheeler process"). 

(d) Sulfur derivatives: 

Liquid sulfur dioxide ("Edeleanu process"); 72 carbon disul- 
fide; 73 sulfo-derivatives of mineral oils and tars. 74 

(e) Sundry solvents: 

Ethyl ether ; 75 carbon tetrachloride, trichlorethylene, ethyl ene 
dichloride, or dichlor-djethyl ether ("chlorex process"); amine 
bases (e.g., iso-amyl amine, di-iso-propyl amine, di-iso-butyl amine, 
etc.). 76 



126 METHODS OF MINING, TRANSPORTING AND REFINING VI 

(f) Mixtures of solvents: 

Petroleum naphtha with amyl alcohol ; 77 pentane with butane, 
or propane with ethane; 7S propane with cresol ("Dusol process") ; 
benzol or toluol with alcohols; 79 benzol with acetone; 80 benzol 
with liquid sulfur dioxide ( u Edeleanu process"); propane with 
liquid sulfur dioxide; 81 ethyl alcohol with ethyl ether; methyl for- 
mate with benzol, carbon disulfide or carbon tetrochloride ; 82 phenol 
with a polyhydric alcohol ; 83 successively with alcohol, or acetone, 
petroleum naphtha, and finally with benzol or toluol. 84 

For the production of high-grade lubricating oils from heavy 
petroleum fractions, the use of liquid propane as a solvent (or 
more accurately, as "antisolvent") has become increasingly popu- 
lar. 85 The following constituents present in ordinary lubricating 
oil fractions must be eliminated, viz. : paraffin wax to obtain a low 
pour-point, asphalt because of its instability and excessive carbon- 
forming tendencies, the heavy ends of the lubricating oils because 
of their high carbon-forming tendencies, naphthenic compounds of 
olefinic or aromatic characteristics because of their low stability and- 
low viscosity index, and color bodies to render the lubricating oil 
more marketable. Refining with liquid propane makes available as 
by-products a whole series of high melting-point waxes, also petro- 
latums of extremely high quality, and new types of asphalt of excel- 
lent ductility and penetration relations. The same is true to a cer- 
tain extent with other light hydrocarbons, including liquid ethane, 
which dissolves much less oil than liquid propane and throws asphalt 
completely out of solution. A mixture of methane and propane 
behaves similarly to ethane. Liquid butane, on the other hand is 
too good a solvent to be effective in removing the asphalt. For 
the complete removal of wax, asphalt, heavy ends, naphthenic com- 
pounds and color bodies, liquid propane is generally more efficient 
than any other solvent known at present 

Propane gas, by simple compression and liquefaction, may be 
converted into a solvent having the unique properties (under proper 
conditions of temperature and pressure) of separating each of the 
foregoing undesirable constituents. It owes its versatility to the 
fact that its properties change rapidly over the particular tempera- 
ture range between 44 and +215 F. Over this range, it 
possesses the properties of a series of solvents, any one of which 
can be obtained by raising or lowering the temperature, or chang- 



VI METHODS OF REFINING 127 

ing the pressure, or by combining these two operations. Pure 
propane boils at 44 F. under i atmosphere pressure, exerts a 
pressure of 126 Ib. per sq. in. at 70 F., and has a critical pressure 
of 643 Ib. at 212.2 F. Over this range propane changes from a 
typical liquid to a fluid possessing substantially the properties of a 
gas. Between 70 and 44 F., its main uses are in connection 
with dewaxing. At temperatures above 70 F., it finds its use as a 
preferential precipitant. Thus, in the range of 100 to 140 F., 
asphalt is only slightly soluble in propane, whereas at these same 
temperatures both oil and wax dissolve completely. Between 100 
and 212 F. and at the vapor pressure of propane, instead of be- 
having as an ordinary liquid and dissolving more of any partially 
soluble substances as the temperature is raised, it actually dissolves 
less. The heavier and more naphthenic compounds are thrown out 
first, but as the properties of propane become increasingly those of 
gases, it dissolves less and less oil, until no viscous oil remains in 
solution at 212.2 F. the critical temperature of propane. This 
property makes it possible to recover by simple decantation a large 
proportion of the propane in a substantially pure state, without 
the necessity to vaporize it by the usual method. 

To utilize these varying properties of propane on a stock con- 
taining all the foregoing undesirable constituents, a typical cycle 
consists in mixing the oil with 4 to 6 times its volume of liquid 
propane at 120 to 150 F., which will throw out of solution prac- 
tically all of the asphalt. The latter may be settled out and drawn 
off as a liquid because it contains a substantial quantity of dissolved 
propane. The remaining solution can then be rapidly chilled by 
the simple expedient of lowering the pressure and allowing a small 
quantity of the propane to evaporate until a temperature of 

20 to 40 F. is attained, whereupon the wax will be 

thrown out of solution and may be removed by settling or prefer- 
ably by filtration. The propane solution is then brought back to 
room temperature, and may either be treated with relatively small 
quantities of sulfuric acid to remove the color bodies and naphthenic 
constituents, or else be heated without any additions, in stepwise 
fashion, to about 200 F. Under these conditions a series of cuts 
of varying composition is separated out; the first is composed of 
very heavy ends, resinous constituents, and the more heavy naph- 



128 METHODS OF MINING, TRANSPORTING AND REFINING VI 

thenic constituents of the oil, and each cut becomes lighter and 
more paraffinic, until the last material left in solution is a rela- 
tively low-boiling, highly paraffinic, light-colored oil. 

The term u propane de-asphalting" is usually applied to those 
cases where the heavy product is a mixture containing black, pitchy 
material. This operation may include removal of only a small 
amount (approximately 3.5 per cent) of high melting-point asphalt 
from a Mid-continental crude, to a much larger percentage from a 
California crude. In the latter case, the separated asphalt had a 
specific gravity at 60 F. of 1.031, a penetration at 77 F. of 35, 
a fusing-point (R. and B. method) of 118 F., and over 99.6 per 
cent soluble in CS 2 , CC1 4 and 86 petroleum naphtha, respectively. 

Attempts have also been made, but without success, to utilize 
the solvent extraction method to recover the bituminous constitu- 
ents and felt respectively from the waste material produced in the 
manufacture of asphalt roofings and shingles. 86 On the other hand, 
it has given satisfactory results in recovering montan wax from 
lignite at Thuringia, Saxony, and from pyropissite at Weissenfels, 
near Halle, Germany. Benzol is generally used for this purpose, 
although in certain cases petroleum distillates have given good re- 
sults. The high market price of montan wax in comparison to 
asphalt undoubtedly accounts for this. 

METHODS OF STORAGE 

Bituminous substances which are capable of liquefying under 
heat are usually stored in metal tanks of various capacities. These 
may be equipped with steam-coils. One device consists in con- 
structing a small metal tank within a larger one, the smaller unit 
being provided w r ith the steam coils to conserve the heat. 87 



CHAPTER VII 

MINERAL WAXES 

OZOKERITE 

Ozokerite is a native mineral wax, composed of the higher mem- 
bers of the C n H 2 n + 2, and C n H 2 n series of hydrocarbons. It occurs 
in deposits usually associated with petroleum. Certain varieties 
carry a proportion of petroleum in solution with the wax, and the 
more petroleum present, the softer will be the consistency and lower 
the fusing-point. Ozokerite as ordinarily found is fairly hard, and 
has a comparatively high fusing-point, ranging from 50 to 180 F. 
The fusing-point has been recorded as high as 200 F. (K. and S. 
method). Ozokerite containing between 10 and 15 per cent of 
petroleum in solution, shows a fusing-point between 140 and 150 F. 
The petroleum can readily be evaporated by applying a moderate 
degree of heat, and is expelled during the refining process. 

The color of ozokerite depends upon the nature and extent of 
the impurities present, and ranges from a transparent yellow to a 
dark brown. In rare instances, ozokerite occurs in a dichroic va- 
riety, showing a dark green color by reflected light, and a pure 
yellow by transmitted light. It breaks with a conchoidal fracture, 
and has a characteristic waxy lustre. Its streak on porcelain varies 
from a transparent white to a pale brown. 

Ozokerite is usually found filling veins or fissures, which are 
very irregular in structure, varying from a fraction of an inch to 
about two feet in thickness. Some extend for comparatively long 
distances whereas others pinch out very suddenly. The veins are 
usually caused by faulting, which accounts for their irregularity and 
gives the vein the appearance of a series of pockets. The indica- 
tions are that the ozokerite enters the faults or veins from below, 
which is borne out by the fact that the material mined at a depth 
is materially softer and has a lower fusing-point than that obtained 
near the surface. 

Ozokerite may occur in a pure state (comparatively free from 

129 



130 MINERAL WAXES VII 

mineral matter), which proves to be the case when it is found in 
vein form, or it may be associated with sandstone or shale. In 
fact, it is quite common for the entire region surrounding the vein 
to be saturated with ozokerite. 

A paraffinaceous petroleum almost invariably occurs in the strata 
underlying the ozokerite, which would seem to indicate that the 
latter must have been produced by the slow hardening and probably 
also the oxidation of petroleum throughout centuries of time. 
Ozokerite, itself, however, is practically free from oxygen. In this 
particular case, therefore, the effect of oxidation is to eliminate 
hydrogen, and form hydrocarbons of higher molecular weight. 

The petroleum underlying the ozokerite usually contains from 
8 to 1 2 per cent of paraffin, which, however, is entirely different in 
its character from the hydrocarbons contained in the ozokerite. 1 
This proves conclusively that ozokerite is not formed merely by the 
evaporation of petroleum, but must have been produced by a process 
of metamorphosis or polymerization. 

On distilling at atmospheric pressure, ozokerite decomposes, 
whereas when it is distilled under reduced pressure, its composition 
changes but little. Still another process consists in distilling the 
ozokerite in retorts with superheated steam, whereupon the residue 
in the retort is known as 44 ozokerite pitch," which when combined 
with rubber has been marketed under the name "okonite." 

Ozokerite as it is mined is assorted by hand-picking to separate 
the pure material from that associated with earthy matter. The 
latter, which is known as "wax-stone," is broken up to remove any 
lumps of rock and purified by extraction with boiling water. The 
method used for this purpose is very crude, and consists merely in 
boiling the wax-stone with water in large open kettles. The sand- 
stone or shale separates to the bottom and the melted ozokerite 
floats in a layer on the surface, whereupon it is skimmed off, boiled 
to evaporate the water and cast into blocks. The commercial ma- 
terial is comparatively free from mineral matter, rarely containing 
over 2 per cent. 

Ozokerite may be refined still further by heating to 120-200 C., 
with 20 per cent by weight of concentrated sulfuric acid, or with 
chromic acid, 2 or by treating ozokerite with alkali and filtering hot 
through fuller's earth, animal charcoal, or magnesium silicate. This 



VII OZOKERITE 131 

bleaches the ozokerite, forming a product almost white in color, 
known as "ceresine." From 10 to 15 per cent of the ozokerite is 
lost during the treatment, but the fusing-point of the product is 
increased. The final traces of acid are removed and the bleaching 
process completed by adding from 5 to 12 per cent of dry residue 
obtained from the manufacture of "ferrocyanides." The main dif- 
ferences between ozokerite and ceresine are in the color and 
fusing-point. 

Ozokerite and ceresine are used in the manufacture of high- 
grade candles, colored lead pencils, for finishing off the heels and 
soles of shoes, manufacturing shoe polishes, electrical insulating 
purposes, as an acid-proof coating for electrotypers* plates, and 
waxing floors. They are readily soluble in turpentine, petroleum 
distillates, carbon disulfide, and benzol, by scarcely soluble in alcohol. 

Purified ozokerite and ceresine comply with the following 
characteristics : 

(Test i)* Color in mass White to yellow to brown 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Dull to "waxy" 

(Test 6) Streak Transparent white to yellow 

(Test 7) Specific gravity at 77 F o. 85-1.00 

(Test go) Hardness, Moh's scale Less than i 

(Test 9^) Penetration at 32 F o 

Penetration at 77 F 20-30 

Penetration at 115 F 150-250 

(Test $c) Consistometer hardness at 32 F. . . Above 100 

Consistometer hardness at 77 F . . . 20-40 

Consistometer hardness at 115 F. . . 5-15 

(Test gd) Susceptibility factor Greater than 80 

(Test i$a) Fusing-point (K. and S. method) 140-200 F. 

(Test 15^) Fusing-point (R. and B. method). . . . 155-225 F. 

(Test 19) Fixed carbon K-IO per cent 

(Test 21) Soluble in carbon disulfide 95-100 per cent 

Non-mineral matter insoluble * . o-i per cent 

Mineral matter 0-5 per cent 

(Test 22) Carbenes 0-3 per cent 

(Test 23) Non-mineral matter soluble in 88 

petroleum naphtha 75~95 per cent 

(Test 26) Carbon 84-86 per cent 

(Test 27) Hydrogen. . . < 16-14 per cent 

(Test 28) Sulfur o-i . 5 per cent 

(Test 29) Nitrogen 0.0.5 per cent 

(Test 30) Oxygen 0-2 percent 

(Test 33) Solid paraffins 50-90 percent 

(Test 34^) Sulfonation residue 90-100 per cent 

(Test 37*) Saponifiable constituents 0-2 per cent 

* The numbers refer to tests, which are described in detail in Chapter XXXII. 



132 MINERAL WAXES VII 

Very often ozokerite and ceresine are adulterated with paraffin 
wax, rosin, tallow, stearic acid or mineral fillers (such as talc, kao- 
lin, gypsum, etc. ) * 

Ozokerite occurs in the following localities : 8 

EUROPE 

Poland (Galicia). 4 The most important ozokerite deposits are 
found in the Carpathian Mountains in the districts of Drohobycz 
(comprising Boryslaw, Wolanka and Truskawiec) and Stanislau 
(comprising Dwiniacz, Straunia, Wolotkow and Niebylow). It is 
known under various names, e.g., "ozokerit," "fossil or montan 
wax," "mineral fat," etc. In the Moldau region it is called "zietris- 
zit," and around the Caspian Sea, "nephtgil," "neftgil," "naphatil," 
etc. The largest deposit is located as Boryslaw, a small town in 
Galicia, and has been exploited since about 1859. ^ ' IS found at 
some depths below the surface, associated with schist and sand- 
stone, and it is mined by means of shafts and galleries. About 
1500 shafts have been sunk in the district. 

The following varieties of ozokerite are recognized in the 
Boryslaw district: 

(1) Marble wax, found 100200 m. below the surface, is very 
hard, of a pale yellow color, with greenish, brownish and black 
markings, giving it the appearance of marble, and has a fusing- 
point of 85 to 1 00 C. 

(2) Hard wax or "crackwax" (Sprungwax) is darker in color 
than marble wax, shows a granular fracture and a fusing-point of 
75 to 90 C. 

(3) Fibrous wax, or "fibrewax," which is characterized by its 
fibrous structure. 

(4) Bagga is dark in color, contains clay, and has a compara- 
tively low fusing-point (40-60 C.). 

(5) Kindebal or "kinderball" is characterized by being soft, of 
low fusing-point (30-50 C.) and a black color. It contains pe- 
troleum and mineral matter. 

(6) Blower wax ("blister wax" or "matka") is a pale yellow, 
soft variety, which is squeezed out of the veins due to the presence 
of the surrounding rocks. 

(7) Lep is a variety of ozokerite associated with a substantial 
proportion of mineral matter. 

The deposit at Wolanka is smaller than that at Boryslaw. The 



VII EUROPE 133 

occurrence at Truskawiec differs from the others by the presence of 
a comparatively large percentage of sulfur. The ozokerite in this 
locality is associated with native sulfur, lead sulfide, gypsum, and 
petroleum. 

At Dwiniacz, Straunia and Wolotkpw, about 70 miles south of 
Boryslaw, the ozokerite veins are located some distance below the 
surface, in beds of clay between layers of shale. Considerable 
ozokerite has been mined in this district, and particularly at 
Dwiniacz. The veins vary in size from J4 * n - to about I ft. The 
rock in the vicinity of the veins is impregnated with wax, contain- 
ing an average of 2 per cent. 

Rumania. Deposits of ozokerite are also found in a spur of the 
Carpathian Mountains in the province of Moldavia in Rumania. It 
has been mined in several localities, the largest vein occurring in the 
city of Slanik, beneath a bed of bituminous shale, associated with a 
vein of cannel coal. This deposit is characterized by its high fusing- 
point, in the neighborhood of 200 F. (K. and S. method). 

Russia. Numerous deposits of ozokerite occur throughout 
Russia, including specifically the following: 5 

Terek Province (Northern Caucasia}. In thq vicinity of Gro- 
zny!, among the narrow passes along the road from Wozdwishensk 
and Chatoi, near the right bank of the Chanti-argun River. 

Kuban Province* (Northern Caucasia] . In the oil fields at Mai- 
kop, near Chadychenskaja, on so-called Wax Mountain, about 5 km. 
from Pshish stream. 

Kutais Province (Transcaucasia}. In the vicinity of Kutais, 2 
km. east of the village Dznucisi, between the rivers Lechidary and 
Merchery; likewise at Achokrua in the same neighborhood; also 
near Charopan, northeast of the village Tedeleti, in a gorge be- 
tween the mountains Gagberula and Syrch-Liberta. 

Tiflis Province (Transcaucasia}. At Sadzluri, in the neighbor- 
hood of Cori, on the banks of Kran River. 

Baku Province (Transcaucasia}. In the Baku oil fields, near 
the town Surachany, also on the Island of Suyatoi in the Cas- 
pian Sea. 

Kars Province (Transcaucasia}. In the region of Chala-Da- 
rasi, in the vicinity of Kars. Occurs in layers containing 1.5 to 2.5 
per cent ozokerite in Uzbekistan, at Sel-rokho and Shorsu. 



134 MINERAL WAXES VII 

ASIA 

State of Turkestan. On the Island of Cheleken in the Caspian 
Sea; 6 also in the vicinity of Ferghana, also at Neftedag (Turkoman 
Republic) in veins containing 50 to 80 per cent ozokerite, termed 
locally "lep." 

Siberia. Along the eastern shore of Lake Baikal. 

Philippine Islands. On the Island of Leyete, veins of ozokerite 
occur at the contact of an intrusive dike with shales and sand- 
stones. 7 

NORTH AMERICA 

UNITED STATES 

Utah. The most important deposit occurs near Colton, in 
Wasatch County, Utah, 8 *in a bed of oil shale. The veins extend 
from about 2 miles west of Colton to within a few hundred yards 
west of the railroad station of Soldier Summit, or a total distance of 
12 miles. The mineral as mined contains about 15 per cent ozo- 
kerite which is extracted by heating the crushed ore with water at 
60*70 C, whereupon the wax floats off. A peculiar feature of this 
deposit is the occurrence of fossil shells together with other animal 
remains. The following analytical results have been reported: 

(Test i) Color in mass Yellowish brown 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Dull 

(Test 6) Streak Pale yellow 

(Test 7) Specific gravity at 77 F o. 899-0. 920 

(Test 9*) Hardness, Moh's scale Less than i 

(Test gb) Penetration at 77 F 30 

Penetration (100 g., 15 sees.): 

at 20 C 0.43 mm. 

at 30 C 0.64 mm. 

at 40 C i . 27 mm. 

at 50 C 2.2 mm, 

at6oC 3.8 mm. 

(Test 111) Coefficient of expansion between 10 and 

50 C., per deg. C o.ooi 

(Test I5/) Fusjng-point 60 to 80 C 

(Test 16) Volatile, 212 F. I hr o.o per cent 

Volatile, 325 F., 5 hrs 45.41 per cent 

Volatile, 400 F., 5 hrs 65.2 per cent 

(Test 19) Fixed carbon 9.6 per cent 

(Test 21 ) Solubility in carbon disulfide 99.46 per cent 

Non-mineral matter insoluble o. 50 per cent 

Free mineral matter 0.046 per cent 



VII NORTH AMERICA 135 

(Test 12) Carbcnes 2. 51 per cent 

(Test 23) Soluble in 88 petroleum naphtha 81 .71 per cent 

(Test 26) Carbon 85.35 P er cent 

(Test 27) Hydrogen 13.86 per cent 

(Test 28) Sulfur 0.29 per cent 

(Test 29) Nitrogen 0.36 per cent 

(Test 58) Dielectric strength across a o.i-in. gap over 30,000 volts 

Dielectric constant 2 .03 

Power factor o . 03 

Resistivity across a i-cm. cube 30 million megohms 

Texas. At Thrall, in the so-called Thrall Oil Field, another 
deposit has been reported. 9 The crude material is soft, due to the 
petroleum associated with it, and of a dark brown color. It has a 
strong odor of petroleum, and a specific gravity at 77 F. of 0.875. 
On being heated to 100 C, it loses 14.72 per cent, and at 180 C. 
a total of 23. 1 4 per cent in weight. On being freed from petroleum, 
it shows a fusing-point of 175 F. 

HATCHETTITE OR HATCHETTINE 

The above names are assigned to a soft variety of ozokerite 
fusing in the neighborhood of 120 F. (Test I5/). It varies in 
specific gravity from 0.90 to 0.98 at 77 F., and has a yellowish- 
white> yellow or greenish-yellow color. It was named after C, 
Hatchett, an English chemist (1765-1847). It is found near 
Merthyr-Tydvil in Glamorganshire, England, also at Loch Fyne in 
Argylshire, Scotland. 

SCHEERERITE 

A native wax found in a bed of lignite near St. Gall, Switzer- 
land. It occurs in the form of crystals (monoclinic) and of a white, 
gray, yellow, green or pale reddish color. It is more or less trans- 
lucent to transparent, and has a waxy feel. It is composed chiefly 
of the members of the paraffin series, and fuses at a temperature 
of 110-115 F. 

KABAITE 

This is a waxy hydrocarbon similar to ozokerite or scheererite, 
which has been found in meteorites. It is only of scientific interest 
and has no commercial importance. 



136 MINERAL WAXES VII 

MONTAN WAX 

As stated previously, montan wax is dissolved from certain non- 
asphaltic pyrobitumens by means of volatile solvents, such as benzol, 
xylol, mixtures of benzol with methyl alcohol or acetone, 10 mixtures 
of toluol and alcohol, 11 etc. By extracting under pressure the yield 
is materially increased, and at 50 atmospheres at 250-260 C., 
benzol will extract about double the weight than at I atmosphere 
at 80 C. 12 The lignite or pyropissite is first dried, then granu- 
lated, and finally extracted. The extract is evaporated to recover 
most of the solvent. The last traces of solvent are expelled from 
the montan wax by distillation with steam, and recondensed. The 
crude wax differs widely according to the source, Thuringian lignites 
yielding a hard and brittle wax, whereas Bohemian lignites yield a 
softer product. 

Ninety per cent of the montan wax present in the lignite is re- 
moved in this manner. About 10 to 15 per cent of the solvent is 
lost, but the high price obtainable for montan wax renders this per- 
missible. Usually 8 to 10 per cent of montan wax is extracted 
from Thuringian lignite based on the dry weight of the latter. In 
exceptional cases, as high as 20 per cent has been obtained. Pyro- 
pissite yields between 50 and 70 per cent of montan wax based on 
its dry weight. Unfortunately, the supply of pyropissite is largely 
exhausted. 

According to Edmund Graefe, 13 the following percentages of 
montan wax are extracted by benzol from the dried minerals : 

Per Cent 

Bohemian Lignite i 29 

Texas Lignite 2.07 

Lignite from the region of the Rhine 4-7 

Lignite from Vladivostok 5-3& 

Lignite from Thuringia, Saxony 9-3 

Pyropissite 69. 50 

The montan wax industry is not practiced in the United States, 
but is localized in Saxony. 

Montan wax contains esters of acids possessing high molecular 
weight, free acids and a small quantity of substances containing sul- 
fur. Various formulae have been assigned to it, including Ci e H 82 O, 
CHO2 C 2 0H 5 8O and C^HgeO. 



VII NORTH AMERICA 137 

At ordinary temperatures it decomposes when distilled. It may, 
however, be purified by distilling with superheated steam in 
In this manner the following products are obtained : 



(i 

(2 

(3 



Pure odorless montan acid; 

Refined montan wax; 

A bright yellow wax containing paraffin; 



(4) A residue containing paraffin; 

(5) An acid-free pitch, 15 known as "montanpitch" or "montan- 
wax pitch," which is a hard waxy material having a dark color. 

On heating with glycerine, an ester is obtained which has a 
much higher fusing-point (in the neighborhood of 200 F.). Mon- 
tan wax may be blown with air, either alone or in the presence of 
oxalic acid, 16 and when chlorinated will be transformed into a resi- 
nous product. 17 

Commercial montan wax complies with the following charac- 
teristics : 

(Test i) Color in mass; 

Crude montan wax Dark brown 

Product obtained by distillation in 

vacuo Almost white 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Waxy 

(Test 6) Streak on porcelain Yellowish brown to white 

(Test 7) Specific gravity at 77 F o. 90-1 .00 

(Test 9^) Penetration at 77 F o to 5 

(Test 9<r) Hardness at 77 F. (consistometer) Above 100 

(Test $d) Susceptibility index > 100 

(Test 10) Ductility at 77 F o.o 

(Test I5/) Fusing-point (K. and S. method) 170-200 F. 

Note. Montan wax obtained from pyropissite has a higher fusing-point than 
that obtained from lignite; namely, between 190 and 200 F. 

(Test 17) Flash-point 55 to 575 F. 

(Test 19) Fixed carbon 2-10 per cent 

(Test 21) Solubility in carbon disulfide Greater than 98 per cent 

Non-mineral matter insoluble 0-2 per cent 

Mineral matter Less than 2 per cent 

(Test 23) Soluble in 88 petroleum naphtha 80-100 percent 

(Test 26) Carbon 82-83^ per cent 

(Test 27) Hydrogen *4~ I 4# per cent 

(Test 28) Sulfur Less than i . 5 per cent 

(Test 29) Nitrogen Trace 

(Test3o) Oxygen 3~6 percent 

(Test 33) Solid paraffins , o-io per cent 

(Test 34^) Sulfonation residue *. . o-io per cent 

(Test 370) Acid value '. 28-33 

(Test 37*) Ester value 28-73 



138 MINERAL WAXES VII 

(Test 37<f) Saponification value 5~95 

(Test 37<r) Saponifiable matter 50-80 per cent 

Resins 20-30 per cent 

Alcohols 5-20 per cent 

Normal wax acids 49~5^K per cent 

Oxy-acids 3-5 per cent 

Sulfur-containing acids 6^-8 per cent 

(characteristic of crude montan wax) 

(Test 38) Asphaltic constituents o per cent 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction No 

Montan wax is used for manufacturing shoe polishes, phono- 
graphic records, electrical insulating materials, and the like, also 
for impregnating timber under vacuum followed by pressure. 1 



18 



CHAPTER VIII 

NATIVE ASPHALTS OCCURRING IN A FAIRLY 
PURE STATE 

Under this heading will be considered the most important as- 
phalt deposits containing less than 10 per cent of mineral matter 
figured on the dry weight. These include exudations or seepages of 
liquid or semi-liquid asphalts, also surface overflows and lakes. 
Most of these are characterized by being liquid to semi-liquid at 
normal atmospheric temperature, and by containing a comparatively 
large proportion of volatile matter. Only a few of these deposits 
are of value commercially. 

The principal deposits are as follows : 

NORTH AMERICA 

UNITED STATES 
Kentucky. 

Breckinridge County. The so-called "Tar Springs" situated 
about 4 miles south of Cloverport on Tar Creek, have been known 
for many years. They occur as seepages of pure, soft asphalt at 
the base of an overhanging cliff of sandstone where it joins a 
stratum of limestone. The asphalt is accompanied by water charged 
with sulfur compounds, and the surrounding rocks abound in ma- 
rine fossils. 

Gray son County. Similar seepages abound along Big Clifty 
Creek and its tributaries, in the vicinity of Grayson Springs station. 
Some exude from sandstone and others from clay or shale. The 
seepages carry between 5 and 10 per cent of free mineral matter, 
the balance consisting of a very soft, "stringy" asphalt containing a 
large proportion of volatile ingredients and yielding about 15 per 
cent of fixed carbon. 

139 



140 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

Oklahoma. 

There are only a few minor occurrences of pure asphalt found 
in Oklahoma in the form of seepages, including the following: 

Carter County. NE J4, Sec. 10, T 2 S, R 2 W; 10 miles north 
of Wheeler. 

Murray County. SW J4, SE ^4, Sec. 15, T i S, R 3 E; 3 
miles south of Sulphur. 

Neither of these has any commercial importance. 

Utah. 

Uinta County. A pure, solid asphalt is found in Tabby Can- 
yon, a branch of the Duchesne River, 8 to 9 miles south and west 
of the town of Theodore and about 30 miles west of Ft. Duchesne. 
It has been exploited under the name "tabbyite" * and tests as 
follows : 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .006-1 .010 

(Test 90) Hardness, Moh's scale Less than i 

(Test 9^) Penetration at 77 F o 

(Test 9<r) Consistency at 77 F 80.0 

(Test i$a) Fusing-point (K. and S. method) 178 F. 

(Test 1 6) Volatile matter, 325 F. in 5 hrs 2.78 per cent 

Volatile matter, 400 F. in 5 hrs 6.40 per cent 

(Test 19) Fixed carbon 8 .08- 9 . 2 per cent 

(Test 21 ) Soluble in carbon disulfide 94.7 -92. i per cent 

Non-mineral matter insoluble 0.5-1.1 per cent 

Free mineral matter 4.8-6.8 per cent 

(Test 22) Carbenes o.o per cent 

(Test 23) Soluble in 88 petroleum naphtha 61 per cent 

(Test 25) Carbon 82 per cent 

(Test 26) Hydrogen n per cent 

(Test 27) Sulfur 2 per cent 

(Test 28) Nitrogen 2-2.5 per cent 

Undetermined 2 per cent 

Boxelder County. .A pure viscous asphalt deposit occurs below 
the bed of Great Salt Lake, about 10 miles south of Rozel, in the 
Promontory Range. 2 It is found in a series of horizontal veins 3 
to 5 ft. thick interposed between beds of clay, continuing to a depth 
of at least 140 ft. It is highly probable that a lake of asphalt 
occurred at this point centuries ago, which in time became covered 
with sediments, giving rise to a series of veins. 



VIII NORTH AMERICA 141 

At the present time, masses of asphalt exude through the uncon- 
solidated material at the bottom of the lake, and float to the sur- 
face in lumps i to 2 ft. in diameter. This occurrence corresponds 
very closely with the Dead Sea deposit. On analysis, the asphalt 
tests as follows: 

(Test 5) Lustre Very bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F 1 .02 

(Test gb) Penetration at 32 F. (200 g. in 60 sees.) 12 

Penetration at 77 F. (100 g. in 5 sees.) 50 

Penetration at 115 F. (50 g. in 5 sees.) 170 

(Test loo) Ductility at 77 F 70 cms. 

(Test 16) Volatile at 325 F. in 5 hrs 2.33 per cent 

Volatile at 325 F. in 7 hrs . . . . 3.4 per cent 

(Test 19) Fixed carbon 4. 56 per cent 

(Test 21 ) Soluble in carbon disulfide 95 .00 per cent 

Non-mineral matter insoluble i . 84 per cent 

Free mineral matter 3.16 per cent 

Note. Has unusually high adhesiveness, ductility and cementing qualities. > 

California. 

Kern County. Deposits of asphalt occur in the so-called "As- 
phalto Region" in the western part of Kern County, about 50 
miles west of Bakersfield, in the form of large springs; also as 
veins. The character of the asphalt varies greatly, both in consis- 
tency and purity. The superficial overflow covers an area of 7 
acres, in a layer 2 to 4 ft. thick overlying sand and clay. Part of it 
has hardened on account of exposure to the elements, and other 
portions are still soft and viscous. A vein of asphalt also occurs in 
the vicinity of the overflow, filling a fault, varying from 2 to 8 ft. 
in width, averaging about 4 ft. The nature of the asphalt in the 
vein is similar to that of the overflow. 

The asphalt carries from 3 to 30 per cent mineral matter, 
mostly sand and clay, also gas, which is evidenced by the fact that 
it loses between 5 and 15 per cent in weight on being heated to 
212 F. for one hour. The run of the mine averages 85 per cent 
asphalt, 10 per cent mineral matter and 5 per cent moisture and 
gas. It is refined by heating, which drives off the water and gas 
and permits a certain amount of the mineral matter to settle out. 
According to Clifford Richardson 8 the refined asphalt tests as 
follows : 



142 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

(Test 4) Fracture Semi-conchoidal 

(Test 5) Lustre Bright to dull 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .06 

(Test 9^) Penetration at 77 F 0-27 

(Test 1 6) Volatile matter, 325 F., 5 hrs 6.6 per cent 

Volatile matter, 400 F., 5 hrs 19.9 per cent 

(Test 19) Fixed carbon 8.0 per cent 

(Test 21) Soluble in carbon disulfide 89.8 per cent 

Non-mineral matter insoluble 3.4 per cent 

Free mineral matter 6.8 per cent 

Total 100.0 per cent 

(Test 22) Carbenes 0.3 per cent 

(Test 23) Soluble in 88 petroleum naphtha 53 .4 per cent 

(Test 340) Saturated hydrocarbons 28 .6 per cent 

The asphalt resembles gilsonite in its outward appearance, but 
is considerably softer, yielding a smaller percentage of fixed carbon. 
Richardson infers that the asphalt has been metamorphized only 
part way to gilsonite. This deposit of asphalt is not being worked 
at the present time, but is of interest from the scientific viewpoint. 

A sample of liquid asphalt taken from seepages in the so-called 
"McKittrick Region," in Kern County, shows specific gravity at 
77 F. of 0.99, and 16 per cent loss on being heated to 400 F. for 
seven hours. In its original state it is very soft and sticky. 

San Luis Obispo County. A large surface deposit of soft asphalt 
produced by seepage from the surrounding shale occurs at Tar 
Spring Creek, a tributary of the Arroyo Grande, 20 miles southeast 
of San Luis Obispo, covering an area of 200 ft. in diameter and 
3-15 ft. deep. As it exudes from the shale, the asphalt is soft and 
accompanied with sulfurous water; near the edge of the deposit it 
appears quite hard, and at the edge it verges towards brittleness. 
No analytical results are available. 

Santa Barbara County. Veins of high-grade asphalt occur in 
La Graciosa hills about 4 to 5 miles east of the town of Graciosa in 
the so-called Santa Maria Region. These are irregular in forma- 
tion, extending through shale and sandstone, and varying from 
several inches to 2 ft. in width. Associated with these veins are beds 
of impregnated asphaltic shale, extending over an area of a mile or 
two, and containing a variable percentage of asphalt. One of the 
striking features of these Recurrences is the presence of marine 
fossils in the veins and surrounding shale, indicating that the asphalt 
is of animal origin^ 



VIII NORTH AMERICA 143 

Oregon. 

Coos County. An unusual type of asphalt occurring in beds of 
coal has been reported at the old Newport Mine at Libby, and old 
Ferrey's Mine at Riverton, in the Coos Bay coal field. It is hard 
and brittle, and similar to coal in appearance. About one-third of 
the non-mineral matter is insoluble in carbon disulfide, yet the ma- 
terial fuses as a comparatively low temperature (about 300 F.), 
and has a specific gravity of less than i.io at 77 F. It may be re- 
garded as a metamorphized asphalt or a glance pitch. It consti- 
tutes one of those substances encountered occasionally, falling on the 
border line, so that it becomes a difficult matter to arrive at its cor- 
rect classification. For a long time it was known as a "Pitch 
Coal." 4 The following data would seem to indicate that it par- 
takes of the properties of an asphalt rather than of a glance pitch: 

(Test 4) Fracture Hackly to conchoidal 

(Test 5) Lustre Fairly dull to brilliant 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F 1 .09 to i . 28 

(Test 9*) Hardness, Moh's Scale About I 

(Test 9^) Penetration at 77 F o 

(Test 9f) Consistency at 77 F Above 100 

(Test 14^) In flame Softens and flows 

(Test i$a) Fusing-point (K. and S. method) 302 to 330 F. 

(Test 16) Volatile at 325 F., 5 hrs o. 5 per cent 

(Test 19) Fixed carbon 10-13 per cent 

(Test 21) Soluble in carbon disulfide 100 per cent 

(Test 22) Carbenes o per cent 

(Test 23) Soluble in 88 petroleum naphtha About 10 per cent 

(Test 27) Sulfur o. 5-1 .o per cent 

MEXICO 
State of Tamaulipas. 

Asphalt springs occur at numerous points along the Tamesi 
River, which, according to Clifford Richardson, 5 show the follow- 
ing characteristics : 

(Test 7) Specific gravity at 77 F i .04-1 . 12 

(Test 9*) Penetration at 77 F 40-16 

(Test 16) Loss at 212 F. until dry 10-20 per cent 

Loss at 325 F. for 5 hrs. (refined material). . . i . 5-4. 8 per cent 

Loss at 400 F. for 5 hrs 4.3-8.9 per cent 

(Test 17) Flash-point 308 F. 

(Test 19) Fixed carbon 12.6-16. i per cent 

(Test 21) Solubility in carbon disulfide (refined material). 89. 0-99 . o per cent 

Non-mineral matter insoluble o. 5- i . 8 per cent 

Free mineral matter 0.5-9.1 per cent 



144 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

Other deposits in the neighborhood show a larger proportion of 
mineral matter, often running as high as 33 per cent 

Chijol. Asphalt springs occur also near Chijol, 25 miles west 
of Tampico. They are comparatively soft in consistency, testing 
over 90 per cent soluble in carbon disulfide, with less than 10 per 
cent mineral matter, 

State of Vera Cruz. 

District of Tuxpan. Similar deposits are found in the neigh- 
borhood of Tuxpan, some distance from the Tuxpan River, having 
the same general characteristics as the preceding. Analyses show 
that 90 per cent is soluble in carbon disulfide, with less than 10 per 
cent of mineral matter. 

District of Chapapote. Similar deposits are found 15 miles 
from Timberdar at the head of the Tuxpan River, of an exceed- 
ingly pure character, testing 99 per cent soluble in carbon disulfide, 
and less than i per cent mineral matter. The asphalt varies in 
consistency from a semi-liquid to a comparatively hard solid, de- 
pending upon the length of time it has been exposed to the weather. 6 

In the early days, the name "chapapote" was applied generally 
to designate viscous, semi-liquid asphalts corresponding in charac- 
teristics to the type of asphalt found in this district 

CUBA 

Province of Matanzas. A pit filled with pure liquid asphalt 
has been reported in the neighborhood of Santa Catalina. This 
occurs in a bed of serpentine, and originally produced in the neigh- 
borhood of 20 barrels of semi-liquid asphalt a day, derived pre- 
sumably from underlying petroleum-bearing strata. Other pits in 
the neighborhood similarly yield liquid asphalt 

Liquid asphalt is also found near Cardenas and extends some 
distance eastwards. Another deposit, known as "Dos Companeros 
Mine," occurs in the Guametos District, near Sabanilla de la Palma, 
testing as follows : 

(Test 7) Specific gravity at 77 F 1.05-1.06 

(Test 16) Volatile at 220 F 2-18 per cent 

Volatile at 325 F., 5 hrs 2.8-6.8 per cent 



VIII NORTH AMERICA 145 

(Test 19) Fixed carbon 10-12 per cent 

(Test 21) Soluble in carbon disulfide 98-99 per cent 

Non-mineral matter insoluble o-i . 5 per cent 

Mineral matter 0.5-2.0 per cent 

(Test 23) Soluble in 88 petroleum naphtha 73-77 per cent 

Another deposit occurs 7 miles south of Hato Nuevo, testing 
similar to the preceding. All of these deposits contain more or 
less adventitious water. 

Province of Santa Clara. A variety of hard asphalt, ap- 
proaching glance pitch, is found in Calabazar District, near the 
town of Mata, in a mine known as "El Provenir." It tests as 
follows : 7 

(Test i) Color in mass Black 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak on porcelain Brownish black 

(Test 7) Specific gravity at 77 F i .09-1 .11 

(Test 19) Fixed carbon 18 .o- 19.2 per cent 

(Test 21) Soluble in carbon disulfide 97 . 5- 97 . 6 per cent 

Non-mineral matter insoluble 0.5- 0.9 per cent 

Mineral matter 2.0- i . 5 per cent 



Total '. 100.0-100.0 per cent 

(Test 23) Soluble in 88 petroleum naphtha 39. 4- 57.4 per cent 

Province of Camaguey. Deposits of pure soft asphalt occur 
near the village of Minas, about 30 miles from Nuevitas and 20 
miles from Puerto Principe City. The asphalt is associated with 
water, and tests as follows: 

(Test 7) Specific gravity at 77 F. (dry) , i .079 

(Test gb) Hardness at 77 F. (dry) 35 

(Test 16) Volatile at 325 F. in 5 hrs 6.2 per cent 

Penetration of residue at 77 F 12 

(Test 21) Soluble in carbon disulfide 94- 5 per cent 

Non-mineral matter insoluble 0.3 per cent 

Mineral matter 5.2 per cent 

Total 100. o per cent 

(Test 23) Soluble in 88 petroleum naphtha 70.0 per cent 



Province of Santiago de Cuba* A small deposit of soft as- 
phalt has been reported in Victoria de las Tunas District, $ l /2 miles 



146 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

southwest of San Manuel, in a mine known as "Punta la Brea," 
which tests as follows : 

(Test 7) Specific gravity at 77 F o. 990 

(Test 16) Volatile at 325 F. in 5 hrs 6.3 per cent 

(Test 21) Soluble in carbon disulfide 99. 1 per cent 

Non-mineral matter insoluble 0.5 per cent 

Mineral matter 0.4 per cent 

(Test 23) Soluble in 88 petroleum naphtha 88 . 8 per cent 



SOUTH AMERICA 

VENEZUELA 

State of Bermudez. The so-called Bermudez "Pitch Lake" 8 
is situated near the town of Guanoco in the District of Benitez, 3 
miles above the confluence of the San Juan and Guanoco Rivers, 25 
miles west of the Gulf of Paria, and 105 miles due west of Trinidad 
Lake. It is covered with vegetation and water in pools. A typical 
view is shown in Fig. 43. The lake represents the exudation of soft 
asphalt from springs distributed at different points over its area, and 
constitutes one of the largest deposits of pure asphalt yet discov- 
ered, extending over mo acres and varying in depth from 2 to 
20 ft, averaging 5 ft. 

Its consistency varies in different parts of the lake. Where it 
exudes from the springs, it is quite soft, and disengages gas freely 
and copiously. The surface of the deposit hardens slowly on expo- 
sure to the weather, forming a crust varying from several inches to 
several feet in thickness, and sufficiently firm to support the weight 
of a man. The asphalt underneath, however, is still soft and semi- 
liquid, and there are numerous breaks through the surface from 
which the soft asphalt oozes. At the edge of the lake the asphalt 
is hard and brittle, due to the evaporation of the volatile constitu- 
ents by the heat of the sun. Certain portions of the lake have been 
converted into a cokey mass as a result of fires which must have 
swept over the lake years ago, due probably to the combustion of 
vegetation growing profusely at the edges. 

To remove the asphalt, a dam is built of slag and waste and 



VIII 



SOUTH AMERICA 



147 




Courtesy of Barber Co. 



FIG. 43. -View of Bermudez Asphalt Lake. 




Courtesy of Barber Co. 
FlG. 44. Transporting Bermudez Asphalt. 



148 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

the water pumped out The asphalt is then dug out by hand and 
loaded into small cars, which are hauled by cable to a railroad run- 
ning to Guanoco, 8 miles distant, where it is either refined or run 
directly to a loading jetty, whence it is transferred to steamers as 
shown in Fig. 44, 

The crude asphalt has the following composition : 9 

(Test 21) Soluble in carbon disulfide 64.39 per cent 

Non-mineral matter insoluble 3 . 53 per cent 

Mineral matter 2 .08 per cent 

(Test 25) Water 30.00 per cent 



Total 100.00 per cent 

According to Clifford Richardson, 10 the dried crude Bermudez 
asphalt has the following composition : 

(Test i) Color in mass Black 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 7) Specific gravity at 77 F i .05-1 .075 

(Test 16) Volatile at 400 F. in 5 hrs. (dried material). . 5.81-16.05 per cent 

(Test 21 ) Soluble in carbon disulfide 90-98 per cent 

Non-mineral matter insoluble o . 62-6 . 45 per cent 

Free mirteral matter o. 50-3 . 65 per cent 

The crude Bermudez asphalt is melted to drive off the moisture 
and gas. The water which is present is derived from the heavy 
rains and by overflows from the surrounding country. It is not 
emulsified with the asphalt as is the case with the Trinidad deposit. 
The percentage of water varies from 10 to about 40 per cent as a 
maximum. 

Refined Bermudez asphalt tests as follows: 11 

(Test 4) Fracture ; Conchoidal 

(Test 5) Lustre Very bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .06-1 .085 

(Test ga) Hardness on Moh's scale Less than i 

(Test 9^) Penetration at 1 15 F 60 

Penetration at 77 F 20-30 

Penetration at 32 F 3 

(Test 9*) Consistency at 115 F , 7.7 

Consistency at 77 F . 22. 7 

Consistency at 32 F 93. 8 

(Test 9<J) Susceptibility index 62. 5 



VIII SOUTH AMERICA 149 



(Test io) Ductility at 115 F ....................... 14.5 

Ductility at 77 F ........................ u 

Ductility at 32 F ........................ o 

(Test n) Tensile strength at 115 F ................. 0.60 

Tensile strength at 77 F .................. 3.45 

Tensile strength at 32 F .................. 10, 5 

(Test 15*) Fusing-point (K. and S. method) ........... 130-140 F. 

(Test 15*) Fusing-point (R. and B. method) ........... 145-160 F. 

(Test 16) Volatile matter, 325 F., 5 hrs .............. 3.0- 6.0 per cent 

Volatile matter, 500 F., 5 hrs .............. 8 .0-10.0 per cent 

(Test 19) Fixed carbon ............................. 12.9-14.0 per cent 

(Test 21) Solubility in carbon disulfide ............... 92-97 per cent 

Non-mineral matter insoluble .............. i . 5-4.0 per cent 

Free mineral matter ...................... i . 5-6. 5 per cent 

(Test 22) Carbenes ____ . ........................... o.o-i .o per cent 

(Test 23) Solubility in 88 petroleum naphtha ........ 60-75 per cent 

(Test 26) Carbon ................................. 82.88 per cent 

(Test 27) Hydrogen ............................... 10.79 per cent 

(Test 28) Sulfur ................................... 5.87 per cent 

(Test 29) Nitrogen ................................ 0.75 per cent 

Total ............................... 100. 29 per cent 

(Test 33) Solid paraffins ........................... Trace 

(Test 340) Saturated hydrocarbons ................... 23-25 per cent 

(Test yjd) Saponification value ...................... 28 . o per cent 

(Test 380) Free asphaltous acids ..................... 3. 5 per cent 

(Test 38^) Asphaltous anhydrides .................... 2.0 per cent 

(Test 38^) Asphaltenes .............................. 35-3 per cent 

(Test 38^) Asphaltic resins .......................... 14.4 per cent 

(Test 38*) Oily constituents ......................... 39.6 per cent 

La Brea Deposit. This also occurs as an overflow in the form 
of a lake at La Brea, in the Pedernales oil field, on the northwest 
coast of the Island of Capure, in the delta of the Orinoco River, 
some distance east of the Bermudez Lake. It is about 3200 ft. 
long and 100 to 200 yards wide, and is fed by several springs and 
one asphalt cone. Similar deposits on a smaller scale are found on 
the neighboring islands of Paquero and Del Plata, likewise in the 
District of Sucre, where cones of asphalt occur 5 ft high and 30 
ft. wide. 

State of Zulia. 

Maracaibo Deposit. A number of asphalt deposits occur in the 
Inciarte region, in the District of Mara, south of the Limon River, 
60 miles west of the city of Maracaibo. Others occur at La Paz, 
a short distance to the east These are in the form of overflows, 
exuding from springs. More than 100,000 tons were collected 



150 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

during 19011905, but operations have since largely ceased. The 
asphalt was gathered by means of picks and shovels and trans- 
ported in barges down the Limon River to the island Toas at the 
head of the Gulf of Maracaibo, where it was loaded on board 
steamers. It melts at a higher temperature than the Bermudez 
asphalt, and possesses a very strong and characteristic sulfurous 
odor. 

According to Clifford Richardson 12 it tests as follows : 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Very bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .06-1 .08 

(Test 90 ) Hardness, Moh's scale Less than i 

(Test 9^) Penetration at 77 F. ... v 20-30 

(Test 16) Volatile at 325 F., 5 hrs i . 5-6 per cent 

Volatile at 500 F., 5 hrs 4.7-6.0 per cent 

(Test 19) Fixed carbon 15.0-19.0 per cent 

(Test 21) Solubility in carbon disulfide 9 2 ~97 per cent 

Non-mineral matter insoluble 1.4-5.0 per cent 

Free mineral matter i . 5-6 . o per cent 

(Test 22) Carbenes 1.5 per cent 

(Test 23) Solubility in 88 petroleum naphtha 45~55 per cent 

(Test 34) Saturated hydrocarbons 25-30 per cent 



EUROPE 

FRANCE 

Department of Puy-de-D6me (Auvergne). In the vicinity of 
Clermont-Ferrand, seepages of soft asphalt exude from crevices 
in the rock, containing 90 per cent of asphalt, 7 per cent water, and 
3 per cent mineral substances. The exudations are comparatively 
small in amount, and the asphalt has never proved of importance 
commercially. 

At Pont-du-Chateau there occur extensive deposits of rock as- 
phalt, from which soft asphalt seeps in moderately large quantities 
and is caught in subsidiary workings excavated for this purpose. 
Prior to 1914, approximately 100 tons of pure liquid asphalt were 
recovered annually in this manner. This represents practically the 
only locality in Europe where an appreciable quantity of pure as- 
phalt is obtained at the mines. 



VIII EUROPE 151 

ALBANIA 

Selenitza (Sclinitza). At the junction of the Vojutza (Vo- 
jusa) and Sauchista Rivers, extending from the towns of Kanina 
to Berat, in the vicinity of the Bay of Avlona (Valona), there 
occurs a fairly large deposit of moderately hard asphalt in sand- 
stone and conglomerate, in veins s wide as 10 ft. Marine fos- 
sils are associated with this deposit, indicating it to be of animal 
origin. The asphalt breaks with a conchoidal fracture, showing a 
high lustre. It contains between 8 and 14 per cent of mineral mat- 
ter, averaging about 10 per cent. Comparatively large quantities 
have been mined during many centuries. 

GREECE 

Zante. An extensive deposit of asphalt occurs in the southern 
portion of the Island of Zante, in the form of springs and seepages. 
The asphalt is very soft in consistency, having a specific gravity of 
i.oo to i. 02 at 77 F., and carrying but a trace of mineral matter, 
with a fairly large proportion of water in emulsion. The springs 
occur in a region of clay and limestone, more or less saturated with 
petroleum. These deposits have been worked for many generations. 
The asphalt is refined in a crude way by the natives who use it for 
calking the seams of ships, and as a mortar for cementing together 
the stones of buildings, following the same method as practiced 
centuries ago. 

RUSSIA 1S 

Kutais Province (Transcaucasia). In the neighborhood of 
Osurgeti, about 3 km. north of the railroad station Notanebi and 
about 400 m. from the railway (near the villages Yakobi and Na- 
rudcha), there occurs a vein of fairly pure asphalt containing 9.66 
per cent ash. Similarly, at Sakuprisgale brook, near the village of 
Sameho, about 4 km. from the railroad station Notanebi, there is 
found a deposit of pure hard asphalt containing 4.98 per cent ash. 

Tiflis Province (Transcaucasia). In the vicinity of Tiflis, on 
the right bank of the Yora River, southwest of the Cloister of Holy 
David of Garedchi, there occurs a deposit of hard asphalt contain- 
ing 3.86 per cent ash. 



152 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

Uralsk Province (Russia in Asia). In the so-called Kirgisen 
Steppes, near where the rivers Emba and Sagis empty into the Cas- 
pian Sea, there occur asphalt deposits at Imankara and Karamurat; 
also about 4 km. east of Alascha-Kasgen there are found two de- 
posits of pure asphalt, one covering 4300 sq. m. and the other 
1600 sq. m., ranging from a hard to a softer material of elastic 
consistency. 

ASIA 

SYRIA (LEVANT STATES) 

Villayet of Beirut. 14 At Jebel Keferie (Kfarieh), a hill near the 
bend of the Nahr el Kebir, about 40 km. from the sea, on the road 
between Latakia and Aleppo, there occurs a large deposit of asphalt, 
covering an area 1400 by 1500 m., part of which runs quite free 
from mineral contamination (contains as low as y 2 per cent ash). 
It has not been worked to any extent, on account of the difficulty in 
transportation to the coast 

MESOPOTAMIA (IRAQ) 

Deposits of pure asphalt have been reported at the following 
places : 

Hit. Containing 64 per cent asphalt and 36 per cent water. 
The extracted asphalt contained 0.5 per cent ash and 8.3 sulfur, 
fusing-point (R. and B.) 47.5 C., penetration at 77 F. 108. 

Ain el Maraj (near Kerkuk). Containing 79 per cent asphalt 
and 21 per cent water. The extracted asphalt contained 3.8 per 
cent ash and 8.8 per cent sulfur, fusing-point (R. and B.) 64 C., 
penetration at 77 F. 25. 

Ain Ma 9 Moura (Ain Mamurah). Containing 72 per cent as- 
phalt and 28 per cent water. The extracted asphalt contained 0.7 
per cent ash and 8.5 per cent sulfur, fusing-point (R. and B.) 
52.5 C., penetration at 77 F. 73. 

Quijarah, Ramadi and Abu Gir. Minor asphalt seepages have 
been noted. 

ASIATIC RUSSIA 
Sakhalin. 

Province of Nutowo. An asphalt lake, known as the "Great 
Okha Asphalt Lake," occurs in Okha, on the east coast of the Island 
of Sakhalin in a swampy valley, associated with a very thick variety 



VIII ASIA 153 

of petroleum, exuding in the neighborhood. Where the asphalt 
emanates from the springs, it is very soft and sticky, but towards 
the edges of the lake it is hard and brittle. The asphalt has a 
rather strong odor, and contains a substantial quantity of volatile 
matter. As mined, it contains: asphalt 89.7 per cent, ash 1.18 per 
cent and water 9.03 per cent, and has a fusing-point of 73 C. (K. 
and S.) and a penetration at 77 F. of 17. This asphalt occupies 
an intermediate position between Trinidad and Bermudez Lake as- 
phalts. 15 After being air-dried, it carries 0.75 per cent of mois- 
ture, 0.22 per cent of ash, and the balance pure asphalt containing 
0.80 to 0.85 per cent sulfur. It is estimated that at least 400,000 
tons of asphalt, averaging 0.9 per cent of mineral matter, are pres- 
ent in the lake. Up to the present, the deposit has not been devel- 
oped commercially. 16 

PHILIPPINE ISLANDS 
Island of Leyte. 

Several asphalt deposits have been found in this region, one 
near the head of the Butason River, about 6 miles from the Barrio 
of Campocpoc, on the northwestern coast of the island, and another 
near the town of Villaba. 17 These occur in limestone and sand- 
stone, and extend over an area 12 miles long. Outcrops of various 
grades of asphalt have been reported, including the solid, viscous 
and liquid types. Both pure and rock asphalts are found, the latter 
carrying a variable proportion of sand. Two varieties of pure, 
hard asphalt were examined by the author, one having a black color 
in mass, and a glossy, black, conchoidal fracture : another having a 
dark brown color in mass, w T ith a hackly, dull fracture. They tested 
as follows: 

Black Asphalt Brown Asphalt 

(Test 4) Fracture Conchoidal Hackly 

(Test 5) Lustre Bright Dull 

(Test 6) Streak on porcelain Black Yellowish brown 

(Test 7) Specific gravity at 77 F 0.978 

(Test 9^) Penetration at 77 F 10 2 

(Test gc) Consistency at 77 F 31.7 Above i oo 

(Test 100) Ductility at 77 F # o 

(Test 15*) Fusing-point (K. and S. method) 287 F. 138 F. 

(Test 1 6) Volatile at 500 F., 5 hrs 3 per cent 1 . 15 per cent 

(Test 19) Fixed carbon 10. 5 per cent 9.4 per cent 

(Test 21) Soluble in carbon disulfide 98 per cent 99 per cent 

Mineral matter 2 per cent i per cent 

(Test 37*) Saponifiable matter o per cent o per cent 



154 NATIVE ASPHALTS OCCURRING IN FAIRLY PURE STATE VIII 

The brown variety is unique. It is somewhat similar in physical 
properties to ozokerite, but it is very much more friable. When 
melted it turns black in mass, becoming lustrous (although it still 
shows a yellowish brown streak). It has been marketed under the 
name "leyteite." The black asphalt is not classed as an asphaltite 
in view of its comparative softness at 77 F. These deposits have 
not yet been exploited commercially. 



CHAPTER IX 

NATIVE ASPHALTS ASSOCIATED WITH MINERAL 

MATTER 

This chapter will include the principal deposits of natural as- 
phalts containing 10 per cent and over of associated mineral matter, 
based on the dry weight. Such deposits include veins, strata and 
lake formations. 

NORTH AMERICA 

UNITED STATES 1 
Kentucky. 

All the deposits in the State of Kentucky are composed of sand 
and sandstone, carrying between 4 and 12 per cent of soft asphalt 
filling the interstices. 2 These deposits occur in strata from 5 to 40 
ft. thick, along the eastern and southeastern border of the coal field 
in Hardin, Grayson, Breckinridge, Edmonson, Hart, Warren, But- 
ler, Logan, and other adjoining counties. 

Hardin County. A deposit of sand asphalt occurs a few miles 
northeast of Summit, in the southwestern portion of Hardin County. 

Carter County. This deposit occurs one-half mile southeast of 
the town of Soldier, and consists of unconsolidated quartz grains 
held together by 4 to 10 per cent of asphalt, which is compara- 
tively soft and contains a goodly proportion of volatile matter. 

Breckinridge County. This deposit is located from 2 to 4 miles 
south of Garfield, and is composed of unconsolidated quartz grains 
carrying 4 to 8 per cent of asphalt It forms a hillside ledge about 
14 ft. thick with an overburden of 10 to 20 ft. The deposit has 
not been worked to any great extent in recent years, although for- 
merly it was of considerable interest in the paving industry. Other 
prospects occur in this neighborhood, but these have not been de- 
veloped* 

Grayson County. Two deposits have been worked in this lo- 
cality in the vicinity of Big Clifty and Grayson Springs Station, one 

155 



156 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

3 miles southwest, and the other 9 miles north of Leitchfield. The 
former occurs in a stratum 5 ft. thick, impregnated with 6 per cent 
of asphalt, in an unconsolidated quartz sand. The second was for- 
merly one of the most active mines in Kentucky, but has now been 
idle for a number of years. It consists of a stratum 10 ft. thick, 
carrying 7-12 per cent of very soft asphalt. A number of seepages 
are in evidence along the side walls of the quarry and since the 
asphalt contains a large proportion of volatile matter, they soon 
harden on exposure to the weather. Some of the seepages exam- 
ined by Richardson contained 30 to 65 per cent of mineral matter, 
the extracted asphalt showing a penetration of between 35 and 45 
at 77 F., and yielded 12 per cent of fixed carbon. Another deposit 
occurs at Tar Hill. 

Edmonson County. Deposits of asphaltic sandstone, estimated 
to exceed 200 million tons, covering over 7000 acres, are located 
about 6 miles due west of Brownsville and about 12 miles northeast 
of Bowling Green. The properties adjoin both Bear Creek and 
Green River, being located on both sides of the former and north 
of the latter. Soil overburden of 5 to 40 ft. covers a horizontal 
stratum of rock asphalt 15 to 30 ft. thick. The latter analyzes as 
follows : 

(Test 21) Soluble in carbon disulfide 4.22- 9.00 per cent 

Matter insoluble 95.64- 90.91 per cent 

(Test 25) Moisture at 105 C o. 14- 0.09 per cent 

100.00 100.00 per cent 

At the present time the only deposits in the State of Kentucky 
worked to any extent occur at Kyrock and at the town of Asphalt, 
on the Nolin River, about 10 miles west of the celebrated Mam- 
moth Cave, near Brownsville. They consist of a stratum of fine sand 
impregnated with 8 to 10 per cent of asphalt, occurring in irregular 
beds 5 to 36 ft. thick in a horizontal stratum below an overburden 
of clay and unimpregnated sandstone, 6. to 30 ft. thick. The over- 
burden is removed by a hydraulic pressure line, and where it does 
not yield to this, a steam shovel is used. The rock asphalt is re- 
moved by quarrying as illustrated in Figs. 45 and 46, and conveyed 
by a gravity tramway to a crusher which reduces the rock from 5- to 
loin, fragments to lumps about the size of an egg. It is then 



NORTH AMERICA 




157 



Courtesy Kentucky Rock Asphalt Co. 
FIG. 45. Asphalt Deposit at Kyrock, Kentucky. 




Courtesy Kentucky Rock Asphalt Co. 
FIG. 46. Hillside Quarry of Kyrock Asphalt Deposit 



158 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

passed through a battery of pulverizers, illustrated in Fig. 47, which 
further reduces the rock asphalt to small grains about the size of 
corn meal. A bucket conveyor transports the asphalt to barges on 
the Nolin River, which in turn are conveyed down to the Green 
River, and up Barren River to the railroad at Bowling Green. It 
is used exclusively for paving purposes, and is reported to give ex- 
cellent results. 

In preparing the paving mixture, rocks of varying asphalt con- 
tent are blended to obtain a product carrying uniformly 7 per cent 
( y per cent) asphalt soluble in carbon disulfide. In applying 




Courtesy Kentucky Rock Asphalt Co. 
FIG. 47. Pulverizing Kentucky Rock Asphalt at Kyrock, Kentucky. 

the asphalt, it is spread loosely over the primed base in a layer 
about 3 in. thick over macadam (9 to 10 in. thick), or a concrete 
base (6 in. thick), and compacted cold with a 1 5-ton steam roller, 
to a thickness of 2 in., provided, however, that the air temperature 
is not lower than 60 F. If necessary, the surface may be planed 
after the first rolling, by which the excess material is shaved from 
the high places and deposited in the depressions. The product has 
the advantages of not requiring a hot mixing plant. It presents 
a rather gritty surface, which prevents slipping, does not become 
svavy under traffic, and may be readily repaired. To offset these, 
it has the disadvantage of being marked by traffic for several days 
after being laid, and moreover it is claimed that the drip from 



IX NORTH AMERICA 159 

autos readily washes out the asphalt content, leaving unconsoli- 
dated sand. 

Warren County. Several deposits of sand asphalt are located 
at Youngs Ferry on the Green River, 12 miles north of the town of 
Bowling Green. One occurs in a bed about 10 ft. thick, and car- 
ries between 6 and 9 per cent of asphalt A second consists of a 
vein 5 to 15 ft. thick containing about the same percentage of as- 
phalt. Both are undeveloped. The extracted asphalt shows a 
penetration at 77 F. of 200, and much volatile matter (13 per 
cent at 400 F. in seven hours). 

Logan County. A quarry has been opened up about 5 miles 
northeast of Russellville, exposing about 15 ft. of asphaltic sand- 
stone in a bed about 100 ft. long. The rock carries about 7 per 
cent of asphalt, which shows very much less volatile matter than 
the preceding (about 4 per cent loss at 325 F. in five hours). This 
mine is no longer active. 

Missouri. 3 

Lafayette County. A bed of asphaltic sand occurs I J^ miles 
northwest of Higginsville, carrying 8^ per cent of asphalt, asso- 
ciated with sandy shale. This deposit has not been worked com- 
mercially. 

Indiana. 

While drilling for oil at Princeton, a bed of asphalt several feet 
thick was found 100 ft. below a vein of coal. Seepages of liquid 
asphalt have also been reported in a well in the neighborhood. 
None of these have been developed.* 

Oklahoma. 

This state is one of the richest asphalt-bearing centers in the 
United States. Asphalts are found in both the liquid and solid 
forms, occurring as springs, seepages and rock impregnations. Prac- 
tically all the deposits are found in the southern portion of the state, 
between the 35th parallel of north latitude, and the Red River on 
the south, and included between the Arkansas line on the east, to the 
city of Granite, Oklahoma, on the west. This area is shown in 
Fig. 48, and includes deposits or prospects in the following counties : 
Comanche, Jefferson, Stephens, Garvin, Carter, Murray, Love, 
Marshall, Johnston, Pontotoc, Atoka, McCurtain and Leflore. 



160 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



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164 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



The deposits consist of asphaltic sands, asphaltic limestone, mix- 
tures of the two, and rarely asphalt impregnated shale. The prin- 
cipal occurrences are included in Table XVL 5 

In the majority of cases the asphaltic impregnation is of liquid 
to semi-liquid consistency, having a comparatively low fusing-point. 
It is contended by some authorities that the vast deposits of sand 
asphalt previously constituted oil-sands which have been laid bare 
by the agencies of erosion, faulting, crumpling and upturning of the 



ASPHALT. 




I* ! AgptaH Sects. 

FIG. 48. Map of Asphalt Region in Oklahoma. 

strata, so that the lighter oils and gases have escaped into the air, 
leaving the sand impregnated with the comparatively non-volatile 
asphaltic constituents. Most of the deposits occur along pronounced 
fault lines, although faulting is not essential, since certain deposits 
haye become impregnated by the uprising of asphalt-bearing pe- 
troleum from regions below, through the porous sandstone or 

limestone. 

A characteristic feature of these deposits is the sand grains, 
which are round and unconsolidated, being held together by the 
asphalt filling the voids. When the asphalt is extracted the grains 



IX 



NORTH AMERICA 



165 



fall apart, and show the same general characteristics as an ordinary 
petroleum-bearing sand. 

The extent of these deposits has been variously estimated from 
2 to 13 million tons. 6 

Most of the asphalt mined in Oklahoma has been used for pav- 
ing purposes, and the author has seen many satisfactory pavements 
laid through the state which have withstood the wear and tear 
of traffic, also exposure to the elements. It is generally necessary 
to modify the rock asphalts either by combining the products ob- 
tained from different deposits, or by incorporating pure sand, until 
a proper balance is obtained between the asphalt and the mineral 
constituents. In general, the best results have been obtained with 
mixtures containing 7 to 10 per cent of asphalt in the finished paving 
composition. 

Numerous water-extraction plants have been erected to separate 
the asphalt from the sand, but most of these have proven unsuc- 
cessful, since the extraction process raises the price of the refined 
asphalt so that it is unable to compete with petroleum asphalts ob- 
tained from other sources in the neighborhood. 

Tests made with sand asphalt taken from the quarry in Carter 
County, Sec. 12 and N y 2 Sec. 13, T 3 S, R 2 W, 18 miles north- 
west of Ardmore, indicated the following. The dry sand asphalt 
contained 12.5 per cent of pure asphalt having a fusing-point (K. 
and S. method) between 65 and 69 F. On subjecting it to the 
water-extraction process, the following results were recorded : 





Products 
Recovered, 
Per Cent. 


Asphalt 
Content, 
Per Cent. 


Total Pure 
Asphalt, 
Per Cent. 




6 


95 


.7 


Impure asphaltic residue 


*? 


60 


1.8 


Separated sand waste 


9! 


2# 


2.3 








2.7 










Asphalt in crude rock 






12.5 










Total 


IOO 















On boiling the crude rock with water, impure asphalt rises to the 
surface, and the "sarid waste" settles to the bottom. Upon dehy- 



166 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



drating the impure asphalt, more sand settles out, constituting what 
is designated u impure asphaltic residue." The pure asphalt drawn 
off from this residue is termed "asphalt recovered." 

The "asphalt recovered" contained 5 per cent of mineral matter 
and tested as follows: 

(Test gb) Penetration at 32 F 85 

Penetration at 77 F Over 360 

Penetration at 115 F Too soft 

(Test 9<r) Consistency at 32 F 10.0 

Consistency at 77 F i . 5 

Consistency at 115 F o.o 

(Test gd) Susceptibility index 15 

(Test 1 5*) Fusing-point (K. and S. method) 65-69 F. 

(Test 15*) Fusing-point (R. and B. method) 78-87 F. 

(Test 16) Volatile at 500 F. in 5 hrs 10 per cent 

Examination of Residue (from Test 16) 

(Test 9^) Penetration at 32 F 7 

Penetration at 77 F 58 

Penetration at 115 F 250 

(Test 9^) Consistency at 32 F 7 2 -*> 

Consistency at 77 F 10.7 

Consistency at 115 F i . I 

(Test gd) Susceptibility index 63. i 

(Test io) Ductility at 77 F Over 100 

(Testi5*) Fusing-point (K. and S. method) ii5F. 

(Test i$b) Fusing-point (R. and B. method) 131 F. 

Upon evaporating the "asphalt recovered" at 250-260 C, the 
following figures were recorded : 



Total Loss, Per Cent. 



20 

25 
27 



Fusing-point F. 
(Test 15*) 



120 
125 

H7 
165 



Penetration at 77 F. 
(Test gb) 



40 

19 
10 



A sample of the "asphalt recovered" upon being blown with dry 
air at 300 C. for nine hours, lost 23 per cent in weight, showed a 
fusing-point of 165 F., and a hardness at 77 F. of 38.0 (Test 9^), 
corresponding to a penetration at 77 F. of 8 (Test gb). It is ap- 
parent that the extracted asphalt is scarcely affected by blowing, and 
thus differs from asphalts obtained upon distilling petroleum. It 



IX NORTH AMERICA 167 

has been reported that blowing decreases the percentage of asphal- 
tous acids, anhydrides, oily constituents and resins. The molecular 
weight of the resins increases from 733 to 1012 and that of the 
asphaltenes from 2219 to 4690 during the blowing process. 7 It 
has been further corroborated by the author's observations on paints 
made from the extracted sand asphalt, which were found to be 
highly resistant to atmospheric oxidation. A sample spread on 
cloth and exposed to air indoors for about a year, showed scarcely 
any diminution in tackiness. 8 Petroleum asphalts of the same con- 
sistency when tested in a similar manner, dry out in a much shorter 
time. 

A mixture containing 82' per cent of the u asphalt recovered" 
fluxed with 1 8 per cent of grahamite, showing the same fusing-point 
(165 F.), tested as follows: 

(Test 7) Specific gravity at 77 F i .09 

(Test 9^) Penetration at 1 15 F 26 

Penetration at 77 F 17 

Penetration at 32 F 9 

(Test 9*) Consistency at 1 1 5 F 14. 7 

Consistency at 77 F 27. i 

Consistency at 32 F 65 . 4 

(Test 9</) Susceptibility index 30.7 

(Test io) Ductility at 115 F 4.5 

Ductility at 77 F i.o 

Ductility at 32 F o.o 

(Test 11) Tensile strength at 115 F 1.8 

Tensile strength at 77 F 6.5 

Tensile strength at 32 F 9.5 

(Test 15*) Fusing-point (K. and S. method) 165 F. 

(Test 15^) Fusing-point (R. and B. method) 183 F. 

(Test 16) Volatile at 500 F. in 5 hrs o. 5 per cent 

Arkansas. 

Seven to eight known deposits of asphalt occur in southwestern 
Arkansas, in Pike and Sevier Counties, only one of which has been 
developed into a mine producing commercial quantities. This is 
located 2 l /2 miles south-southeast of Pike, in Pike County. The 
asphalt impregnates nearly horizontal strata of unconsolidated 
sand, except in one locality, where it impregnates gravel. The veins 
run from i in. to 12 ft. thick. 

Pike County. The most important deposit occurs on the west 
side of the road connecting the towns of Pike and Delight, about 
2 y 2 miles south-southeast of Pike. It has been mined in an open 



168 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

cut 100 ft wide, 200 ft. long and 15 ft. deep. The sand carries 
from 5 to 1 6 per cent asphalt, averaging 7^2 per cent, and is used 
for paving purposes. Prospects occur about 4 miles north-north- 
west of Delight in a bed 3 to 5 ft. thick, carrying up to 17 per cent 
asphalt associated with sand carrying a few nodules of iron pyrites; 
also about I mile northeast of Murfreesboro, on the east bank of 
Prairie Creek, in which the asphalt impregnates gravel. 

Sevier County. Prospects occur y* mile southeast of Lebanon, 
alongside of the road adjoining the Salina River bottom, in len- 
ticular formations up to i ft. thick; another about 2 l / 2 miles west- 
southwest of Lebanon; another on the south side of the road 4 
miles west-southwest of Lebanon; and still another 6y 2 miles west- 
southwest of Lebanon along the road just northwest of Moody 
Shoal Ford on Cossatot River. 

Alabama. 

An area occurs in northern Alabama measuring about 72 miles 
by 8 miles in which i to 15 per cent of asphalt is associated with 
unconsolidated sand granules. It extends through the following 
counties : 10 

Colbert County. A fairly extensive deposit of sand asphalt has 
recently been developed near Florence, on the banks of the Ten- 
nessee River, in the vicinity of Muscle Shoals, which has been used 
in the vicinity for paving purposes. Another deposit occurs i mile 
south of Margerum, on the Southern Railroad, w r ithin an area 3 
miles square, consisting of asphaltic limestone. Others have been 
reported 2 miles southeast of Cherokee, consisting of asphaltic 
limestone and sand; likewise sand asphalt deposits i to 7 miles east 
of Littleville, and at Leighton and Russelville (extending into 
Franklin County). 

Lawrence County. Asphalt sand is found at Wolf Springs on 
the summit of Little Mountain, about 6 miles southwest of Town 
Creek Station on the Southern Railroad. Another deposit occurs 
at Caddo, midw r ay between Moulton and the Morgan County line, 
in the southeast section. 

Morgan County. A sand asphalt deposit occurs about 3 miles 
northwest of Flint Station on the L. & N. Railroad, and another 
in the vicinity of Hartsville, to the east and southeast thereof. 



IX NORTH AMERICA 169 

Louisiana. 

Lafayette Parish. A sand asphalt deposit has recently attracted 
attention about 5 miles from Lafayette, covering about 50 acres on 
the surface. 11 

Texas. 12 

Montague County. Deposits are reported 3 to 3 J4 miles north- 
east of the City of St. Jo, carrying between 5 and 1 1 per cent of 
asphalt, averaging in the neighborhood of 7 per cent, although the 
percentage varies in different localities. They contain sandstone, 
or a mixture of sandstone and limestone, but are of no commercial 
importance. 

Burnet County. This occurrence is at Post Mountain near the 
town of Burnet, and consists of an asphaltic limestone, containing 
about 10 per cent of asphalt of a very soft consistency (having a 
penetration of 20-250 at 77 R). 

Uvalde County. The most important Texas deposits are found 
in the southwestern part of this county near Cline, about 18 to 25 
miles west of the city of Uvalde, in the region of the Anacacho 
Mountains. They consist of limestone, carrying 10 to 20 per cent 
of asphalt, averaging about 15 per cent Crystalline calcite is pres- 
ent, also numerous fossil remains of molluscs, indicating the asphalt 
to be of animal origin. The deposits have been traced for several 
miles, but their exact extent is not accurately known. A large quan- 
tity has been quarried, and from recent reports the mines are still 
being operated. The impregnating asphalt is quite hard, showing 
a conchoidal fracture and brilliant lustre. It has a moderately 
high fusing-point, and analyzes: carbon 81 per cent, hydrogen 12 
per cent, sulfur 6^2 per cent, nitrogen l /2 per cent; total 100 per 
cent. The rock asphalt is too hard for a paving material if used 
alone. It is therefore mixed with about 25 per cent of trap rock 
and the requisite amount of flux. The mixture is adapted to be 
rolled cold in surfacing a pavement. One ton will cover 20 sq. yd. 
I in. thick. Fig. 49 illustrates the principal mine, with about 80,000 
tons of asphalt rock blasted loose and ready to be loaded into the 
cars by the steam shovel. It is then transported to the mixing and 
crushing plant. Fig. 50^ shows the equipment for crushing and 
screening the rock asphalt; Fig. $oB the device for mixing the trap 



170 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



rock with the rock asphalt; and Fig. 5oC shows a 42 cu. ft. capacity 
twin pug-mill which is used for pulverizing the asphalt. The pure 
asphalt extracted from the rock has been marketed under the name 
"litho-carbon" 13 which may also be blown. This constitutes the 
most important deposit in Texas. 




Courtesy Uvalde Asphalt Compan;. 
FIG. 49. Rosk-asphalt Quarry in Uvalde County, Texas. 

Litho-carbon shows the following tests : 



Color in mass ..... . . . . ...... ................. Black 

Fracture ................................... Conchoidal 

Lustre... ...... ..... ....................... Bright 

Streak ..................................... Brownish black 

Specific gravity at 77 F ...................... i ^9 

Penetration at 115 F ........ ................ 16 

Penetration at 77 F ......................... 4 

Fusing-point (K. and S. method) .............. 1 16 F. 

Volatile at 500 F., in 5 hours ................. 2.76 per cent 

Soluble in carbon disulfide ..................... 96 . 35 per cent 

Non-mineral matter insoluble ................. 0.75 per cent 

Mineral matter ........... ................... ^-9Q per cent 



(Test i) 

(Test 2) 

(Test 3) 

(Test 4) 

(Test 7) 

(Test 9^) 

(Test 15*) 
(Test 16) 
(Test 21) 



100 . oo per cent 
(Test 23) Soluble in 88 petroleum naphtha ............. 53 .08 per cent 

Other deposits of the same general character are found in the 
neighborhood. One 20 miles south-southwest of Uvalde and 5 



IX 



NORTH AMERICA 



171 





OS 

a 



bfl 



we 
5! 



p 

0- 



1 a 

IB 

a> 



2 
75 

tD 

i 



172 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

miles south of the preceding quarry showed 12 per cent of asphalt 
with 17 per cent of fixed carbon. 

Kinney County. The Uvalde deposits extend westward into 
Kinney County, with outcroppings near Blewett, where mining op- 
erations have been undertaken. 

Anderson, Jasper, and Cooke Counties. Minor deposits are 
reported in these counties, but are of no commercial value. 1 



14 



Utah. 

Carbon County. 19 A deposit of asphaltic limestone occurs at 
the head of the right-hand branch of Pie Fork, a canyon northwest 
of the town of Clear Creek. The rock is non-uniform in composi- 
tion, some containing between 6 and 14 per cent of asphalt (having 
a penetration at 77 F. of 7 to 15), and some as high as 75 per 
cent (showing a penetration at 77 F. of 45) with scarcely any 
fixed carbon. Another deposit of asphaltic sand has been reported 
8 miles from Sunnyside on the tributaries of Whitmore Canyon, 
in the Brook Cliffs on the West Tavaputs Plateau, carrying 1 1 per 
cent of soft asphalt, which upon being extracted tested as follows: 

(Test 16) Volatile at 325 F., 5 hrs 6.6 per cent 

(Test 19) Fixed carbon 5.0 per cent 

(Test 23) Soluble in 88 petroleum naphtha 91 . 8 per cent 

Utah County. A large area underlaid with asphaltic limestone 
occurs just north of Colton, and south of Strawberry Creek, extend- 
ing from Antelope Creek on the east to Thistle on the west. The 
principal deposit is at the town of Asphalt, carrying 12 per cent of 
asphalt. 

Grand County. At the head of the West Water Canyon about 
20 miles north of the town of West Water, there is an asphaltic 
limestone deposit containing 50 per cent asphalt and 50 per cent 
limestone. Investigations indicate that this asphalt is a progenitor 
of gilsonite. The extracted asphalt is reported by Clifford Rich- 
ardson to test as follows : 

(Test 7) Specific gravity at 77 F 1 .037 

(Test oi) Penetration at 77 F 22 

(Test 16) Volatile at 212 F 2.8 per cent 

(Test 19) Fixed carbon ' 8 .o per cent 

(Test 23) Soluble in 88 petroleum naphtha 88.7 per cent 



IX NORTH AMERICA 173 

Vint a County. The largest deposit of asphaltic sandstone 
occurs 3 to 4 miles southwest of Vernal, north of the Green River, 
between the Ashley and Uinta Valleys, in an outcrop about n l / 2 
miles long, known as "Asphalt Ridge." 16 It contains 8 to 15 per 
cent by weight of asphalt, averaging 11^2 per cent A typical 
specimen analyzed as follows: 

(Test 21) Soluble in carbon disulfide 12.8 per cent 

Mineral matter on ignition 86.45 per cent 

(Test 16) Volatile at 105 C. in i hour 0.20 per cent 

The extracted asphalt tested as follows: 

(Test 7) Specific gravity at 77 F 0.980 

(Test 19) Fixed carbon 7.1 per cent 

* 

The asphalt' has been used successfully just as it is mined, for 
paving the streets of Vernal. 

Another deposit, or rather a series of deposits, occur in Argyle 
Creek, a tributary of the Minnie Maud Creek, which in turn flows 
into the Green River about 20 miles south of Ouray. The ma- 
terial consists of an asphaltic sandstone, exploited under the name 
"argulite," carrying between 8 and 10 per cent of asphalt. The 
extracted asphalt tests as follows : 

(Test 5) Lustre Bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F o. 997-1 .013 

(Test 9^) Penetration at 77 F 14 

(Test 16) Volatile at 325 F. in 5 hrs 25. 8 per cent 

(Test 19) Fixed carbon 8.55 

(Test 23) Soluble in 88 petroleum naphtha , 88 

(Test 26) Carbon 89.9 per cent 

(Test 27) Hydrogen 9.0 per cent 

(Test 28) Sulfur o.o per cent 

(Tests 29 and 30) Nitrogen and oxygen i . i per cent 



Total 100.0 per cent 

(Test 340) Saturated hydrocarbons 25 per cent 

Wyoming. 

Fremont County. Asphalt and semi-solid asphalt seepages 
were used for many years as fuel by shepherds on Copper Moun- 
tain in section T. 4 N., R. 9293 W., in northeastern Fremont 
County. 



174 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



California, 17 

Mendocino County. Deposits of asphaltic sand are found 2 
miles north of the town of Point Arena and l / 2 mile from the coast, 
carrying between 6 and 7 per cent of asphalt. A similar deposit 
occurs just north of Port Gulch. 

Santa Cruz County. Large deposits of asphalt sand occur 4 to 




FIG. 51. Sand Asphalt Quarries in Santa <Jruz county, v;ai. 

6 miles northwest of the city of Santa Cruz, near the summit of 
Empire Ridge, a spur of the Santa Cruz Mountains, 3^ miles 
from the coast. A number of quarries have been opened up in this 
region, and the product used for constructing pavements in Santa 
Cruz and San Francisco. The rock contains between 10 and 17^ 
per cent asphalt of variable hardness, containing a substantial pro- 
portion of volatile matter. The veins vary from 2 to 32 ft thick, 



IX 



NORTH AMERICA 



175 



as shown in Figs. 51 and 52. Three strata are found, an upper 
8 ft thick containing 2-3 per cent asphalt, a middle one 32 ft. 
thick containing 14 per cent asphalt, and a lower 25 ft. thick carry- 
ing 1 6-1 8 per cent asphalt. 

Monterey County. Several deposits of asphaltic sandstone are 
scattered throughout the Salinas Valley. A prospect occurs about 
10 miles from King City, composed of particles of quartz, feldspar 
and mica, impregnated with a varying percentage of asphalt. An- 
other deposit occurs 7 miles southeast of Metz at the head of 




A-UJ. 5*. oanu -mspnair uuarnes in Santa Cruz County, Cal. 

Chelone Creek, of the same general character. A large vein, about 
125 ft. thick and 3 miles long, has been reported near San Ardo, 
composed of coarse quartz grains, and a little feldspar, impregnated 
with a small percentage of asphalt. 

San Luis Obispo County. Sand asphalt deposits occur about 
80 miles southwest of the town of San Luis Obispo, consisting of 
a number of actively worked quarries. The rock is fine grained, of 
even texture, consisting mostly of quartz, with a small quantity of 
feldspar. The percentage of asphalt varies from 8 to 18 per cent, 
averaging about 10. 



176 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

+ 

Santa Barbara County. Santa Maria Region. Associated 
with the pure asphalt deposits already described* zones of asphalt- 
impregnated shale have been reported on the western slope of the 
Azufre Hills, containing 30 to 40 per cent of asphalt. 

Sisquoc Region. Deposits of sand asphalt occur in the neigh- 
borhood of the town of Sisquoc, carrying between 14, and 18 per 
cent of asphalt. The largest vein occurs in Bishop's Gulch, about 
100 ft. thick, running fairly uniform in composition. 'Some time 
ago an attempt was made to remove the asphalt by extraction with 
solvents, but the process proved too costly and had to be abandoned. 
Similar deposits are found in the neighborhood of La Brea Creek, 
where a vein of sand asphalt occurs 20 to 60 ft. thick; also at Los 
Alamos Creek. 

Gaviota Region. A prospect has been reported in this locality 
consisting of a bed of sandstone and conglomerate about 25 ft. 
thick, containing 7 to 8 per cent of asphalt. 

Mores' Landing, This deposit is found on the seacoast about* 7 
miles west of Santa Barbara, occurring as veins and irr$gul|| masses 
in massive sandstone cliffs, at least too ft. thick. Acceding to 
Eldridge it contains 30 to 60 per cent of asphalt and has a strong 
resemblance in structure, brilliancy, and fracture to gilsonite, al- 
though it is very much softer in consistency. 

La Patera Region. A vein of asphalt of historical interest only, 
occurs about 10 miles west of Santa Barbara, close to the coast. It 
varies in width from 2 to 12 ft, with a number of lateral branches 
several inches thick. The asphalt is associated with 30 to 50 per 
cent of mineral matters composed of shale, sand, and clay. It is 
stated that 30,000 tons have been removed from this mine, testing, 
when dried, as follows : 18 

(Test 4) Fracture Irregular 

(Test 5) Lustre Dull 

(Test 6) Streak *.-. Black 

(Test 7) Specific gravity at 77 F i .38 

(Test 94) Hardness on'Moh's scale 1 

(Test 9$) Penetration at 77 F o 

(Test 16) Volatile at 400 F., 5 hrs 2, 5 per cent 

(Test 19) Fixed carbon 14,9 per cent 

(Test a i) Soluble in carbon disulfide Approx. 50 per cent 

Mineral matter. . ,. i v Ab ut 5 per cent ., 

(Test 13) Soluble in 88 petroleum naphtha 21 , 6 per cent 

(T*stl8) Sulfur ^ ,-, 6,2 per cent >\ 

(Test 34*) Saturated hydrocarbons 8. i ; per cent r 



IX 



NORTH AMERICA 



177 



Carpinteria Region. This deposit, composed of asphaltic sand 
about 15 ft. thick, lying along the ocean's shore at Benham, 2 miles 
southeast of Carpinteria, is illustrated in Fig. 53. It contains 18 to 
20 per cent of asphalt filling the interstices of unconsolidated quartz 
grains. Some time ago a process was installed for extracting the 
asphalt with water, but this never proved successful commercially. 




FIG, 53. Asphaltic Sand on the Shore at Carpinteria, Cal. 

Orange County* Bituminous sands have been reported 4 miles 
southwest of Chino, in a layer about 6 ft. thick, containing varying 
percentages of asphalt. 

CANADA 
Alberta Province. 

McMurray Region. Vast deposits of asphaltic sands occur on 
both banks of the Athabaska River, and its tributary, the Clear 
Water River, covering probably not less than 750 square miles. 19 
The deposit varies in thickness to a maximum of 225 ft. Character- 
istic views of the outcrop on the Athabaska River are shown in 
54 (A and B). The material contains 12 to 20 per cent as- 



178 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

phalt, averaging between 15 and 18 per cent, associated with an 
unconsolidated sand consisting of betw r een 93 and 99 per cent pure 





(B) 

Courtesy S. C. Ells. 

FIG. 54. Asphaltic Sand on Banks of Athabaska River, Alberta, Can. 

silica. A marked variation in the size of the sand grains is charac- 
teristic of almost every exposed section of the deposit, ranging from 
40 to 80 mesh. The asphalt is amenable to the water extraction 



IX NORTH AMERICA 179 

process. A specimen of the extracted asphalt examined by the 
author tested as follows: 

(Test 7) Specific gravity at 77 F 1.022 

(Test 9^) Penetration at 77 F Too soft for test 

Penetration at 32 F 120 

(Test 9^) Consistometer hardness at 1 15 F o.o 

Consistometer hardness at 77 F o.o 

Consistometer hardness at 32 F 2.7 

(Test io*) Ductility at 115 F 2.0 

Ductility at 77 F 7?o 

Ductility at 32 F 12.5 

(Test 154) Fusing-point (K. and S. method) 50 F. 

(Test 15^) Fusing-point (R. and B. method) 63 F. 

(Test 16) Volatile at 500 F. in 5 hrs 17.9 per cent 

Volatile at 325 F. in 5 hrs * 1 1 . 2 per cent 

(Test 19) Fixed carbon 7,23-10. 55 per cent 

(Test 21) Soluble in carbon disulfide. 97.3 per cent 

Mineral matter 2.7 per cent 

(Test 23) Soluble in 88 petroleum naphtha 78 . 2 per cent 

(Test 26) Carbon 84.49 per cent 

(Test 27) Hydrogen 1 1 . 23 per cent 

(Test 28) Sulfur 2 . 73 per cent 

(Test 29) Nitrogen 0.04 per cent 



Total 98 .49 per cent 

(Test 340) Saturated hydrocarbons 39.6 per cent 

The, non-volatile matter tested as follows : 

Residue at 
500 F. 325 F. 

(Test 7) Specific gravity at 77 F 1.028 1.021 

(Test gb) Penetration at 115 F no 

Penetration at 77 F 62 262 

Penetration at 32 F 18 

(Test 9^) Consistency at 115 F 3.7 

Consistency at 77 F 8.5 

Consistency at 32 F 49 . 3 

(Test gd) Susceptibility index 36. 5 

(Test lot) Ductility at 115 F 34. 5 +100 

Ductility at 77 F 45.0 +100 

Ductility at 32 F 0.5 

(Test 1 1) Tensile strength at 115 F 0.3 

Tensile strength at 77 F 1.5 

Tensile strength at 32 F 25. 5 

(Test 150) Fusing-point (K. and S. method). 125 F. 106 F. 

(Test 15*) Fusing-point (R. and B. method) 142 F. 121 F. 

(Test 19) Fixed carbon 12.33 P 61 " cent 8.99 per cent 

A sample of extracted Alberta asphalt having a K. and S. 
fusing-point of 84 F. was blown 2 l / 2 hours at 500 F. during which 



ISO ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

process it lost 17 per cent in weight, and the resultant product tested 
as follows: 

(Test 5) Lustre. Bright'and tough 

(Test g&) Penetration at 115 F 5.6 

Penetration at 77 F 3.0 

Penetration at 32 F i .o 

(Test 150) Fusing-^point (K. and S. method) 208 F. 

A duplicate sa'mple was evaporated in air until it lost exactly 
1 7 per cent by weight, whereupon the residue showed a f using-point 
of 128 F. (K. and S.), demonstrating that the material was sus- 
ceptible to the process of blowing. 

The crude asphalt, after being tempered with additional pure 
sand to reduce the percentage of asphalt, has given successful results 
for paving purposes in Edmonton, Canada. ( 

Manitoba Province. Similar deposits are reported to occur in 
the Clear River District in this province. 20 

MEXICO 

States of Vera Cruz and Tamaulipas. Several deposits of 
sand asphalt have been reported in the neighborhood of Tampico 
and Vera Cruz, containing 8 to 14 per cent of asphalt, but none 
have been developed commercially. 

CUBA 2 * 

Province of Matanzas. Semi-solid asphalts have been mined for 
many years at the bottom of Cardenas Harbor, 22 The most im- 
portant deposit, known as the u Constancia Mine," occurs about 12 
ft. below the level of the water, and is consequently mined with 
difficulty. Other deposits of semi-liquid asphalt containing more or 
less mineral matter, occur at the mouth of the La Palma River, 
about 20 miles from Cardenas; also near Sabanilla de la Palma, 
about 30 miles east of Cardenas and 4 to 5 miles west of Hato 
Nuevo. Analyses are not available. 

Province of Pinar del Rio. Deposits of sand asphalt have been 
reported at Bahia Honda and Mariel, in the neighborhood of 
Mariel Bay> also at Vuelta Abajo. No analyses are available. 

Province of Havana. An extensive deposit approaching glance 



IX NORTH AMERICA 181 

pitch in properties, known as the u Angelo Elmira Mine/' has been 
found near Bejucal, about 18 miles south of Havana, associated 
with mineral matter composed of calcium carbonate, silica, and sili- 
cates, which, according to Clifford Richardson, 28 tests as follows : 

(Test i) Color in mass Brownish black to black 

(Test 4) Fracture SemUconchojdal to conchoidal 

(Test 5) Lustre Dull 

(Test 6) Streak Reddish brown to brown 

(Test 7) Specific gravity at 77 F i . 30-1 . 35 

(Test 9*) Hardness, Moh's scale 2-3 

(Test 9*) Hardness, penetrometer at 77 F. . . o 
(Test 16) Volatile at 325 F., 5 hrs, (dry sub- 
stance) About i per cent 

Volatile at 400 F., 5 hrs. (dry sub- 
stance) About i# per cent 

(Test 19) Fixed carbon 17.4-25.0 per cent 

(Test 21) Soluble in carbon disulfide 70-75 percent 

Non-mineral matter insoluble 3#- 4 per cent 

Mineral matter (calcium carbonate, 

etc.) 21-18 per cent 

(Test 23) Soluble in 88 petroleum naphtha, . 32-50 per cent 
(Test 28) Sulfur About 8.3 per cent 

Five miles east of Bejucal, there is another deposit, similar to 
the preceding. 

Province of Camaguey, Impure soft and hard asphalt deposits 
are found near Minas, a small town about 30 miles from Nuevitas, 
and 20 miles from Puerto Principe. 

Province of Santiago de Cuba. A deposit of hard impure 
asphalt occurs 5 to 10 miles south of Puerto Padre in Victoria de 
las Tunas district, testing as follows : 

(Test i) Color in mass Black 

(Test 4) Fracture Hackly 

(Test 5) Lustre Dull 

(Test 6) Streak Dark brown 

(Test 7) Specific gravity at 77 F 1 . 106 

(Test 94) Hardness, Moh's scale I . 

(Test 19) Fixed carbon 9.9 per cent 

(Test 21) Soluble in carbon disulfide 78.4 per cent 

Non-mineral matter insoluble 18.2 percent 

Mineral matter , 3,4 per cent 

Total 100,0 per cent 

(Test 23) Soluble in 88 petroleum naphtha ,,..,,.,.,. 60, 6 per cent 



182 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



SOUTH AMERICA 
TRINIDAD 

St. Patrick County. One of the largest deposits of asphalt in 
the entire world occurs on the Island of Trinidad 24 on the north 
coast of South America, situated a short distance from the main- 
land of Venezuela, between the Caribbean Sea on the west and the 
Atlantic Ocean on the east. 

Small deposits are scattered all over the Island, but the largest 
one known 'as the "Trinidad Asphalt Lake/' is situated on La Brea 
Point, in the Wards of La Brea and Guapo, on the western shore. 
The lake is situated on the highest part of La Brea Point, 138 ft. 
above sea level. It covers an area nearly circular comprising 115 
acres, in a slight depression or shallow crater at the crest of the 
hill. The exact location of the lake is shown in Fig. 55. The lake 

measures about 2000 ft. across 
and is over 135 ft. deep in the 
center, becoming shallower to- 
wards the edges. A panoramic 
view is shown in Fig. 56. 

The asphalt surface is broken 
up into a series of large folds with 
accumulations of rain water in the 
creases. A typical view is shown 
in Fig. 57. The entire mass of 
asphalt is in constant but slow mo- 
tion from the center towards the 
edges, probably due to the con- 
tinual influx of solid material at 
the center, accompanied by a 
strong evolution of gas which im- 
parts a porous or honeycombed 
structure. The evolution of gas 
through the water is shown in Fig, 58. Wherever a hole is dug in 
the surface, it slowly fills up and disappears. The asphalt is softest 
in the center of the deposit, and gradually hardens towards the 
circumference. Even in the center, the consistency is such that it 




\3*fo ^ 

\{ Vyo 

V V .._. Mi>*tff n jffl 

^^ 



NwaWt. t 
foileaad track 



FIG* 55. Map of Trinidad .Asphalt Lake. 



IX 



SOUTH AMERICA 



183 







O 

Is 



J 



12 
*3 

5 



O 

c 

el 

[ 

vo 

& 



184 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 




Courtesy of Barber Co, 
FIG. 57. Folds in the Surface of Trinidad Lake. 




Courtesy of Barber Co. 
FIG. 58. Evolution of Gas from Trinidad Lake. 



IX 



SOUTH AMERICA 



185 



will bear the weight of a man, and can be readily broken out in 
large masses with picks as shown in Fig. 59. 

Shrubs and small trees grow on the surface in isolated patches 
known as "islands," which slowly migrate from place to place with 




Courtesy of Barber Co. 



FIG. 59. Gathering Trinidad Lake Asphalt. 




Courtesy of Barber Co. 
FIG, 60. Transporting Trinidad Lake Asphalt. 

the movement of the asphalt. Grassy vegetation extends along the 
edges of the lake merging into the surrounding country. 

The crude asphalt is loaded on small cars run by cable over the 
lake in a loop, the rails being supported by wooden ties which must 
be replaced from time to time as they gradually sink into the surface 
of the asphalt. The asphalt is transferred to an inclined cable way 



J86 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

at the end of the loop which runs to the shore, and thence to a long 
pier where it is dumped on board steamers (Fig. 60). 

It has been estimated that the lake still contains 10 to 15 million 
tons of asphalt. Although vast quantities have been removed in 
the past, the level of the lake has not sunk more than 8 to 10 ft, 
since the rate of influx closely approximates the quantity removed. 
In the past ten years approximately 10 million tons of asphalt have 
been removed, during which period the level has sunk approximately 
i l /2 meters. 

The fresh material consists of an emulsion of asphalt, gas, water, 
sand and clay. According to Clifford Richardson 25 oil sands occur- 
ring at a depth carry an asphaltic petroleum and natural gas under 
high pressure, which on coming in contact with a paste of colloidal 
clay and silica are converted into the asphalt which emerges at the 
surface. 

The crude Trinidad Lake asphalt is extremely uniform in com- 
position, as is evident from analyses of samples taken from different 
points over the surface, calculated on a water- and gas-free basis. 
The crude material, when freshly sampled at the center of the lake, 
is composed of: 

Water and gas volatilized at 100 C 29.0 per cent 

Asphalt soluble in carbon disulfide 39.0 per cent 

Asphalt adsorbed by mineral matter 0.3 per cent 

Mineral matter on ignition 27 . 1 per cent 

Water of hydration in mineral matter 4.3 per cent 

Total 99 . 8 per cent 

Specimens taken from the various portions of the lake's surface, 
after pulverizing and drying to constant weight in air at room tem- 
perature, appear fairly uniform in composition, averaging: 

Soluble in carbon disulfide 53 .0 to 55 .o per cent 

Free mineral matter 35. 5 to 37.0 per cent 

Water of hydration, etc. . , * 9,7 per cent 

The so-called "water of hydration, etc." includes water chemi- 
cally combined with the clay, asphalt adsorbed by the clay and not 
removable by carbon disulfide, and the inorganic salts which are 
volatilized on ignition upon determining the mineral matter. 

The mineral constituents consist of extremely finely divided 
silica and colloidal clay, and have the following composition : 



IX SOUTH AMERICA 187 



SiOs 




70.68- 


66 . 9 pet cent 


AlaO* 




17.04- 


20 . 9 per cent 






7.62- 


4 4 per cent 


CaO 


I 


\ \ 


i . o per cent 


MgO 




2.46- 1 


i . i per cent 


K*OandNa 2 O 




I 

1.22- 


i . 6 per cent 


SOt 




O.Q7 


3 . 8 per cent 


Cl 




O.22- 


o . 3 per cent 











Total 100,00- 100. o per cent 

The mineral matter shows the following granularmetric com- 
position when separated into fractions by means of air: 

* Ignited Ash Unignited Mineral 
Residue 

O-IOM v , . . 37 per cent 47 per cent 

io-20/u 1 5 per cent 1 1 per cent 

20-30^1 9 per cent 7 per cent 

30-40/4 5 per cent 5 per cent 

40-50;* 5 per cent 6 per cent 

50-60/4 4 per cent 6 per cent 

Over 60^ 25 per cent 18 per cent 



Total 100 per cent 100 per cent 

The mineral constituents of Trinidad asphalt may be separated 
by treating with bromoform (specific gravity at 77 F. 2.59 to 
2.62). The lighter constituents will float to the surface and the 
heavier constituents present, including titanite, zircon, rutile and 
glaucophane will settle out. The latter upon examination under the 
microscope will disclose the characteristic blue color of glaucophane, 
which although not very plentiful, will aid in the identification of 
Trinidad asphalt, whenever present in a mixture. 26 

The emulsified water contains mineral constituents in solution 
to the extent of 82.1 grams (at 110 C) per kilo, composed largely 
of sodium chloride. The gas is a mixture of methane, ethane, car- 
bon dioxide, and nitrogen. 

The crude asphalt is subjected to a refining process by heating 
it to 1 60 C. to drive off the water. A small amount of volatile 
matter is also removed during this treatment The refined asphalt 
has been termed "parianite." * 7 A process has been suggested for 
expelling the water, when the asphalt is to be used for constructing 



188 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

pavements, which consists in mixing the crude asphalt with a suitable 
proportion of mineral aggregate heated sufficiently high (e.g., 
400 F.) to drive off the water. 28 Another process consists in com- 
minuting the crude asphalt, and drying it at a low temperature to 
preserve its granular condition. 29 The refined asphalt tests as 
follows : 

(Test i) Color in mass Black 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Dull 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .40-1 .42 

(Test ga ) Hardness, Moh's scale i -2 

(Test 9^) Penetration at 115 F 10 -15 

Penetration at 77 F* 1.5-4.0 

Penetration at 32 F 0.25-0.75 

(Test gc) Consistency at 115 F 32.7 

Consistency at 77 F 74. 9 

Consistency at 32, F Above 100 

(Test 9</) Susceptibility index Greater than 80 

(Test 10*) Ductility (Dow Method): 

At 115 F 8.0 

At77F '. 1.8 

At32F o.i 

(Test io) Ductility (Author's Method): 

At 115 F 1.5 

At 77 F i .o 

At32F o.o 

(Test n) Tensile strength (Author's Method): 

At 115 F 4.15 

At 77 F.. 21.0 

At 32 F 27.0 

(Test 13) Fraas breaking-point 57 F. 

(Test I 5*) Fusing-point (K. and S. method) 188 F. 

(Test 1 5^) Fusing-point (R. and B. method) 206 F. 

(Teat 15*) Fusing-point, pure asphalt extracted from mineral 

matter (K. and S. method) 131^ F. 

(Test I $) Fusing-point ditto (R. and B. method) 149 F. 

(Test 16) Volatile at 335 F., in 5 hrs 1.1-1.7 per cent 

Volatile at 409 F., in 5 hrs 4.0-5. 25 per cent 

(Test 19) Fixed carbon 10.8-12.0 per cent 

(Test 21) Soluble in carbon disulfide 56-57 per cent 

Asphalt retained by mineral matter 0.3 per cent 

Mineral matter on ignition with tricalcium- 

phosphate. , 38 . 5 per cent 

Water of hydra tion (clay and silica) 4.2 per cent 

(Testaa) Carbenes 0.0-1.3 percent 

(Test 23) Soluble in 88 petroleum naphtha (pure asphalt) . . 62-64 per cent 

(Test 26) Carbon (ash-free basis) 80-82 per cent 

(Test 27) Hydrogen (ash free basis) io-n per cent 

(Test 18) Sulfur (ash-free basis), 6-8 per cent 

(Test 29) Nitrogen (ash-free basis) 0.6-0, 8 per cent 

(Test33) SoKd paraffins 1 Trace 



IX 



SOUTH AMERICA 



189 



(Test 344) Saturated hydrocarbons 24.4 per cent 

(Test 37*0 Saponification value , 40.0 per cent 

(Test 380) Free asphaltous acids 6.4 per cent 

(Test 38^) Asphaltous acid anhydrides 3 . 9 per cent 

(Test 38*) Asphaltenes 33.0-37.0 per cent 

(Test 38^) Asphaltic resins 23 ,0-26. o per cent 

(Test 38^?) Oily constituents 31.0-32.0 percent 

The following more detailed tests have been reported: 80 



Test 

No. 


Description 


Refined 
Trinidad 


Extracted 
Asphalt 


7 


Specific gravity at 77 F * . * 


1 .4.0 


I O70 


*d 


Float test at 212 F 


14.02 


A .t-/W 

64? 


loa 


Ductility at 77 F 


3 


Q 


n 


Fraas breaking-point , 


66 F. 


<T9F. 


ita 


Fusing-point (K.. and S. method) 


171 F. 


jy * * 
I4QF 


i& 


Fusing-point (R. and B. method) 


* / * * 
203 F. 


*Ty c * 
l64F. 


i$h 


Ubbelohde drop-point 


270 F. 


IQOU F. 


16 


Volatile at 325 F.; 5 hours 


o.o?% 


0.08% 


16 


Loss (D.I.N. method) 


1.10% 


1.18% 


lib 


Flash-point (open-cup) 


460^ F. 


460^ F. 


18 


Burning-point 


529 F. 


529 F. 


21 


Soluble in carbon disulfide 


58.62% 


99-8<% 




Non-mineral matter insoluble 


0.2O 


o oo 




Mineral matter (ash) ......*/ 


4I.I8 


0. 1? 












Total 


IOO.OO% 


IOO OO% 


28 


Sulfur 


4.65% 


f r % 


33 


Solid paraffins: 
Alcohol-ether-fuller's earth 


O,25% 


0.44% 




Alcohol-ether-sulfuric acid 




O.40% 




Alcohol-ether-D.LN. method 




O,28% 


-S7<2 


Acid value ...... 


6 o 


O. J.C 


i8f 


Asphaltenes 


15 1<% 


26 14% 


JUl, 

lid 


Asphaltic resins 


I7.1<% 


20 . 42% 


i$e 


Oily constituents 


1 8 . 70% 


11 . QO% 




Soft asphalt constituents (diff.) 


7-1?% 


12. C4% 












Total 


58.6<% 


IOO.OO% 


11 


Solid paraffins in oily constituents 


0.81% 


1. 18% 


Js> 









So-called Trinidad u land asphalt^ represerits material which 
overflows from the lake at its edges, where it has been exposed to 
the action of the weather for centuries. It is derived from the 
same source as the lake asphalt, and has the same general physical 
and chemical characteristics* It is known under vairious names ; for 
example: u cheese pitch 1 ' is a variety which resembles the lake as-* 



190 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

phalt most closely with respect to its containing gas cavities; "iron 
pitch" is a variety which has hardened on exposure to the weather 
to such a degree that it resembles refined lake asphalt; "cokey 
pitch" is a variety which has been coked or carbonized by brush 
fires, etc. 

The land asphalt varies in its composition from place to place, 
but differs from the lake asphalt in the following respects : 

( i^ It contains less gas and water than the lake asphalt 

(2) It contains a slightly higher percentage of mineral matter 
(from i to 2 per cent). 

(3) More of the volatile ingredients have been evaporated. 

These influence the tests as follows : 

The specific gravity is somewhat higher (up to 1.45). 
The hardness is greater. 

The fusing-point is higher (between 30 and 40 F.). 
The volatile matter is less (about i per cent). 
The percentage of fixed carbon is slightly higher (about 2 per 
cent). 

BRAZIL 

State of Parana. Asphalt occurrences are reported in many 
localities in the Sierra da Baliza, in the crevices and pores of the 
igneous rocks. 81 

State of Sao Paulo. Asphalt is similarly reported in crevices of 
a dyke at Fazenda Saltinho, in Rio Tiete, 9*^ miles above Porto 
Martins. 82 

ARGENTINA 

Province of Jujuy. An asphalt lake, known as the "Laguna de 
la Brea," occurs some distance northeast of the City of Jujuy. JThe 
asphalt is sulfurous, of a semi-liquid consistency which hardens at 
the edges. It is mixed with more or less earthy constituents. Seep- 
ages of mineral oil are also found locally. 

Province of Chubut. Deposits of soft, impure asphalt are 
reported in the village of Cornodoro Rivadavia, associated with 
seepages of asphaltic petroleum. The asphalt has not been devel- 
oped, and no analyses are available. 

Province of Mendoza. Asphalt deposits, probably resulting 
from seepages of petroleum, occur in the San Rafael District at 
Cerro de los Buitres, in the south of Mendoza Province. 33 



IX EUROPE 191 

COLOMBIA 84 

Department of Bolivar. Numerous seepages of liquid to semi- 
liquid asphalt, more or less associated with mineral matter, occur 
along the Caribbean Sea south of Cartagena. These were origi- 
nally reported by Humboldt in 1788, and have been utilized largely 
for calking ships. 

Department of Antioquia. Numerous occurrences of asphalt 
have been reported between Nare and Puerto Berrio. 35 

Department of Santander. Similar seepages of soft asphalt, 
mostly associated with sand and pebbles, occur north of the Soga- 
moso River which empties into the Magdalena River south of 
Puerto Wilches. Such asphalts have been reported at Morokoi; at 
a brook called Puente, a few kilometers north of the foregoing; 
and still another farther north, at Las Monas. 

Department of Boyaca. Deposits of soft asphalt associated 
with sand and clay are found at Tunja and Sogamoso, north of 
Bogota, in the Cord Oriental mountain range. These have been 
used for paving the streets of Bogota. Similar deposits have been 
reported at Macheta, Tuta, Paipa, Pesca, La Puerta, Topaga, Cor- 
rales and San Francisco in the south-central part of this province. 



36 



ECUADOR 

Province of Guayas. In the Santa Elena peninsula, seepages of 
asphalt have been reported in pits which have been dug in pros- 
pecting oil. 87 

EUROPE 

FRANCE 8a 

Department of Landes, Near Bastenne, about 24 km. from 
Orthey, a moderately large-sized deposit of asphaltic sand is found, 
associated with fossil shells, indicating that this asphalt is of animal 
(marine) origin. These shells are distributed throughout the as- 
phalt bed, which measures between 10 and 14 ft thick. On expo- 
sure to the air, the shells fall to pieces in a fine powder and the 
asphalt hardens materially, due to the loss of volatile matter. An 
analysis by Leon Malo shows the material to contain: asphalt 38.45 
per cent, calcium carbonate 4.9 per cent, and sand 56*59 per cent. 



192 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

This deposit has been worked for many years and was used for 
constructing the earliest asphalt mastic pavements. 39 Similar de- 
posits were formerly worked at Dax. 

Department of Gard. Large deposits of rock asphalt have been 
mined in the Concession of St. Jean-de-Marvejols since the first 
Concession was granted by a Royal Ordinance on February 17, 1844. 
Deposits also occur in the southern part of this Department, includ- 
ing the Concessions of Servas, Cauvas, Les Fumades and Puech. 
These have long been known (since 1844), but are no longer 
worked. Lignite and coal occur in the same region. The asphalt 
is associated with limestone, sandstone and shale, and varies in per- 
centage between 5 and 16 per cent An average analysis shows it 
to contain: asphalt 10 to 12 per cent, clay 0.5 to 0.8 per cent, cal- 
cium carbonate 8486 per cent, magnesium carbonate about 2 per 
cent, and moisture 0.5 per cent The penetration of the extracted 
asphalt runs as follows: at 25 C. 98, at 20 C, 58, at 15 C. 32, 
at 10 C. 20 and at 5 C. 10. At St. Jean-du-Gard it is necessary 
to sink shafts 1000 ft. deep to reach the stratum of asphalt, which 
was probably introduced into the limestone as an asphaltic petro- 
leum, the lighter fractions of which evaporated, leaving the asphalt 
behind/ 

Department of Haute-Savoie. Deposits of asphalt associated 
with limestone and sandstone occur at Mussiege, Frangy, Lovagny, 
Bourbonges, and Chavaroche, in strata between 13 and 16 ft thick. 
An analysis of the rock asphalt mined at Chavaroche shows it to 
contain: asphalt 29.2 per cent, calcium carbonate 51.6 per cent, and 
sand 19,2 per cent This is used for paving purposes. The Lo- 
vagny deposit contains: asphalt 4.5 per cent, volatile at 100 C. 2.3 
per cent, and ash 93.3 per cent. The ash consists of CaCO 8 97.60 
per cent, MgCOa 0.44 per cent, CaSO 4 0.48 per cent, Fe 5 O s 0.62 
per cent, and A1 2 O 3 0.82 per cent 41 

Department of Ain. The asphalt dejposits extend across the 
boundary line, separating the Departments of Haute-Savoie and 
Ain, ranging in a northeasterly direction, and culminating in the 
ISFeuchatel (Swiss) region in the north. At Bellegarde, in the north- 
eastern part of the Department, occurs a deposit of asphaltic lime- 
stone, unevenly impregnated with asphalt, and associated in part 
heavy petroleum oils* The well-known Seyssel deposit also 



IX 



EUROPE 



193 



occurs in this Department, at Pyrimont 42 Minor deposits occur 
also at Volant, Belley, Challenges, Forens, Obagnoux, Corbonod, 
Confort, etc., consisting of a fine-grained limestone impregnated 
with asphalt. This region is illustrated in Fig. 61. The deposits 
consist of a series of hillside quarries on both banks of the Rhone 



Bllllat 



* 

* 



I 
Q 



Bcyrlat 



L'hoprtal 



Chancy 




FIG. 61. Map of Seyssel Asphalt Deposit, France. 

River. The asphalt impregnation varies from 2 to 8 per cent as a 
maximum, the balance consisting almost exclusively of calcium car- 
bonate. Fossil shells, also crystalline calcite, are frequently encoun* 
tered. The deposits at Pyrimont have been worked for many years 
by a series of underground tunnels, in eight beds, varying in thick*. 



194 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



ness from 2 to 5 meters, on the eastern bank of the Rhone River. 
Three grades of asphalt have been produced, containing 3 per cent, 
5-6 per cent, and 8 per cent of asphalt respectively. The chief 
merit of this product lies in the intimacy of its impregnation with 
asphalt, and the fine granular structure of the associated calcium 
carbonate. Prior to 1914 from 5000 to 20,000 tons were mined 
annually. The following analysis represents the average composi- 
tion of the Seyssel product: 

Water ........................................... i-9 - - percent 

Asphalt (fusing-point, 87 R, K. and S. method) ...... 8.00- 8. 15 per cent 

Magnesium carbonate .............................. o. 10 per cent 

Calcium carbonate .... ............................ 89 . 55~9i - 30 per cent 

Iron and aluminium oxides. ......................... 0.15 P 61 " cent 

Insoluble in acid .................................. o. 10- 0.45 per cent 

^ etc .......................................... o. io- o. 20 per cent 



The extracted asphalt shows the following penetrations (Test 
gb) : at 77 F. too soft; at 60 F. 136; at 50 F. 76; at 40 F. 40. 

Fig. 6 1 shows the location and extent of the Seyssel deposit. 
Occurrences of asphalt have also been reported at Lelex and 
Chezery, in the valley of the Valserine, north of Bellegarde. 

Department of Basses-Alpes. Two deposits have been de- 
scribed in the vicinity of Forcalquier, one (A) associated with lime- 
stone and the other (B) with a siliceous base, testing as follows: 43 





SiOa 


CaCOs 


Fe2O 8 andAl 2 O8 


H 2 and Loss 


Asphalt 


* > 

f\ * * . 

"B" 


Trace to 0.54% 
58.34-59.13% 


90.63-80.58% 
31.34-28.40% 


0.01-0.80% 
0.56-0.93% 


o.i3"3-52% 
1.31-0.27% 


9.33-14.50% 
8.45-11.27% 



Department of Puy-de-D6me (Auvergne). Rock asphalt de^ 
posits occur in numerous localities. The only present source of 
production is at Pont-du-Chateau (also at Chamalieres, near Cler* 
mont-Ferr and),. where 12,000 to 20,000 tons of rock asphalt com- 
posed of n.o per cent asphalt associated with SiO 2 (suitable for 
an acid-resisting mastic) are produced annually. Limited opera- 
tions have been carried on at various times in the past at Lussat, 
Malintrat, Gites-des-Roys, Puy-de-Croville, du Cortal, Pontgibaud 
(west of the Chain of Puys), Plain of Limagne, and other minor 
localities." 



IX 



EUROPE 



195 



Department of Haute Vienne. Minor occurrences have been 
reported at Limoges, in quartz veins traversing gneiss. 

SWITZERLAND 

Extensive deposits of asphalt-impregnated limestone occur west 
of Neuchatel Lake, in the so-called Val de Travers region. These 
have been exploited for many years and marketed under the names 




FIG. 6a. Neuchatel and Val de Travers Asphalt Deposits. 

"Neuchatel Asphalt" and "Val de Travers Asphalt." 45 The exact 
location of the region is shown in Fig. 62, The percentage of as- 
phalt varies considerably; thus, the "ordinary" grade contains 8~~io 
per cent of asphalt, the so-called "rich" grade contains 10-12 per 
cent of asphalt. 

The average product contains: asphalt 10.15 per cent (fusing- 
point 50 F., K. and S. method), calcium carbonate 88.4 per cent, 



106 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



calcium sulfate 0.25 per ceiit, iron and aluminium Oxides 0.25 per 
cent, magnesium carbonate 0.3 per cent, matter insoluble in acid 
0.45 per cent, and loss 0.5 per cent The extracted asphalt shows 
the following penetrations (Test $b) : at 77 F. too soft; at 60 F. 
1 12; at 50 F. 57. The fusing-point (Test 15^) is 43 C, and the 
ductility at 77 F; (Test 100) over 115 cm. 

The theory has been advanced that these asphalts have been 
produced by the decomposition of marine animal and vegetable 
matters, which is borne out by the associated fossils. 

Outcrops occur at Auvernier, Bevaix, Bois-de-Croix, Presta, 
Bulles, and St. Aubin, south of Neuchatel, on the western shore of 
Lake Neuchatel, carrying smaller percentages of asphalt than the 
preceding. 

ALSACE-LORRAINE 

The deposits in this region occur in a well-defined area in the 
neighborhood of Lobsann a short distance north of Strasbourg, as 
shown in Fig. 63. The asphalt strata have been traced 6 to 7 miles 



Schacht Pechelbronn 

* SOULTZ-SOUS-FOR 
Walbourg 




FIG. 63, Map of Lobsann Asphalt Region, Alsace-Lorraine, 



extending through Soultz-sous-Forets, Pechelbronn and Lamperts- 
loch. 46 They occur as asphalt-impregnated limestone and sandstone 
associated with lignite. Petroleum is also found locally. The asphalt 
strata average about 80 ft. in thickness and carry many fossils. The 



IX EUROPE 197 

region is badly faulted. The bituminous limestone has the following 
average composition: 

Asphalt (fusing-poin t 77 F., K. and S. method) 1 1 . 9 -i 2 . 32 per cent 

Calcium carbonate 69.0 -71 .43 per cent 

Iron and aluminium oxides 4.3 - 5.9 per cent 

Sulfur 5.0-5.6 per cent 

Magnesium carbonate 0.3 per cent 

Silica 3 * * 5~ 3-65 per cent 

Loss, etc * 1.7 - 3.4 per cent 

The asphaltic sandstone at Pechelbronn occurs in veins 3 to 6 ft. 
thick, containing 1518 per cent of a soft, viscous asphalt associated 
with 82-85 per cent of sand. The asphalt when extracted shows a 
gravity between 0.90 and 0.97 at 77 F. Large quantities of as- 
phalt have been mined in this region for paving purposes, 

SPAIN 

Burgos Province. At Maesta there has been reported an as- 
phalt deposit containing: 8.80 per cent asphalt, 68.75 per cent SiO 2 , 
9.15 per cent CaCO 3 , 8.10 per cent MgCO 3 , 4.35 per cent Fe 3 O 3 
and Al 2 O a , and 0.85 per cent water and loss. 

GERMANY 47 

Province of Hanover. At Limmer, a small village near Ahlem 
in the plains of Acker, about 18 miles west of Hanover there occurs 
a deposit of asphaltic limestone measuring 1600 by 2250 ft. which 
was discovered by Dr. Eirinis d'Eyrinys about 1730 and first mined 
in 1843 by D. H. Hennig. 48 The rock carries between 8 and 20 
per cent of asphalt and contains numerous fossil shells. As freshly 
mined it has a brownish to gray-brown color, and the asphalt im- 
pregnation is very soft in consistency containing a large proportion 
of volatile constituents. The average analysis shows: 

Asphalt 8 . 3 per cent 

Calcium carbonate 56 . 5 per cent 

Magnesium carbonate , 27 . o per cent 

Iron and aluminium oxides 8.2 per cent 

Total 100. o per cent 

The richer portions of the vein test as follows : 

Asphalt (fusing-point 61 F. s K. and S. method) 13.4-14.3 per cent 

Calcium and magnesium carbonates 67 per cent 

Iron and aluminum oxides, etc 17- 5~ J 9* 5 P er cent 

t ...,., * 0.3- 1.18 per cent 



198 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



At Waltersberge, near Limrner, a very large deposit of asphaltic 
limestone is found, containing 5 to 7 per cent of asphalt* It is esti- 
mated that about 3,000,000 tons occur in this deposit, but the ma- 
terial is so poor in asphalt that it must be enriched before it can be 
used for paving purposes, although it has not given good results as 
such, on account of the large percentage of clay present 







/,-/;//'; 

'" t f A'- 1 

W% f ' 7 ' 




10 10 20 30 40m. 

i..,,.,.,,! ^ ^^^^ 

1 : 1500 
FIG. 64. Herzog Wilhelm Mine at Holzen, Germany. 

In the District of Holzminden, in the Dukedom of Braun- 
schweig, a short distance west of the village of Holzen, on the west 
bank of the River Ith, there occurs one of the most productive de- 
posits in Germany, which has been identified with the neighboring 
towns of Eschershausen and Verwohle, 49 discovered in 1601 by 
woodsmen, who first utilized the substances as fuel. This includes 
the u Herzog Wilhelm" mine, the u Augusta Victoria," "Verwohle," 
"Greitbergbruch," "Wintjenberg" and "Stolln Gustav" quarries, 
the first two of which are illustrated in Figs* 64 and 65. A plan of 
the entire region is shown in Fig. 66. The deposits consist of as- 



IX EUROPE 199 

phaltic limestone, containing 10 per cent asphalt at the top, which 
gradually diminishes to 3 per cent at the lower levels, averaging 6 
to 8 per cent, and characterized by the presence of fish scales. 

The asphalt stratum has been traced for approximately 14,500 
ft. and forms a succession of layers 65 ft thick carrying a variable 




FIG. 65. Augusta Victoria Quarry at Holzen, Germany. 

percentage of asphalt associated with limestone, and separated by 
clay and shale. The average asphalt analyzes as follows : 

Asphalt (fusing-point 65-7o F., K. and S. method) ... 5-4 - 8 . J per cent 

Calcium carbonate 80.0 -90.9 per cent 

Iron and aluminium oxides 4.0-5.0 per cent 

Silica 2. 55- 4-77 P^ cent 

Loss o. 15- a . ii per cent 

The Verwohle rock asphalt shows the following average com- 
position : 

(Test 7) Specific gravity at 77 F 2.326 

Voids 2.8 per cent 

(Test 21) Soluble in carbon disulfide 7 -.73 P er cent 

Non-mineral matter insoluble o . 60 per cent 

Mineral matter 9* -67 per cent 



200 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



DC 



Legend. 

Deutsche Asphalt Ahtien GeseUsckaft (Eschershausen). 
Hannoversckt Baugesettschaft Akt. Ges. (Hannover}. 
Indus tr it gesellschaf t G. m. b. UJttr Steine u. Erden. (Etcher shavsen). 
VorwoUer Asphalt Co. Limited (Eschershauscn). 
Union Co. 

Vorwohkr Asphalt Fabrik L. Hoarmnn u. Co. G. m. 6. JET. 
Asphdt Con-panic Limited. 
Tkomae. 

Herkulcs Gcwerkschaft* 
Bits Kalkwrk. 




FiG. 66. Verwohle and Escherahausen Asphalt Deposits, Germany. 



IX EUROPE 201 

The extracted asphalt tests as follows: 

(Test 7) Specific gravity at 77 F f 1 .019 

(Test 9^) Penetration at 77 F 95 

(Test 13) Fraas breaking-point Below 20 C. 

(Test 15^) Fusing-point (R. and B. method) 47 C. 

(Test 15^) Ubbelohde drop-point 57 C. 

(Test 28) Sulfur i . 67 per cent 

This material must be enriched by the addition of Trinidad, 
Limmer, or petroleum asphalt, before it becomes suitable for con- 
structing pavements. It is marketed in three forms, viz. : 

1 I ) Mastic cake, which is prepared by first grinding the rock 
asphalt to a powder, which is heated to 180-200 C. for 4-6 hours, 
whereupon sufficient asphalt is added to enrich same to 14-16 per 
cent, and finally cast into the form of cakes, suitable for use in 
mastic work. 

(2) Powder, which is prepared by heating the ground rock 
asphalt in steam-jacketed kettles to 80 C. with an "enricher" and 
under strong agitation, until it forms so-called "clinker" containing 
about 1 1 per cent asphalt, which in turn is cooled and ground to a 
powder, suitable for use under compression to form sheet-asphalt 
pavements. 

(3) Asphalt-tiles, which are made by heating the ground rock 
asphalt and compressing same into plates 28 by 25 cm. and 1.5 to 
6.0 cm. thick by means of hydraulic presses operating at 180 to 400 
atmospheres. The resulting tiles are used for surfacing factory 
floors, bridges, viaducts, etc. 

A small deposit has been reported at Wintjenberg in this same 
neighborhood, but has not been worked to any extent. 

Province of Westphalia. Minor deposits have been found near 
the villages of Darfeld, Buldern, Hangenau, and Appelhiilsen, asso- 
ciated with clay and shale. 

Province of Hessen. At Mettenheim 50 between Worms and 
Appenheim, occurs a deposit of asphaltic limestone and clay carry- 
ing a large quantity of fossil fish remains. The rock contains be- 
tween 74.4 and 82.6 per cent of asphalt of a comparatively high 
fusing-point. 

Province of Baden. Minor occurrences have been reported 
near Dossenheim, north of Heidelberg, 51 also near Ottenau, north- 
east of Baden-Baden. 52 



202 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



Province of Silesia. Asphalt has been found in the granite of 
Striegau and in the northern part of the Black Forest, associated 
with calcite and hematite, 53 

JUGOSLAVIA 

Province of Dalmatia. 54 A deposit of asphaltic limestone occurs 
at Vrgorac, having a specific gravity at 77 F. of 1.697 containing 
an average of 26 per cent of asphalt. Analyses show the following 
ingredients : 





Analysis I, 
Per Cent 


Analysis 2, 
Per Cent 


Analysis 3, 
Per Cent 


Asphalt 


2.94 


7.12 


38.92 


Silica. ... . 


21 .70 






Iron and aluminium oxides 


7 12 


<8. 10 




Iron carbonate 




I . IO 




Calcium carbonate 


l6.6o 




61.08 


Magnesium carbonate 




12. C8 




Sodium chloride 




O. 07 




Water 


4. 10 














Total 


lOO.OO 


99.87 


IOO.OO 











The first analysis represents an asphaltic limestone, containing 
silica, the second analysis represents an asphaltic shale, and the 
third an asphaltic limestone (pure) . Considerable asphalt has been 
derived from this deposit for paving purposes. 

Asphaltic shales have been reported near the town of Skrip, on 
the Island of Brazza, situated about I mile from the mainland, in 
the Adriatic Sea, containing between 5 and 40 per cent of soft as- 
phalt, analyzing as follows: asphalt 7.1 per cent, calcium carbonate 
58.1 per cent, calcium sulfate 32.6 per cent, silica 2.1 per cent, and 
undetermined o. i per cent. The layers are between 2 and 4 ft. in 
thickness. There also occurs a deposit of asphaltic limestone con- 
taining about 13 per cent of asphalt and 87 per cent of calcium 
carbonate, having a brownish-black color and containing a substan- 
tial proportion of volatile matter. 

At Morowitza near Sebenico, on the Adriatic Sea, occurs a 
deposit of asphaltic limestone carrying 10 to 15 per cent of asphalt, 
95 per cent of calcium carbonate, and about 4 per cent of mag- 
nesium carbonate. 



IX EUROPE 203 

At Porto Mandorlo, near the town of Trau on the Adriatic Sea, 
occur beds of crystalline limestone of a brownish color containing 
9.2 per cent of asphalt and 90.8 per cent of calcium carbonate. 
Further deposits have been located in this region at Biskupija and 
Vinjisce, also at Suhidol, Bua and Dernis-Knin. 

Province of Herzegovina. 55 A deposit of asphaltic limestone 
occurs at the village of Popovo Polje, having a black to grayish- 
black color, and carrying between 1 6 to 20 per cent of asphalt It 
contains a large percentage of volatile matter, which causes the 
crude material to ignite very readily and burn with a luminous flame. 

A little south of the village of Misljan, and east of, the town of 
Popovo Polje, occurs another and larger deposit of asphaltic lime- 
stone 6 to 20 ft. thick. The asphaltic impregnation is sticky and 
semi-liquid, varying between 3 and 35 per cent The richer varieties 
ignite readily and burn with a luminous, smoky flame. 

A deposit of asphaltic limestone about 100 ft wide and 10 ft. 
thick occurs at Dracevo, about 2 }/2 miles east of the city of Met- 
kovic. The rock is of a brownish black to dull black color, carrying 
5.4 per cent of asphalt It is not rich enough to be worked 
profitably. 

Province of Styria (Steiermark). Traces have been found at 
Trenchtling, northeast of Trofaiach, and in the neighborhood of 
Messnerin. 56 

AUSTRIA 

Province of Tyrol. 57 A very peculiar asphaltic shale occurs at 
See f eld, 5000 ft. above the sea-level, in beds several feet thick with 
numerous fossil fish remains, in between layers of dolomite. This 
deposit constitutes one of the main sources of supply of ichthyol, 
which is recovered upon subjecting the material to a process of 
destructive distillation in suitable retorts. The material best suited 
for this purpose is composed of the following: 

Asphalt 26,41 per cent 

* Calcium and magnesium carbonates 38 . 22 per cent 

Clay 6.67 per cent 

Silica * 9 . 03 per cent 

Iron oxide 5, 95 per cent 

Loss and moisture 3-7^ per cent 

Total loo.oo per cent 



204 ASPHALTS ASSOCIATED WITH MINERAL MATTER DC 

HUNGARY 5S 

Province of Bihar. Deposits occur at Tataros, Derna and 
Bodonos, located east and northeast of the town of Nagy-Varad 
(Grosswardein), between the Sebes Koros and Berettyo Rivers. 
The Tataros deposit consists of sand containing a soft, sticky as- 
phalt with a characteristic, penetrating odor, which has been ex- 
ploited under the name u Derna Asphalt.'' It i$ associated with a 
consolidated sandstone in strata between 6 and 25 ft thick, 5000 
ft. long and 4000 ft. wide. Large quantities of asphalt have been 
mined from this deposit, which constitutes one of the largest sources 
of supply iniiungary. Analysis shows between 15 and 22 per cent 
asphalt, fusing at 83 F. (K. and S. method). The water-extrac- 
tion process has been used to separate a semi-liquid asphalt from 
the sand, leaving a residue containing 3 per cent of asphalt which 
could not be separated. The pure, soft asphalt thus separated is 
distilled to recover the heavy oils and the residue, comprising about 
44 per cent of the extracted asphalt, is converted into mastic by 
mixing with limestone. The product has been used with success for 
paving the streets of Budapest. During the World War, the puri- 
fied asphalt was shipped to Germany and used in the manufacture 
of rubber goods. 

A short distance east of Felso Derna there occurs a bed of sand 
asphalt, very similar in character and composition to that found at 
Tataros, carrying 15 to 22 per cent of asphalt. The extracted as- 
phalt contains 0.73 per cent of sulfur, 5.4 per cent of ash, and 1.6 
per cent of crystallizable paraffin/ 9 

CZECHOSLOVAKIA 

Province of Trecsen. At Strecno, on the River Waag, near 
Zsolna (Sillein), at the foot of the Lipovec Mountains, there occurs 
a deposit of dolomitic limestone containing 6.0 per cent asphalt, 60 
fusing at 37 C. (K. and S. method) . The asphalt contains asphal- 
tic acids 1.37 per cent, asphaltenes 2.11 per cent, asphaltic resins 
41.29 per cent, and oily constituents 51.25 per cent. 61 

Provinces of Moravia and Silesia. Occurrences of rock asphalt 
have been reported at Malenowitz and Zin (northeast of Napa- 
gedl), Palkowitz, Chlebowitz (near Friedek), Wiseck (near Letto- 
witz),etc. 



IX 



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205 



RUMANIA 

At Matitza, on both sides of the Matitza River, there occurs a 
large deposit in veins 30 to 40 m. thick. It is brittle at ordinary 
temperatures, has a dull, dark color, and a characteristic odor. The 
material contains 25 to 33 per cent asphalt, having a specific gravity 
of 1.07 to 1.09 at 77 F., and a fusing-point of 41 C. (K. and S. 
method). An average analysis shows: water 4.36 per cent, asphalt 
30.23 per cent, silica 41.10 per cent, iron and aluminium oxides 
1 8.08 per cent, calcium carbonate 4.43 per cent, and the balance 
sodium and potassium salts. Large quantities of paraffin wax are 
produced upon distillation. 62 

ALBANIA 

Selenitza (Selinitea). A fairly extensive vein of hard asphalt 
in lenticular form occurs at Selenitza, 25 km. west of Valona 
(Avlona), near the junction of the Vojutza (Vojusa) and Sauchista 
Rivers, close to the railway line. This deposit was first mentioned 
by Aristotle (384-322 B.C.), and subsequently described in detail 
by the Roman writer Aelianus Claudius (Aelian), about 100 A.D. 88 
It has been used for paving compositions, for manufacturing paints 
and composition roofings. Between 4000 and 6000 tons are pro- 
duced annually. It is on the border line between true asphalts and 
"glance pitch," and tests as follows: 64 



Test 

No. 


Description 


Refined 
S616nitza 


Extracted 
Asphalt 


i 


Color in mass 


Glossy black 


Glossy black 




Fracture 


Conchoid al 


Conchoid al 


6 


Streak 


Black 


Black 




Specific gravity at 77 F 


1.21 


1 .080 


<& 


Penetration at 77 F , 


O 


o 


ioa 


Ductility at 77 F 


o 


o 


i ^ 


Fraas breaking-point 


>77F. 


>77F. 


I C/2 


Fusing-point (K. and S. method) - * 


210 F. 


217 F. 


* j** 
ic 


Fusing-point (R. and B. method) 


264 F. 


*o l * 

2$iM 9 F, 


* j v 

I eh 


Ubbelohde drop-point * . . . , 


284 F. 


20CF. 


*j f * 

16 


Volatile at 325 F., 5 hrs 


0.0% 


0.0% 




Loss (D.I.N. method) 


0.6% 


0.7% 


nb 


Flash-point (open-cup) 


566^ F. 


?6c F. 


18 


Burning-point r ,..,. 


628 F. 


628 0? F* 


21 


Soluble in carbon disulfide . , , , 


84.62% 


QQ . 86% 




Non-mineral matter insoluble , , 


0,20% 


yy uv /Q 
o.00% 




Mineral matter (ash) 


I<M8% 


O.I4% 












Total 


100,00% 


IO6. 00% 











206 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



Test 
No. 


Description 


Refined 
S&gnitza 


Extracted 
Asphalt 


18 


Sulfur 


6.2C% 


7.4.0% 


33 


Solid paraffins: 
Alcohol-ether-fullers 1 earth 


O <Q% 


0.70% 




Alcohol-ether-sulfuric acid 




o. ?8% 




Alcohol-ether-D.I.N. method 




0.4.0% 


Tja 


Acid value 


^35 


2.QO 


3$c 


Asphaltenes 


18 20% 


AC 2O% 


l&d 


Asphaltic resins 


I< QO% 


1 8 80% 


JWt* 
38* 


Oily constituents . , , 


20 . 70% 


2A . CO% 




Soft asphalt! c constituents 


Q 72% 


II CO% 












Total 


84.52% 


100.00% 


11 


Solid paraffins in oily constituents 


1.72% 


2.01% 











ITALY 65 

The general location of the asphalt deposits in Italy are shown 
in the map illustrated in Fig. 67. 

Compartment of Marches. 

Province of Pesaro ed Urbino. Impure, solid asphalt is found 
at Sant' Agata Feltria associated with sulfur, but is not mined ac- 
tively. At Tallamello and Urbino, deposits of solid and semi-liquid 
asphalt occur associated with more or less sulfur. These are of no 
commercial importance, but are of interest merely from a geological 
standpoint 

Compartment of Abruzzi e Molise. 

Province of Chieti. In the neighborhood of San Valentino, 
extensive deposits of asphaltic limestone have been worked in strata 
2,1/2 to 3 miles long and about 100 ft. thick. Quarries have been 
opened up in the Valley of the Pescara River at the villages of 
Roccamorice, Abateggio, Manopello, Lettomanopello, Tocco, and 
Papoli. Three distinct zones are distinguished. The lower carries 
between 9 and 10 per cent of asphalt, the middle an average of 17 
per cent, and the upper 9 to 30 per cent In certain localities the 
asphalt has a rubbery consistency, and is deep black in color, and in 



IX 



EUROPE 



207 




ASPHALT DEPOSITS 



FIG. 67. Map of Italian Asphalt Deposits. 



208 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



others it is very soft and semi-liquid. The deposits are rich in fossil 
shells. Analyses show the following composition : 66 





San 
Spin to, 

Per Cent 


Piano 
dei 
Monaci, 
Per Cent 


Cusano, 
Per Cent 


San 
Giorgio, 

Per Cent 


Acqua- 
fredda, 

Per Cent 


Fonti- 
celle, 

Per Cent 


Letto- 
mano- 
pello, 
Per Cent 


Rocca- 

morice, 

Per Cent 


Moisture 


0.64 

10.72 
82.25 
5.50 


0.40 
11.70 
62,23 
24.80 


0.98 
15.70 
49.70 
32.00 


0.46 
12.06 

85-30 
i .40 


0.66 
10.62 
86.40 
1.50 


O.22 
10.96 

86.00 

I .20 






Asphalt 


7.15 
73-76 
14.26 
1.72 
3.02 
o.n 


12.46 
77-53 
4-71 
2.63 
2.17 
0.50 


CaCOj 


MgCOi 


CaSO 4 


Clay 


0.74 
0.15 


0-37 
0.06 

0.44 


0.32 
0.42 
0.82 


0.16 
0.42 

0.20 


0,52 
0.30 


1.18 
0.32 


SiOi 

















These deposits are especially suited for pavements in tropical 
climates and have been used with good results in Cairo, Bombay, 
Rio de Janeiro, etc. A number of mines have been opened up along 
this valley amidst precipitous mountains attaining elevations up to 
10,000 ft. The rock asphalt is transported by aerial ropeway and 
narrow gauge surface tracks and the development has been effected 
in the face of great natural difficulties. 

Compartment of Calabria 

Province of Baslllcata (Potenza). Asphaltic limestone pros- 
pects have been reported at Tamutola, Magliano Setere and 
Leviano. 

Compartment of Campania 

Province Terra dl Lavoro (Caserta). One of the largest as- 
phalt quarries in the entire region, which, however, has not been 
very active in recent years, occurs at Colle San Magno. Analyses 
of the product as mined show it to be composed of the following : 

Asphalt 7. 15 per cent 

Calcium carbonate 73 , 76 per cent 

Calcium sulfate i . 72 per cent 

Iron and aluminium oxides 3 .02 per cent 

Magnesium carbonate* 14. 24 per cent 

Silica, o. 10 per cent 

Prospects of asphaltic limestone occur, at Liri, Frosione, Monte 
San Giovanni, Banco, Castro dei Volsci, Filletino and Collepardo. 



IX EUROPE 209 

Compartment of Sicily 

Province of Syracuse* 7 The largest and most important Italian 
asphalt deposit occurs at Ragusa, about 8 miles from the southern 
coast of Sicily, on the River Irminio, in a bed 10 to 50 ft thick and 
1600 to 2000 ft. long. It was discovered in 1838 and first utilized 
for building stone, and later, about 1856, exploited for compressed 
asphalt work. Fig. 68 shows a general view of the principal mine, 
Fig. 69 illustrates the tunnelling operations, and Fig. 70 shows the 
rock asphalt sawn into blocks and slabs as it is blasted from the 
deposit. The rock contains variable percentages of asphalt, ranging 




nu 05. /ispnait mine at Kagusa, Italy. 



from 2 to 30 per cent, associated with a soft consolidated limestone 
composed largely of fossil shell remains. Several grades of rock 
asphalt are mined, including a brown variety relatively poor in 
asphalt, carrying between 3 and 7 per cent, also a black variety 
carrying about 15 per cent. Commercial grades usually contain 6 
to 10 per cent, and occasional pockets are encountered running as 
high as 12 to 1 8 per cent. The rock containing 6 to 9 per cent is 
marketed for use as mastic, and the leaner varieties containing an 
average of 3 per cent of asphalt are distilled in retorts to recover 
the oils. In 1924, there were 16 furnaces in operation, yielding 
30,000 tons of distillate per annum. The retorts are arranged in 
groups of four. Each oven is 15.5 meters high and of rectangular 



210 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



cross section. The waste gases are used to promote combustion of 
the rock. The maximum temperature is about 730 C. and the 
distillation zone ranges from 200 to 600 C. The distillate is 
practically free from paraffin and contains up to 2 per cent phenols. 
It compares with crude petroleum of Ohio and Texas origin. To 




FIG. 69. Tunnelling Operations at Ragusa Mine. 

obtain I ton of distillate, 1 8 to 20 tons of asphaltic rock are re- 
quired. The distillate is refined with sulfuric acid and fractioned 
into different grades of lubricating oil. 68 These deposits have been 
worked for many years, and over 100,000 tons are mined annually 
for use on the continent of Europe. The material as mined requires 
no further treatment, other than grinding. It is shipped from the 



IX EUROPE 211 

ports of Siracuse, Mazzarelli and Catania. Analyses show the fol- 
lowing compositions : 

Range Average 

Per Cent Per Cent 

Asphalt 8.80-14.05 9.24 

Calcium carbonate 82.15-88.21 87.98 

Iron and aluminium oxides 0.91 1.90 0.93 

Magnesium carbonate 0.96 0.72 

Silica o . 60- o . 73 o . 69 

Moisture and loss 0.40- i . 17 0.76 

The extracted asphalt shows the following penetrations (Test 
9&) : At 77 F. too soft; at 60 F. 168; at 50 F. 94; at 40 F. 50. 
The fusing-point (Test i$b) ranges between 36 and 44 C. 




FIG. 70. Sawing Ragusa Asphalt into Blocks. 

The rock asphalt is also removed in large blocks which are 
capable of being sawed, bored, or carved in the form of paving 
stones, stair treads, or ornamental work for buildings. The dark 
color of the asphalt as freshly mined soon disappears upon expo- 
sure to the weather, turning to a bluish gray. 

Smaller deposits occur at Modica and Scicli, south of Ragusa, 
in the same region, testing as follows: moisture 0.60 to 0.72 per 



212 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

cent, asphalt 9.00 to 9.50 per cent, CaCO 8 87.27 to 86.78 per cent, 
Fe 2 O 3 2,05 per cent, SiO 2 0.78 to 0.72 per cent, and loss 0.30 to 
0.23 per cent. Asphalt is abundant in the basalt at Cozzo Grillo, 
near Cape Passero, at the southeastern tip of Sicily, also at Vizzini, 

north of Ragusa. 

GREECE 6 * 

Department of Triphylia. At the village of Marathonpolis, on 
the west coast of the Pteloponnesus District, there occurs a deposit 
of asphaltic limestone well suited for the preparation of asphaltic 
mastic pavements, analyzing as follows: asphalt 14.75 per cent, si- 
lica 1.07 per cent, iron and aluminium oxides 0.80 per cent, calcium 
sulfate 0.21 per cent, magnesium carbonate 0.45 per cent, calcium 
carbonate 82.27 per cent, moisture and loss 0.45 per cent This de- 
posit is shown in Fig. 71, location 2. 

Department of Achaia (Peloponnesus District). Asphalt has 
also been reported at location 3, likewise at location 4 (Fig. 71) 
near Divri, south of Mount Olonos, and north of the town Souli. 

lolian Islands. Liquid asphalt deposits occur on the island of 
Zante (Zacynthus or Zakynthos) at location 5 (Fig. 71 ), 70 and 
asphaltic limestone on the islands of Paxos and Antipaxos, as shown 
at location 6. 

Department of Phocis. A deposit has been reported near 
Galaxidi, shown at location 7 (Fig. 71). 

Department of Phthiotis. Occurrences are found near Dremisa 
(Dramesi) as indicated at location 8 (Fig. 71). 

Departments of Eurytania and Arta. Occurrences of soft 
asphalt and asphaltic limestone are found in the Pindus Mountains, 
up to the town of Pinde, as shown in locations 9, 10, n and 12 
(Fig. 71). Location n is at Vordo, in the valley of the Molitsa 
River, a branch of the Kalamas River. 

Northern Departments. Various outcrops of asphalt have been 
found at Bajousous (location 13), Lavdani (location 14) and 
Eleousa (location 14), in the Northern Provinces, Fig 71. 

, PORTUGAL 

Province of Estremadura. At Serra de Cabagoa deposits of 
asphaltic sandstone have been reported, and at Monte Real, north 
of <Leiria, layers of asphaltic sandstone impregnated with a very 



DC 



EUROPE 



213 



soft and viscous asphalt exist None of these have been worked to 
any great extent An asphalt pit, known as "Azeche," was formerly 
worked south of Nuestra Senora de la Victoria. 71 



25 50 75 100 

I ii db 
KILOMETRES 




FIG, 71. Map of Greek Asphalt Deposits. 
SPAIN r2 

Province of Santander. In the neighborhood of Puerto del 
Sscudo, deposits of asphaltic sandstone are found in beds about 5 ft. 
:hick. No analyses are available. At Suances similar deposits of 



214 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

asphaltic sandstone have been reported containing approximately 
1 1 per cent of asphalt, also in the Reviere of Lucara. 

Province of Alava. At Alauri, Maestu, and other localities in 
the Pyrenees, asphaltic sandstone deposits containing 12 to 20 per 
cent of asphalt have been worked for a number of years. A mine 
about 10 miles from Vittoria consists of a calcareous sandstone in> 
pregnated with 8 to 9 per cent of asphalt. It shows the following 
average composition: 

Asphalt 8 . 80 per cent 

Silica 68.75 per cent 

Iron and aluminium oxides 4.35 per cent 

Calcium carbonate 9. 15 per cent 

Magnesium carbonate 8.10 per cent 

Water and loss 0.85 per cent 

Province of Navarre. Similar deposits have been reported at 
Bocaicoa, which have been worked to a limited extent. 

Province of Gerona. Asphalt and asphaltic shales have been 
found in the neighborhood of Can Dabano, associated with ozo- 
kerite. The asphalt melts at 61.5 C. (K. and S. method). 

Province of Tarragona. Asphalt occurs in the District of 
Campius, in the precipices of Montseng, also at Sot del Bosch, Port 
B6, Can Call, Sot de Puig and El Sotas. Likewise in the District 
Manresa in the Santa Catalina Mountains. Asphaltic shales occur 
in the District Saedes *at Ribas de la Pega, Serrat Negre, Clara 
and Canal de Dordella. 

Province of Soria, At Santander, Sierra de Frentes, and 
Fuente-toba-Cidones, 73 several deposits of asphaltic sandstone have 
been operated, from which fairly large quantities have been mined. 

Province of Burgos. In the Reviere of Huidobro, Asphalt pits 
have been worked at Narcisa and Felicia. 

Province of Almeria. Asphalt has been reported at Cobdar, 
Tijola and Bayarque. 

Province of Valencia. Asphalt has been reported at Mogente. 



74 



RUSSIA (IN EUROPE) 

Simbirsk Province. The principal occurrences are found along 
the banks of the Volga River in the vicinity of the estuaries of vari- 
ous small streams, including the Syzranka, extending to Samarskaya- 



IX EUROPE 215 

Louka, between the village Perewoloki and the city Syzran. These 
contain 6-13 per cent asphalt (rarely 37 per cent) associated with 
dolomite. In the same region, north of Samarskaya-Louka and 
3 km. from the Volga River, there occurs a deposit containing 6-20 
per cent asphalt associated with sand, known as "garj," covering an 
area 1300 by 320 ft., in a layer 32 ft. deep. The extracted asphalt 
has a fusing-point of 96-147 C. T5 

Kazan Province. Deposits have been reported at Chistopol on 
the Kama River. 

Samara Province. Asphalt is found at the mineral wells at 
Sergievsk, also at Sarabik-Ulowo and Chugorowo in the vicinity of 
Bugulma. Deposits are found near Samara, at the hair-pin bend of 
the Volga, also at Tzarevstchina and on the banks of the Krunza 
and Oussa Rivers, between Kostyachi and Petcherskoi'e. 

Terek Province (Northern Caucasia). At Vladikavkaz there 
occurs a deposit containing 612 per cent soft asphalt associated 
with earthy matter. This is known as "kir" when found in a fairly 
pure state, and "katran" when associated with much mineral mat- 
ter. Also 4 km. north of Staniza-Miailovskaja there occurs a de- 
posit in a ravine of the mountain Besimyannya-Gora, containing 70 
to 86 y^ per cent asphalt associated with clay. The extracted as- 
phalt is hard and brittle, melting at about 300 C, and has a specific 
gravity of about i.2. 76 Deposits also occur at Goriatchevodsk, like- 
wise on the banks of the Little Chetchna River, between the Terek 
and Argun Rivers. Asphaltic sands, sandstone and clay occur near 
the town Sernowodsk. North of the Groznyi oil fields there occurs 
a deposit containing 6 to 1 2 per cent asphalt, likewise several small 
deposits on the Groznyi and Terek rocky prominences in the vi- 
cinity of the oil wells. 

Kutais Province (Transcaucasia). In the vicinity of Sukhum, on 
the left bank of Bzyb River, there occur veins of asphalt in dolomite, 
in the Bsyschro basin. Near Ozurgeti, about 3 km. north of the 
railroad station Notanebi there occur deposits of asphaltic sandstone 
containing 20 per cent asphalt. A large deposit occurs i km, from 
the left bank of Supsa River, near where it empties into the Black 
Sea, to the west of Chrialeti mountain. Deposits are reported near 
the village Guriamta and asphaltic sands in the vicinity of Tamara- 
sauli, likewise in the valley of Bekwis-Zchali River, near the town 



216 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

Bekwi, also at the village Dsmuisi about 25 km. northeast of the 
city Kutais* 

Tiflis Province (Transcaucasia). Asphalt deposits occur in the 
neighborhood of Gori, also the village Dschawa at the overflow of 
the Big Ljachwa River. Near Signach, about 2 km. northeast of 
the Mirsaani oil field, in the Kwamianzkaro ravine, there occur four 
veins of hard asphalt containing 26.3-30.6 per cent ash. Asphaltic 
sandstones are found on the right bank of the Yora River near 
Chatma, Kapitschi, and in the rocky prominences of Eilar-Augi near 
the town Kasaman. 

Baku Province (Transcaucasia). Near Baku there are a num- 
ber of deposits of asphalt in the vicinity of the oil wells, and in the 
region of the numerous large mud volcanos. In the Adzhikabul 
(Adza Kabul) district, about 75 km. southeast of Baku, a deposit 
of rock asphalt has been reported containing 42-67 per cent soluble 
in carbon disulfide. The extracted asphalt has the characteristics 
of gilsonite, testing as follows : 77 

(Test 7) Specific gravity at 77 F 1.026-1.081 

(Test 9^) Penetration at 77 F o to 9 

(Test 15^) Fusing-point (R. & B. method) 196-268 F. 

(Test 19) Fixed carbon 13.6-15.9 per cent 

On the Island Suyatoi there is an area of about 14 hektar cov- 
ered with asphalt, which however is not utilized. 

ASIA 

SYRIA (LEVANT STATES) 78 

The deposits which follow are indicated on the map shown in 
Fig. 72. 

Vilayet of Aleppo. Various deposits of asphaltic limestone have 
been reported about 5 miles south of Alexandretta, also near An- 
takia (Antioch). 

f Vilayet of Beirut At Jebel Keferie (Jebel Kfarieh), a hill near 
the bend of the Nahr el Kabir, near the town Babenna, about 38 
km. from the sea, on the road between Latakia and Aleppo, exten- 
sive deposits of asphalt are* found covering an area of 1400 by 
1500 m., estimated to contain about 2,000,000 tons. Most of these 
consist of a dolomitic marl (containing 28.0 per cent silica, 2.9 per 
cent MgCO 8 and 3.0 per cent clay) with asphalt, of which 21.0 to 



IX 



ASIA 



217 




FIG. 72. Map of Asphalt Locations in Syria and Palestine. 



218 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

23.6 is soluble in carbon tetrachloride and 10.9 to 10.3 per cent of 
the non-mineral matter remains insoluble. The bituminous con- 
stituents are associated with 68.1 to 66.1 per cent mineral con- 
stituents (total = 100 per cent). These deposits have not been 
worked to any extent, on account of the difficulty in transportation 
to the coast. 79 They occur in three separate valleys or canons, i.e., 
Chandak bu Sfgherie, Chandak Shehade, and Chandak el Barbura; 
likewise on the neighboring mountains, Jebel Harf and Jebel Nobeh. 
Similar deposits, but of a smaller size, pccur west of the foregoing, 
and north of a small canon through which the Nahr el Kebir passes, 
at Dahana (Derhana, or Derk'ah'a), consisting of limestone and 
serpentine impregnated with asphalt, of which 10.7 to 12.3 per cent 
is soluble in CC1 4 ; also at Milik, consisting of asphaltic marl, of 
which 6.93 per cent is soluble in CC1 4 and 4.34 per cent non-mineral 
matter remains insoluble; likewise at Jebel Sullas (Sulas), consist- 
ing of limestone and marl impregnated with asphalt, of which 6.99 
per cent is soluble in CC1 4 A still smaller deposit lies north of the 
last three, at Djukr Djak, near Kabara. Still another deposit oc- 
curs close to the city of Beirut, and a small one near Tyre (Es Sur). 
Other deposits are reported at Ain Ibl (Ain Ebel) 20 miles south- 
east of Tyre; at Aidib (Aideb) 15 miles east of Tyre; and at 
Hereika. 80 

Vilayet of Sham (Syria). 81 Asphaltic limestone deposits are 
reported at Khaliwet, between Hasbaya (Hasbeya) and Rashaya 
(Rasheye), also at localities 5 miles southeast of Hasbaya; another 
10 miles south of Hasbaya; another at Sohmor (Sahmur) 10 miles 
north of Hasbaya on the eastern bank of the Nahr Litani ; another 
at Ain-et-Tineh 7 miles north of Hasbaya on the western bank of 
the Nahr Litani; and still another 4 miles north of Hasbaya at Ain 
Tannura (Ain Tadjoura). Asphaltic limestone deposits occur in 
the Yarmuk (Jarmuk) River valley, along the Damascus-Haifa 
railroad, at Marani (Mrani) containing 10 to 30 per cent asphalt; 
also at El-Makarin (Mekarim) containing 18 to 20 per cent asphalt. 
Rock asphalt also occurs northeast of Latakia, north of Horns, and 
about 25 miles west of Tyre. 

Palestine. Deposits of asphaltic limestone occur at the Sea of 
Galilee (Lake Gennesaret, or Bahr Tubariya), at Tubariya (Ti- 
berias) and Hammath (Amman, Hamath, or Hammam) on the 



IX ASIA 219 

western shore, also at Muskes on the River Jordan south of the Sea 
of Galilee* Asphaltic limestone deposits also occur at the Dead Sea, 
the largest being at Nebi Musa (Neby Musa) 4 miles west of the 
northwest shore. This is reported to carry 4 to 6 per cent of as- 
phalt and has a black color. A typical analysis is as follows : asphalt 
soluble in chloroform 5.07 per cent, CaCO 3 70.20 per cent, MgCO 3 
trace, CaSO 4 1.20 per cent, SiO 2 4.51 per cent, A1 2 O 3 and Fe 2 O 3 
6,56 per cent, insoluble organic mattter 12.52 per cent, total 100,06 
per cent. Other deposits are found on the western shore near Es 
Sebba (Es Sebbe, or Es Sebeh) and Wadi Sebba (Wadi Sebeh, or 
Wadi Sebbeth). A short distance from these localities, there occurs 
a peculiar deposit consisting of flint pebbles cemented together with 
varying percentages of asphalt, in juxtaposition to a vein of asphal- 
tic limestone. Deposits of asphaltic limestone are also reported on 
the eastern shore near El Kerak. On the southwestern shore, at 
the foot of Jebel Usdom ( Jebel Esdom) mountain, is found a con- 
glomerate carrying asphalt as the binding medium, and close to this 
locality, about 300 yards from the mouth of the Wadi Mahawat 
(Wadi Mayawat) stream there occurs a deposit of asphaltic lime- 
stone associated with fossil marine remains, carrying 13 to 25 per 
cent asphalt, which is used by the natives as fuel. 82 

MESOPOTAMIA (IRAQ) 

Villayet of Baghdad. At Hit, to the west of Baghdad, on the 
west bank of the Euphrates River, deposits of asphaltic limestone are 
still found and collected by the natives in a crude way, exactly as 
was the case many centuries ago. The occurrences are found a short 
distance south of Hit, between two streams, the Kubessah and the 
Mohammedieh. The asphalt is collected and sold in the form of 
small cakes, which the Turks call "karasakiz" and the Arabs "jir" 
or "ghir" or "gir" referring to a mastic containing sand or lime- 
stone. The term "seyali" is used to designate the fluid or semi- 
fluid varieties of asphalt of recent origin, and the term u qasat" to 
denote the ancient forms of natural asphalt. Upon being melted 
and mixed with sand or earth, it is used for calking ships. Asphalt 
deposits 4 to 5 m. thick are found at Tuz-Khurmatli on the west 
bank of the Tigris River, about 50 miles north of Baghdad. South- 
west of this locality there occurs a deposit about 2 m. thick, at the 



220 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

springs of Kifri, about 2 miles east of the settlement at the foot of 
Neft-Dagh (Naphtha Mountain). 88 Another deposit occurs on 
Karum River, north of Dizful, a short distance north of the Persian 
Gulf. Another deposit has been reported on the southeastern slope 
of Jebel El-Hamrin mountain along the Tigris River. 

ASIATIC RUSSIA 

Uralsk Province. A deposit of asphaltic sand occurs on the road 
from Chiwa and Kungrad towards Uil and Uralsky, about 25 km. 
northeast of the village Tersekan, on the southern shore of a small 
salt lake. 

State of Turkestan. Asphalt deposits occur on the island of 
Cheleken at so-called Naphtha Mountain (Neftjanaja Gora) and 
in several other localities, particularly in the vicinity of Ferghana, 
from which region about 1500 tons of rock asphalt are exported to 
Europe annually. 

Kamchatka Peninsula (Eastern Siberia). On the tundra of the 
western coast of Kamchatka, north of the River Sopotschnyi, as- 
phalt deposits have been reported. 

Sakhalin Island. More or less developed deposits of rock 
asphalt occur on the northern portion of the island. 

TlJRKEY-IN-AsiA (ASIA MlNOR) 

Anatolia. Several minor deposits of rock asphalt have been 
reported to occur in Anatolia, 84 and at Olty (Olti) in the State of 
Georgia, but these are of no particular commercial importance. 

ARABIA 

Vilayet of El Hasa. 85 In 1902 an extensive deposit was dis- 
covered on the island of Bahrein, in the Persian Gulf, which on 
analysis was found to consist of: 

Asphalt. . . , aa. 77 per cent 

Ash 76 . 68 per cent 

Moisture ,, o, 59 per cent 

Total , 100,04 P r cent 

The ash consists almost exclusively of calcium-aluminium silicate. 
The product is mixed with limestone powder and used for paving 



IX ASIA 221 

purposes. Another deposit is found near Burgan on the west shore 
of the Persian Gulf and west of Ai-Koweit (Koweyt) near the town 
of Benaid-el-Qar. 

Sinai Peninsula. Asphaltic petroleum seepages occur at Abu 
Durban and Jebel Tanka. 

EGYPT 

Springs of asphalt oil have been known as far back as Roman 
times to exist at Jebel Zeit, termed by them "Mons Petrolius," be- 
tween the Nile and the Gulf of Suez. Layers of asphaltic sand- 
stone have recently been reported at Helwan, on the right bank of 
the River Nile, a short distance south of Cairo. 86 

INDIA 

Kashmir District. Rock asphalt has been reported near Isakhel 
ontheBasti River. 

Hazara District, Seepages of impure liquid asphalt occur in 
the Sierra Mountains at Gunda. 

Baluchistan District. Asphalt seepages similarly occur at Gan- 
dava and Khalan (Khar an), 

Bombay Island. Deposits of u mineral pitch" and basalt have 
been reported in Bombay Island, off the western coast of India. 87 

CHINA 

Chinese Turkestan (Sin-Kiang), In Sungaria (Dzungaria), 
asphalt deposits have been reported at Lake Telli-Nor in the Dzung 
Gobi, southeast of Jair Mountains; also at the Orchu Basin of the 
Jeun River, on the southern slope of Jair Mountain. 

JAPAN 

Akita Prefecture. 88 A series of asphalt deposits occur in the 
villages of Toyokawa (embracing the hamlets of Tsukinoki, Riuge, 
Magata, Iwase and Urayama) and Kanaashi (embracing the hamlet 
of Kurokawa}. These are situated between i to \y 2 miles east of 
the Okybo railway station on the Ou railroad line, in the neighbor- 
hood of Lake Hachiro and the pond Iwase. From the area cov- 
ered by the deposits, about 180,000 sq. ft., it is estimated there exist 
a total of 2,360,000 cu. ft in volume. They are found on the sur- 



222 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



face of the hills about 30 to 50 meters above sea level, also among 
the swamps surrounding the hills. It is apparent that this region 
is underlaid with an asphaltic petroleum which seeps out between 
the fissures in the shales and flows out of springs in the bottom 
of the swamps or marshes. For example, in the pond Iwase, the 
natives stir the bottom with a long bamboo pole, which detaches 
masses of soft asphalt, which are then ladled from the water's 
surface. The asphalt occurs in various forms, depending upon the 




FIG. 73. Mining Asphalt at Toyokawa, Japan. 



state of weathering and the associated ingredients, ranging from 
a thick viscous maltha to a hard solid form associated with sand 
or clay, and in swamps with the decayed remains of aquatic plants. 
As the asphalt exists near the surface of the earth, it is mined by 
hand with a spade or mattock, as illustrated in Fig. 73. After ex- 
posing it to the sun for a while, it is melted in shallow pans to expel 
the water and permit the coarse earthy matters and organic im- 
purities to settle, whereupon the asphalt is cast into moulds and 
marketed as such. This operation has been performed in much 
the same way since ancient times. The good, rich ore is lustrous 



IX 



AUSTRALIA 



and black, whereas the lean, poor ore appears dull brown, 
made by the author gave the following results: 



223 
Tests 





Crude 


Fluxed 




Asphalt 


Asphalt 


(Test i) Color in mass 


Black 


Black 


(Test 2) Homogeneity 


Non-homogeneous 


Homogeneous 


(Test 4) Fracture 


Conchoid al 


Conchoidal 


(Test 5) Lustre 


Dull 


Bright 


(Test 6) Streak 


Brown 


Black 


(Test 7) Specific gravity at 77 F 


1.280 


1.075 


(Test 9^) Penetration at 1 1 5 F 


13 


65 


Penetration at 77 F 


0-3 


!5-5 


Penetration at 32 F 





2.3 


(Test 9^) Consistency at 1 1 5 F 


30-7 


10.6 


Consistency at 77 F 


83-4 


27.6 


Consistency at 32 F 


Over too 


66.9 


(Test 9^) Susceptibility index 


Over 33 


31.8 


(Test io) Ductility at 77 F 


o 


i 


(Test i $) Fusing-point (R. and B. ) 


210 F. 


i54iF. 


(Test 1 6) Volatile at 325 F., 5 hrs 


2 . 2 per cent 


2.8 percent 


(Test 19) Fixed carbon 


20.7 percent 


20.9 percent 


(Test 21) Soluble in carbon disulfide. . . . 


47.72 per cent 


86.88 percent 


Non-mineral matter insoluble. . 


36.85 percent 


9.25 per cent 


Mineral matter 


15.43 P^ cent 


3.87 per cent 


Total 


loo.oo per cent 


loo.oo per cent 


(Test 22) Carbenes 


0.42 per cent 


0.12 per cent 


(Test 23) Asphalt soluble in petroleum 






naphtha 


23 . 2 per cent 


60.3 percent 


(Test 33) Solid paraffins 


0.2 percent 


0.5 percent 


(Test 340) Asphalt as saturated hydrocar- 






bons 


10.5 percent 


26.8 percent 



The production ranges from 2000 to 4000 tons annually. 

Prefectures of Yamagata, Aomori and District of Hokkaido. 
Minor deposits have been reported at these localities, but have 
attained no commercial importance. 



AUSTRALIA 

New South Wales. Several occurrences have been reported in 
New South Wales. 89 

Western Australia. Minor deposits have been found in the 
Ord River basin, 150 miles south of Wyndham, near the junction 
of the Ord and Negri Rivers; likewise along the Stirling River. 90 

Northern Territory. An occurrence has been reported at the 
Waggon Lagoon, on Roper River, 350 miles east of Port Darwin. 90 



224 



ASPHALTS ASSOCIATED WITH MINERAL MATTER 



IX 



Tasmania. Asphalt deposits have been reported between Re- 
cherche Bay and New River in southern Tasmania. 81 

New Zealand. Asphalt deposits have been located in the Man- 
gawai and Arai Districts, between Bream Tail and Rodney Point. 



DUTCH EAST INDIES 

Buton (Boeton) Island. An extensive asphalt deposit occurs 
on Buton Island, south of Celebes Island. 92 Illustrated in Figs. 74 
and 75, Four different mines have been reported. 

(1) Kaboengka, estimated to contain approximately 1,200,000 
tons of asphaltic limestone, 

(2) Lawele, estimated to contain 100 million tons of asphaltic 
marl. 

(3) Waisioe. 

(4) Wariti. 

The composition of the asphalt is as follows : 





Kaboengka 


Lawele 


Waisioe 


(A) 


(B) 


(A) 


(B) 


Crude Asphalt: 
Water 


i-S% 
37-39% 

0,2-!% 

58-6i% 

1.09-1.12 
6-1 8 
61-69 

1 2-1 IO 
23.7-29.0% 


2% 
26-27% 

.5~ 2 % 
70-72% 

i. 06 
65 

5i ' 
no 

24-5% 


2% 

25-35% 
0.5-2% 

65-75% 


10-20% 
50-60% 
2-10% 
10-40% 


1-5% 
35~37% 

0.2-1% 
61-63% 

I.Op 
10 

64 

32 
25.9% 


Asphalt 


Organic matter. . . , . , , 


Mineral matter. . , > 


Extracted Asphalt: 
SD. ffr. at 77 F 


1. 06 

73 
47 
no 

25.7% 


Penetration at 77 F. . . ... 


Fusing-point (R. and B.) C. 
Ductility at 77 F 


Insol. in petr. naphtha (88). 



The mineral matter of all the deposits consists of microscopic 
shells (globigerina ) mixed with clay, and has the following com- 
position: CaCOa 81.62-85.27 per cent; MgCO 3 1.98-3.55 per cent; 
CaSQ* 0.55-1.70 per cent; CaS 0.17-0.33 per cent; combined water 
1*06-2.16 per cent; SiO 2 6.95-9.15 per cent; Fe 2 O s and A1 S O 3 2.15- 
3<ii p&r cent; undetermined 0.32*1*12 per cent 



IX 



DUTCH EAST INDIES 



225 



10 20 30MU&S 




74, Map of Buton Asphalt Deposits. 




FIG. 75. Mining Buton Asphalt. 



226 ASPHALTS ASSOCIATED WITH MINERAL MATTER IX 

AFRICA 

ALGERIA 

Province of Oran. At Constantine, asphaltic limestone is found 
in veins 32 ft. thick, containing as much as 40 per cent of asphalt. 
In many places the rock is so saturated that the asphalt seeps out 
and forms pools having a fusing-point of about 140 F. (K. and S. 
method), a penetration of 1 1 at 77 F., and containing 0.9 per cent 
of sulfur. The limestone is largely crystalline. Deposits have also 
been reported at Sidi Messaoud. 93 

NIGERIA 

Bituminous sands are reported in southern Nigeria a short dis- 
tance from the coast Attempts have been made to purify the 
asphalt by the water-extraction process, but so far this has resulted 
in failure. The extracted material contains about 70 per cent of 
asphalt, 10 per cent of organic substances other than asphalt and 
20 per cent of sand. 

RHODESIA 

Rock asphalt has recently been reported in northern Rhodesia 
but is not thoroughly investigated. 94 

MADAGASCAR 

Bituminous sandstones containing 3 to 6 per cent asphalt have 
been reported. 95 



CHAPTER X 



ASPHALTITES 

Asphaltites 1 are natural asphalt-like substances, characterized by 
their high fusing-points (over 230 F.). They are grouped into 
three classes, namely: gilsonite, glance pitch, and grahamite. Since 
all are presumably derived from the metamorphosis of petroleum, 
one would naturally expect the classes to merge into one another, 
and such actually proves to be the case. 

The author has adopted the following means of differentiating 
the three classes, one from another : 





Streak 


Specific 
Gravity 
at 77 F, 


Softening-point 
(K. and S, Method), 
Deg. F. 


Fixed Carbon, 
Per Cent 


Gilsonite or Uintaite . . . 
Glance Pitch or Manjak* 
Grahamite * 


Brown 

Black 
Black 


i .05-1 .10 
i . 10-1 . 1 5 
1.15-1.20 


230-350 
1130-350 
350-600 


10-20 
20-30 
3-55 













* When substantially free from mineral matter. 

In all three classes the non-mineral constituents are almost com- 
pletely soluble in carbon disulfide. The physical and chemical 
characteristics will be described in greater detail under the respective 
headings. 

GILSONITE OR UINTAITE 

This asphaltite is found in but one region, 2 extending from the 
eastern portion of the State of Utah across the boundary line into 
the western portion of Colorado. It occurs in a number of parallel 
vertical veins, varying in width from thin fissures to several feet. 

Gilsonite was first discovered by the early settlers in about 1862, 
at what was then known as the Culmer vein, several miles south of 
the present town of Myton in Duchesne County. All of the present 
veins are vertical and run from northwest to southeast. The gilson- 

227 



228 ASPHALT1TES X 

ite runs fairly uniform in composition, and complies with the fol- 
lowing general characteristics: 

(Test i) Color mass Black 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright to fairly bright 

(Test 6) Streak Brown 

(Test 7) Specific gravity at 77 F 1.05-1.10 

(Test 90) Hardness on Moh's scale 2 

(Test 9^) Hardness, needle penetrometer at 115 F, 3-8 
Hardness, needle penetrometer at 77 F. 0-3 
Hardness, needle penetrometer at 32 F. o 

(Test gc) Hardness, consistometer at 115 F 40-60 

Hardness, consistometer at 77 F 90-120 

Hardness, consistometer at 32 F Too hard for test 

(Test 9^) Susceptibility index > 100 

(Test lo*) Ductility at 77 F. (Author's Method) . . o 

(Test t$a) Fusing-point (K. and S. method) 230-350 F. 

(Test 15^) Fusing-point (R and B method) 270-400 F. 

(Test 16) Volatile at 325 F., 5 hrs. (dry substance) Less than 2 per cent 

Volatile at 400 F., 5 hrs Less than 4 per cent 

Volatile at 500 F., 5 hrs Less than 5 per cent 

(Test 19) Fixed carbon 10-20 per cent 

(Test 21) Soluble in carbon disulfide Greater than 98 per cent 

Non- mineral matter insoluble o-i per cent 

Mineral matter Trace-i per cent 

(Test 22) Carbenes o-J per cent 

(Test 23) Soluble in 88 petroleum naphtha 10-60 per cent 

(Test 26) Carbon 85-86 per cent 

(Test 27) Hydrogen 8. 5-10.0 per cent 

(Test 28) Sulfur 0.3-0.5 per cent 

(Test 29) Nitrogen 2.0-2.8 per cent 

(Test 30) Oxygen 0-2 per cent 

(Test 33) Solid paraffins o-Trace 

(Test 34^) Sulfonation-residue 85-95 per cent 

(Test 37*) Saponifiable matter Trace 

(Test 39) Diazo reaction No. 

(Test 40) Anthraquinone reaction No. 

Gilsonite is assorted and marketed in two varieties, known as 
"selects'' or "firsts," and "seconds" respectively. The "firsts" are 
taken from the center of the vein and are characterized by a con- 
choidal and lustrous fracture. The "seconds" occur near the vein 
walls and are characterized by a semi-conchoidal and semi-lustrous 
fracture. They are graded at the mine chiefly by their appearance. 
The firsts have a higher lustre, a lower fusing-point, a greater solu- 
bility in petroleum naphtha, and as produced at the mines run more 
uniform in physical characteristics than do the seconds. From the 
middle of the Cowboy vein, there is obtained a variety of gilsonite of 
unusually high lustre, having a deep black color with a bluish under- 



X 



GILSON1TE OR VINTAITE 



229 



tone, known to the trade as "jet gilsonite," and is used chiefly in the 
highest grades of baking enamels and japans. It melts about 90 F. 
higher than the "selects." The "selects" show the least tendency 
to gelatinize when dissolved in solvents, the "seconds" a moderate 
tendency, and the "jet" the greatest tendency. The three grades 
test as follows: 

Selects 

Color in mass Black 

Fracture Conchoidal 

Lustre Bright 

Streak Brown 

Specific grav. at 77 F. i .044 



Seconds 
Black 
Conchoidal 
Fairly bright 
Brown 



'(Test i) 
(Test 4) 
(Test 5) 
(Test 6) 

(Test 7) . _. ,. 

(Test go) Hardness (Moh's) 2 

(Test i$a) Fusing-point (K. and S.) 230-240 F. 240-280 F. 
(Test 1 5^) Fusing-point (R. and B.) 270-300 F. 275-325 F. 
(Test 23) Sol. in 88 petroleum 

naphtha 50-60% 20-50% 



1.049 

2 



Bluish black 
Pencillated 
Very bright 
Brown 
1.076 
a 

320-350 F. 
350-400 F. 



10-20% 



Figure 76 shows the hardness, tensile strength (multiplied by 
ro) and ductility curves of a mixture of gilsonite and residual oil, 
fluxed together so as to have a hardness of exactly 25.0 at 77 F. 



100 
90 

eo 

70 
60 

? 
40 

A 


32* 77 115 




^ 


ttntrT~" 


91.0 












umumuiromim-m / 

.._.. 7 


lardness 
"ensf/e Strength x 10 
luctfltty 
Point* 142 F. 
itib/Iiiy/ndex*4i7 


/ 


'"" 






'"X 


N, 








Fusing 
Suscef 






\ 








\ 












t 






% 


N 




























S, 






> 


55.0 


























v 


S k 






^ 




























V 


k 




\ 




* 


.. 


5 


in 








5V 

to 

10 

i 
















S 


2510 s 

< 


\ 


/ 
/ 




\ 
























S 


^ 


^s 




J! 

S 


IT- 
\ 


X 




















'2 


% ^ 


^ 


*N 
6 


r 


> ' 
a^ 


N 
-^^ 


V 




> K> 20 -50 40 50 60 70 60 90 100 110 180 150 14? 150 tt 
Temperature, Degrees Fahrenheit 
FIG. 76. Chart of Physical Characteristics of Fluxed Gilsonite. 



(Test 9<;), equivalent to a penetration of 20 at 77 F. (Test gb). 
The resulting mixture contained gilsonite, 47 per cent and resi- 
dual oil, 53 per cent- The fusing-point of the gilsonite used was 
285 F. (K. and S. method), and that of the resulting mixture 
~ 



230 ASPHALTITES X 

Gilsonite is one of the most valuable asphalts for manufactur- 
ing paints and varnishes. Gilsonite and glance pitch mix readily 
in ail proportions with fatty-acid pitches, thus differing from gra- 
hamite. Products involving the use of gilsonite formed the basis 
of several patents granted to S. H. Gilson, after whom the ma- 
terial was named. 8 

Gilsonite may be distilled until the vapors reach a temperature 
of 550 F., when an exothermic reaction takes place and the evo- 
lution of gaseous products becomes exceedingly rapid. The source 
of heat must be reduced at this stage, but when the critical point 
has been passed, the heating may be continued until the tempera- 
ture of the solid coke at the bottom of the still reaches 850 F. 4 
When the vapor temperature reaches 475 to 650 F. an oily dis- 
tillate is obtained, which upon refining with sulfuric acid, produces 
a reddish brown oil suitable for use as an oil substitute in making 
paints, 5 and the sulfonation product may be used to hydrolyze fats 
and oils. 6 

NORTH AMERICA 

UNITED STATES 
Utah. 

Uinta County. Practically all gilsonite is mined in the "Uinta 
Basin/' at the junction of the Green and White Rivers south of Fort 
Duchesne, Utah, from a point 4 to 5 miles within the Colorado 
boundary line (Rio Blanco County), extending westward about 60 
miles into Utah. A large number of veins have been located in this 
area, extending from a northwesterly to a southeasterly direction, 
and all of them parallel or nearly so. The veins vary in width 
from a fraction of an inch to 1 8 ft., and some of the longest, such 
as the Cowboy or Bonanza, have been traced 8 miles. The veins 
are almost vertical with fairly smooth and regular rock walls, and 
although they are usually continuous, they may in certain cases be 
interrupted in the direction of the fissure. Very frequently branch 
veins join the main one, forming very acute angles. 

Near the outcrop where it has been exposed to the weather, 
gilsonite loses its brilliant lustre, changing to a dull black. Along 
the vein walls it shows a columnar structure, extending at right 
angles to the wall, which is characteristic of all asphaltites. The 



X GILSONITE OR VINTA1TE 231 

rock walls are often impregnated with gilsonite */ 2 to 2 ft, so there 
is no visible line of demarcation between the impregnated and non- 
impregnated portions. In shale formation the impregnated zone 
is smaller than when the gilsonite is found in a porous sandstone. 
The following are the principal veins occurring in this region: 

Duchesne Vein. This occurs about 3 miles east of Fort Du- 
chesne, filling a vertical crack in sandstone and shale. The vein 
has been traced for 3 miles, and is 3 to 4 ft. wide for about I y 2 
miles, tapering at the ends, until it completely disappears, A com- 
paratively large quantity of gilsonite has been mined from this vein. 

Culmer Vein. This is also known as the "Pariette Mine," 
and occurs in the Castle Peak mining district. It has been traced 
7 miles and varies in width from a fraction of an inch to 30 in., 
averaging about a foot. Several branch veins are connected with 
the main one at very acute angles. It also shows a number of 
transverse faults as illustrated in Fig. 77, in which the lateral dis- 
placements vary from I to 10 ft. The associ- 
ated rock consists of sandstone and shale. 

Bonanza and Cowboy Veins. These em- 
brace three veins, known as the Cowboy vein, 
the East Branch and the West Branch respec- 
tively of the Bonanza Vein. The last two are 
joined together near the southern end. These 
veins occur in sandstone and shale. The shale 
being harder than the sandstone, seems to have 
offered greater resistance to the intrusion of 
gilsonite, and the veins are not therefore as wide 
when they occur in the latter. The disappear- 
ance of the veins to the northwest also occurs 
in shales, and as the gilsonite passes from sand- * fr * * *** 
stone into shale, it splits up into a number of FIG. 77. Faults in Gil- 
smaller veinlets which gradually thin out into sonite Vein, 
fine hair-like fissures. The Cowboy is the 
widest vein and attains a maximum width of 18 ft., maintaining for 
4 miles a width of 8 to 12 ft, as shown in Fig. 78. Its total length 
is 7 to 8 miles. The Bonanza veins have similarly been followed 
for 7 miles, but they are not as wide as the Cowboy. 

Dragon group of veins includes the original Dragon vein, the 
Country Boy and Rector veins, also the Rainbow vein abo*t 8 miles 
northeast. These occur southwest of Evacuation Creek, a tributary 
of the White River, near the Colorado boundary line. They extend 
about 4 miles in length and average between 2 and 3 ft. in width. 




232 



ASPHALTITES 



X 



In some places the adjacent rock is impregnated with the gilsonite 
i to 3 ft. alongside of the vein proper. In 191 1 an explosion shut 
down the Dragon vein, whereupon the operatives have been trans- 
ferred to the Rainbow, Country Boy, and Rector veins. 




Courtesy of American Asphalt Association. 
FIG. 78. View of Cowboy Gilsonite Mine, Utah. 

A number of smaller veins occur in this region, including the 
Uintah vein, with its branch the Little Emma vein, also the Harri- 
son, Colorado, and other veins. 



X 



GILSONITE OR UlNTAITE 



233 



A branch railroad, known as the Uintah Railroad, about 60 
miles long, runs from Dragon, Utah, connecting with the Denver & 
Rio Grande Railroad at Mack, Col., and then extends to a terminus 
at Watson, where the Rainbow mine is located. The product from 
the Country Boy and Rector mines must be trucked 3 to 5 miles, 




FIG. 79. Gilsonite Vein, Rainbow Mine, Utah. 

and that of the Little Emma mine is trucked to Craig, Colorado. 
These four mines were the only ones which are operated, producing 
in aggregate about 130 tons daily. Figures 79 and 80 show two 
typical views of the Rainbow mine. 

The method of mining is very crude, and consists in digging into 
the veins until a slope of 45 deg. is obtained. The gilsonite is then 



234 ASPHALTITES X 

dug from the face of the slope, rolled down to the bottom, sacked 
and hoisted out. The hoisting is done by horses at shallow levels, 
but when the mine becomes over 200 ft. deep, machinery must be 
used. Since the ore is brittle, there is always a cloud of dust in the 
stopes where the men work, which is soluble in the lubricating oil 




FIG. 80. Interior of Rainbow Mine, Utah. 

used with compressed-air mining tools, thus interfering with the 
operation of such tools. Experience has therefore shown that the 
production per man is greater with pick and shovel. One man can 
mine and sack an average of 2 tons per ten-hour day. Fires are a 
constant danger, as the dust is highly inflammable, and explosions 
have been caused by a chain dropping into a pit and striking against 
the rocky walls, causing sparks. 



X GILSONITE OR UINTA1TE 235 

Very little timber is required, as the veins are nearly vertical, and 
the surrounding rock is firm and self-supporting. Boulders of rock 
are frequently encountered in the veins, originally detached from 
the sidewalls, and prove a serious obstacle. Blasting can only be 
done where the ventilation is perfect and there is no gilsonite dust, 
and it frequently becomes necessary to abandon portions of the vein 
on this account. It is not feasible to work a vein less than 2 ft. 
wide. It is estimated that approximately 25 million tons of gilsonite 
are still available in this region. 

Oregon. 

Wheeler County. Minor deposits of a gilsonite-like material 
have been reported by E. T. Hodge T in the vicinity of Clarno 
(Type A) ; also 10 miles east of Post (on the Post-Paulina high- 
way) ; also on the south bank of Pine Creek near Clarno (Type B), 
testing as follows: 

A" Type"B" 



(Test i) Color in mass ............... Black Black 

(Test 4) Fracture ................... Conchoidal Conchoidal to hackly 

(Test 5) Lustre ..................... Brilliant Brilliant to dull 

(Test 6) Streak ..................... Brown Brown 

(Test 7) Specific gravity at 77 F ...... i .07-1 .08 1 .07-1 .08 

(Test 90) Hardness ................... 2 . aj 

(Test 1 5/*) Fusing-point (Note) ......... 525-550 F* 625-650 F. 

(Test 16) Volatile 325 F., 5 hrs ........ o-i per cent o-i per cent 

(Test 19) Fixed carbon ................ 5 . i per cent 23 per cent 

(Test 21) Soluble in carbon disulfide . . . 98-99 per cent 75 per cent 

Non-mineral matter insoluble 1-1.5 per cent 24. 5 per cent 

Mineral matter .............. 0.5 per cent o . 5 per cent 

(Test 22) Carbenes ................... i-i . 5 per cent 22 per cent 

(Test 23) Soluble in 88 petroleum naph- 

tha ...................... 30 per cent p per cent 

NOTE. The fusing-points are somewhat high for a gilsonite, and approach that of graham- 
ite. The above materials are examples of border-line cases. Both types are undoubtedly 
similar materials, and Type B has been weathered, so that its original characteristics have 
been altered. Huntly classes "A" as a gilsonite and " B " as a grahamite. 

Crook County. A prospect has been located 38 miles south- 
east of Prineville, on Sec. 33, T 16 S, R 20 E. (Willamette meri- 
dian) , It occurs both inside and outside of chalcedony-quartz-calcite 
geodes, also in the interstices of tuffaceous sandstone, likewise in 
jasperoid rock alongside a dyke of rhyolite. It appears that the 



236 ASPHALTITES X 

rhyolite penetrated and fractured an oil-bearing stratum, allowing 
the oil to ascend along the wall of rhyolite. It tests as follows: 

(Test i) Color in mass Black 

(Test 4) Fracture. . , Conchoidal 

(Test 5) Lustre Very bright 

(Test 6) Streak Reddish brown 

(Test 7) Specific gravity at 77 F 1.162 

Behavior on heating in flame Softens, froths, and burns 

(Test i$a) Fusing-point (K. and S. method) 275 F. 

(Test 21) Soluble in carbon disulfide 83.00 per cent 

Non-mineral matter insoluble 16.39 per cent (Note) 

Mineral matter o. 61 per cent 

Total 100.00 per cent 

NOTE. Consists of brown powder, which swells up in carbon disulfide, or when heated. 

This asphaltite appears to be a metamorphized gilsonite. Only 
part is soluble in residual oil (asphaltic), also linseed oil, but on 
prolonged heating the insoluble matter depolymerizes and gradually 
goes into solution. 

ASIA 

RUSSIA 

Archangel Province. A hard asphaltite, closely resembling gil- 
sonite, having a specific gravity at 77 F. of 1.0887 and a fusing- 
point (K. and S. method) of 240 F. has been reported 8 in the 
Ukhta district on the Izhma River. 



GLANCE PITCH 

Glance pitch resembles gilsonite in its external appearance, with 
the exception of the streak, which is a decided brown in the case of 
gilsonite, and black in the case of glance pitch. It also differs in 
having a higher specific gravity and producing a larger percentage of 
fixed carbon. It always has a brilliant conchoidal fracture, and a 
fusing-point between 230 and 350 F. (K, and S. method). In 
general, glance pitch complies with the following characteristics: 

(test i) Color in mass Black 

(Test 4) Fratture, , * Conchoidal to hackly 

(Test 5) Lustre Bright to fairly bright 

(Test 6) Streak on porcelain Black 

(Test 7) Specific gravity at 77 F 1.10-1.15 



X GLANCE PITCH 237 

(Test 90) Hardness, Moh's scale 2 

(Test 9^) Hardness, needle penetrometer at 77 F, o 

(Test 9^) Hardness, consistometer at 77 F 90-120 

(Test gd) Susceptibility index > 100 

(Test 10) Ductility at 77 F o 

(Test 15*) Fusing-point (K. and S. method) 230-350 F. 

(Test 15^) Fusing-point (R. and B. method) 270-375 F. 

(Test 1 6) Volatile at 325 F., 5 hrs. (dry substance) Less than 2 per cent 

Volatile at 400 F., 5 hrs Less than 4 per cent 

(Test 19) Fixed carbon 20-30 per cent 

(Test 21) Soluble in carbon disulfide Usually greater than 95 per cent 

Non-mineral matter insoluble Less than i per cent 

Mineral matter Usually less than 5 per cent 

(Test 22) Carbenes ; Less than i .o per cent 

(Test 23) Soluble in 88 petroleum naphtha 20-50 per cent 

(Test 26) Carbon 80-85 per cent 

(Test 27) Hydrogen 7-12 per cent 

(Test 28) Sulfur 2- 8 per cent 

(Test 29) Nitrogen and oxygen Trace to 2 per cent 

(Test 33) Solid paraffins o-Trace 

(Test 34^) Sulfonation residue 80-95 per cent 

(Test 37*) Saponifiable matter Trace 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction No 

Glance pitch appears to be intermediate between the native 
asphalts and grahamite. It is probably derived from a different 
character of petroleum than gilsonite, having nevertheless reached 
a parallel stage in its metamorphosis, under approximately the same 
external conditions. 

NORTH AMERICA 

WEST INDIES 

Barbados. Glance pitch was first reported in 1750 by Griffith 
Hughes, and since 1896 has been mined almost continuously. De- 
posits occur in a number of localities throughout the island, espe- 
cially in the Conset district, at Groves, Springfield, St. Margaret, 
Quinty, and Burnt Hill. This asphaltite has been marketed under 
the name of "manjak," which was originally applied to the Barbados 
product, although the name was subsequently associated with a 
variety of grahamite mined in Trinidad. 9 The deposits were first 
worked on a commercial scale by Walter Merivale in 1896, who also 
accurately described the deposit, and the properties of the mineral. 

Barbados manjak contains a very small percentage of sulfur 
(between 0.7 and 0.9 per cent), and about 1-2 per cent of mineral 
matter. Its specific gravity at 77 F. is in the neighborhood of no> 



238 ASPHALTITES X 

fusing-point 320-340 F. (K. and S. method), the percentage of 
fixed carbon as reported by different observers varies between 25 
and 30 per cent and its solubility in carbon disulfide 97-98 per 
cent Near the surface, the rnanjak is hard and brittle with a high 
fusing-point, but at the lower levels of the mines it is found softer, 
and with a much lower fusing-point, partaking of the nature of an 
asphalt, rather than an asphaltite, and clearly proving the meta- 
morphosis of one from the other. It also indicates that the manjak 
originated in the lower strata, having been thrust upward in the 
form of a dyke (see also Trinidad grahamite). 

It is used largely for the manufacture of varnishes and japans on 
account of its high purity, gloss, and intense black color. 10 

Santo Domingo (Haiti). A deposit of glance pitch similar to 
the preceding has been reported near Azua on the Bay of Ocoa. 
This has not been developed commercially, nor are analyses avail- 
able. 

CUBA 

There are numerous deposits of glance pitch occurring through- 
out Cuba, including the following : 

Province of Pinar del Rio. Several mines, under the names 
"Constancia," "San Jose," etc., occur in the district of Mariel, near 
the village of Banes, on both sides of the Alfene River, testing as 
follows : 

(Test i) Color in mass Black 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Dull 

(Test 6) Streak Brownish black 

(Test 7) Specific gravity at 77 F i . 29-1 .34 

(Test 90) Hardness, Moh's scale 2-3 

(Test 19) Fixed carbon 24.3-27. 8 per cent 

(Test 21 ) Soluble in carbon disulfide 70-74 per cent 

Non-mineral matter insoluble 2-3 per cent 

Mineral matter 24-27 per cent 

(Test 23) Soluble in 88 petroleum naphtha 37. 5-49. o per cent 

This glance pitch carries considerable adventitious mineral mat- 
ter, thus differing from the preceding. 

Province of Santa Clara. Veins of glance pitch have been re- 
ported in the northern portion of Sancti Spiritus district, likewise 
in Yaguajay district along the eastern bank of River Jatibonico del 
Norte. The latter are probably a continuation of the veins occurring 
on the west side of this same river in Province of Camaguey, de- 
scribed below. 



X 



GLANCE PITCH 



239 



Province of Camaguey. In the Moron district, on the west side 
of River Jatibonico del Norte, several mines of glance pitch resem- 
bling gilsonite have been developed, known as "Esperanza," u San 
Rafael/' "Manocal" and "Talaren." The last named is the 
largest, and the product is shipped from Port Tariffa. The material 
tests as follows: 



Selects 



Seconds 



(Test 
(Test 
(Test 
(Test 
(Test 


I) 
4) 
5) 
6) 
7) 


Color in mass 
Fracture 
Lustre 
Streak 
Specific gravity at 77 F 


Black 
Conchoidal 
Bright 

Black 

1. 12 


Black 
Conchoidal 
Bright 
Black 

1. 12 


(Test 


8*) 


Hardness, Moh's scale 


2 




2 








(Test 


15*) 


Fusing-point (K. and S. method) 


315 


F. 


345 


o 


F. 




(Test 


15*) 


Fusing-point (R. and B. method) 


284 


F. 


372 


o 


F. 




(Test 


19) 


Fixed carbon 


26 per cent 


28 per cent 


(Test 


) 


Soluble in carbon disulfide 


99- 


25 per cent 


97- 


3 


per 


cent 






Non-mineral matter insoluble 


o. 


23 per cent 


0, 


2 


per cent 






Mineral matter 


o. 


52 per cent 


2. 


5 


per 


cent 


(Test 


22) 


Carbenes 


0. 


i per cent 


0, 


2 


per 


cent 


(Test 


23) 


Soluble in 88 petroleum naphtha. . . . 


18. 


o per cent 


I4 


5 


per 


cent 


(Test 


26) 


Carbon 


79- 


7 per cent 


. . . 


. 






(Test 


27) 


Hydrogen 


8. 


2 per cent 


. . . 


. 






(Test 


28) 


Sulfur 


7- 


4 per cent 


. . . 


. 










Undetermined (nitrogen and oxygen) . 


4- 


8 per cent 


... 










Total 100.0 per cent 



MEXICO 



State of Vera Cruz. 



District of Chapapote. As stated previously, deposits of very 
pure asphalt occur in this locality, varying from very soft consist- 
ency to a hard and brittle asphaltite, properly classified as "glance 
pitch." They show a lustrous and conchoidal fracture, a black 
streak, fuse in the neighborhood of 250 F. (K, and S. method), 
contain over 20 per cent of fixed carbon, and are more than 99 per 
cent soluble in carbon disulfide. 

District of Papantla. Glance pitch occurs near the village of 
Talaxca, about 6 miles north of Papantla, within 30 miles of the 
port of Gutierrez-Zamora on the Tecolutla River, whence it is trans- 
ported by lighters to vessels at Tecolutla on the Gulf of Mexico. 
The glance pitch fills a fissure in hard conglomerate in a vein 2 to 3 
feet wide, running north and south for a length of about 35 kilo- 



240 ASPHALTITES X 

meters. It has been mined to a depth of 80 feet, and tests as 
follows : 

(Test i) Color in mass Black 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .093-1 . 108 

(Test 1 5^) Fusing-point (R. and B. method) 298-317 F. 

(Test 19) Fixed carbon 21 . 5-24.0 per cent 

(Test 21) Soluble in carbon disulfide 99.76 per cent 

Non-mineral matter insoluble 

Mineral matter o . 24 per cent 

Total 100 .00 per cent 

(Test 22) Soluble in carbon tetrachloride , 99 . 72 per cent 

(Test 23) Soluble in 88 petroleum naphtha 27-35 per cent 

(Test 28) Sulfur 7. 13 per cent 

TT , UNITED STATES 

Utah. 

Emery County. Deposits of glance pitch occur at Temple 
mountain, 45 miles southeast of the town of Greenriver on the 
eastern flank of San Rafael swell, also at Flat Top mountain, 
2 1 /2 miles to the southeast Occur as glistening black nodules rang- 
ing in size up to 2 J^ in. in diameter in a bed of sandstone con- 
glomerate about 60 ft. thick. The asphaltite is characterized by the 
fact that it carries uranium and vanadium, which are assumed to 
have been incorporated in it during its migration from the under- 
lying strata, thereby hardening the asphaltite and "fixing" it in the 
present associated rocks. The material contains an average of 1.75 
per cent U S O 8 and 4 per cent V 2 O 5 . Specimens taken from the 
Cowboy claim (Shinarump conglomerate), designated "A," and 
from the lower part of sandstone on the west slope of Temple 
mountain, designated "B," analyze as follows: 

Specimen" A? Specimtn"B" 
Per cent Per cent 

Loss on ignition * 49-57 67 . 1 1 

Ash soluble in HC1: 

Uranium oxide (UsOg) i . 13 2.88 

Vanadium oxide (V A) 0.23 1.17 

Sulfur 4-98 i -37 

Arsenic Trace Trace 

Selenium. I............. None None 

Ash insoluble in HC1 4^-3 a * 6 <$4 

Total - 102*13 99.07 



X GLANCE PITCH 241 

In many places the asphaltite has completely weathered away/ 
leaving deposits of the metals and metalloids in the form of uranium 
and vanadium hydroxides, uranium vanadate, calcium vanadates 
(i.e., red and green varieties), calcium-uranium vanadate, potas- 
sium-uranium vanadate, copper-uranium arsenate, etc, 1 



11 



CENTRAL AMERICA i 2 

NICARAGUA 

District of Chontales. A vein of glance pitch has been reported 
about 10 miles northeast of Santo Tomas, northeast of the moun- 
tain range, about i in. thick, in a fault plane of small displacement, 
cutting water-laid volcanic tuffa. 

SALVADOR 

Department of San Miguel. At the waterfall in Quebrada 
Granda, one mile southwest of the "Otuscal 1 Ranch," glance pitch 
is present as a fracture filling, associated with calcite and chalcedony. 

SOUTH AMERICA 
COLOMBIA 

Department of Tolima. A large deposit of glance pitch occurs 
at Chaparral on the Saldana River, which empties into the Magda- 
lena River. The deposit is about 100 miles southwest of Bogota. 
It is transported by boats down the Magdalena River to the coast, 
whence it is exported. About 2000 tons are shipped annually 
having a high fusing-point and over 99 per cent soluble in carbon 
disulfide. 13 It is used largely for the manufacture of varnish and 
tests as follows: 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre , . Bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i , 12 

(Test 8a) Hardness, Moh's scale, a 

(Test 8i) Hardness, penetrometer o 

(Test 15) Fusing-point (K. and S. method) 275 F. 

(Test 19) Fixed carbon , 26,45 per cent 

(Test 21) Solubility in carbon disulfide 96,0 per cent 

Non-mineral matter insoluble o.>per cent 

Mineral matter 3.3 per cent 



242 ASPHALTITES X 

Department of Bolivar. A similar deposit occurs at Simiti, on 
the western bank of the Magdalena River, north of the foregoing 
deposit 

EUROPE 

GERMANY 

Bentheim. Deposits of asphaltite, probably of the nature of 
glance pitch, are found in the vicinity of Bentheim, These were 
first regarded as a coal, and have been worked since 1732. The 
material is hard, shows a glossy, conchoidal fracture, a black streak, 
specific gravity of 1,07 to 1.09, and 0.53 to 11.24 P^ r cent ash. 



14 



ASIA 

SYRIA (LEVANT STATES) 

Vilayet of Sham (Syria). An extensive series of glance pitch 
deposits occur in the vicinity of Hasbaya (see map, Fig. 72) in the 
upper Jordan valley, on the western slope of Mount Hermon ( Jebel 
esh Sheikh). The principal mine, known as "Suk el Chan" or 
"Bir el Hummar" is located on the eastern slope of Jebel ed Dahr, 
a hill separating the Jordan River (Nahr Hasbani) and the Nahr 
Litani, where a deposit of glance pitch of brownish black color is 
found in a vein up to 4 m. thick. It has a brilliant lustre and a 
black streak, specific gravity at 60 K of 1.104, contains from a 
trace to 5 per cent mineral matter, fuses at 275 F., and yields 27 
per cent fixed carbon. An average specimen on analysis shows: 
carbon 77,18 per cent, hydrogen 9,07 per cent, sulfur 0,40 per 
cent, nitrogen 2.10 per cent, and mineral matter 0.50 per cent. 
This deposit is said to have been worked since about 1600 B.C. 
Some of the ancient pits are still to be seen, as deep as 60 m. 
From 1890 to 1900, about 66,000 tons were mined, and a quantity 
exported to the United States for the manufacture of varnishes, for 
which it is well suited. . In this same region there is, found an 
asphaltic limestone impregnated with an average of 10 per cent 
asphalt of comparatively high fusing-point (presumably glance 
pitch) associated with petrified fish remains. 15 



X 



GRAHAMITE 



243 



Palestine. The Dead Sea deposits are merely of historical inter- 
est, as they constituted one of the principal sources of supply of 
asphalt for the ancients. There appear to be large veins of asphalt 
at the bottom of the Dead Sea, the water of which is saturated with 
salt (25 per cent solution) having a gravity of about 1.21. The 
asphalt has a specific gravity at 77 F. of 1.104, an d as masses be- 
come detached at the bottom by earthquake shocks or otherwise, 
they float to the surface, where they are gathered up by natives. A 
section through the Dead Sea showing the veins of asphaltite is 
illustrated in Fig. 81. Deposits also occur at Es Sebba (Es Sebbe) 




FIG. 8 1. Vertical Section, through Dead Sea Showing Glance Pitch Veins. 

and Masada on the west shore, and at Seil-el-Modschib on the east 
shore of the Dead Sea. This glance pitch shows a lustrous, con- 
choidal fracture, and a black streak. Its fusing-point is 275 F., 
over 99 per cent is soluble in carbon disulfide, and it yields 20 per 
cent of fixed carbon. The supply is limited and the material is 
used only to a small extent locally. 1 



16 



MESOPOTAMIA (IRAQ) 

A deposit occurs at Abu Gir on the Euphrates River, west of 
Baghdad, containing 86.5 per cent soluble in carbon disulfide, 10.0 
per cent mineral matter and 3.5 per cent water; having a fusing- 
point (R. and B.) of 172 C. and containing 7.3 per cent sulfur. 
The mineral constitutents contain Ca, Mg and Fe, with a trace of 
vanadium. 

GRAHAMITE 

This asphaltite varies considerably in composition and physical 
properties, some deposits occurring fairly pure and others are asso- 



244 ASPHAJLTITES X 

dated with considerable mineral matter, running as high as 50 
per cent 17 In general, however, it complies with the following : 

Test i) Color in mass Black 

(Test 4) Fracture Conchoidal to hackly 

(Test 5) Lustre Very bright to dull 

(Test 6) Streak on porcelain Black 

(Test 7) Specific gravity at 77 P.: 

Pure varieties (containing less than 10 per 

cent mineral matter) 1 . 15-1 .20 

Impure varieties (containing more than 10 

cent mineral matter) 1 . 175-1 .50 

(Test 90) Hardness, Moh's scale 2-3 

(Test gk) Hardness, needle penetrometer at 77 F o 

(Test 9<r) Hardness, consistometer at 77 F Over 150 

(Test gel) Susceptibility index > 100 

Behavior on heating in flame: 
Variety showing a conchoidal fracture and a 

black lustre Decrepitates violently 

Variety showing a hackly fracture and a 

fairly bright to dull lustre Softens, splits and burns 

(Test 150) Fusing-point (K. and S. method) 350-600 F. 

(Test 1 5$) Fusing-point (R.. and B. method) 370-625 F. 

(Test 1 6) Volatile at 500 F., 5 hrs Less than i per cent 

(Test 19) Fixed carbon 30~55 per cent 

(Test 21) Soluble in carbon disulfide 45-100 per cent 

Non-mineral matter insoluble in carbon disul- 
fide Less than 5 per cent 

Mineral matter Variable (up to 50) per cent 

(Test aa) Carbenes , 0-80 per cent 

(Test 23) Soluble in 88 petroleum naphtha Trace-5o per cent 

(Test 30) Oxygen in non-mineral matter o-a per cent 

(Test 33) Solid paraffins o-Trace per cent 

(Test 34^) Sulfonation residue 80-95 per cent 

(Test 37*) Saponifiable matter Trace 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction , , . . . No 

In general, grahamite is characterized by the following features : 
i) High specific gravity; 



Black streak; 

High f us ing-point; 

High percentage of fixed carbon, 

Solubility of non-mineral matter in carbon disulfide. 



A process has been proposed for reducing the fusing-point of 
grahamite, by heating the material either alone, or with a propor- 
tion of serni-asphaltic residual oil (12 to 14 Baurne) in a closed 
retort at 400 F, for twenty- four hours, under a pressure of 50 Ib. 
per sq. in. This converts the asphaltite into a product similar in 



GRAHAMITE 



245 



appearance to gilsonite, having a black streak. The percentage of 
carbenes is reduced and the proportion soluble in 88 petroleum 
naphtha is increased. 18 Processes have been described for fluxing 
grahamite with coal tar 19 ; also for fluxing grahamite and adding 
a mineral filler. 20 

Deposits of grahamite occur in the following localities: 



NORTH AMERICA 

UNITED STATES 



West Virginia. 



Ritchie County. The original deposit of grahamite was dis- 
covered in West Virginia. 21 It was first described by Prof. J. P. 




FIG. 82. View of Grahamite Vein, Ritchie County, West Virginia. 



246 



ASPHALTITES 



X 



Leslie in a paper read before the American Philosophical Society, 
March 20, 1863. It is found in but a single locality in Ritchie 
County, about 25 miles southeast of Parkersburg. The grahamite 
fills an almost vertical fissure in sandstone, a mile long, varying in 
width from 2 in. at the ends to 4 and 5 ft. in the center. Its depth 
is assumed to be 1500 to 1600 ft 

The mine has long been abandoned, as the available supply of 
grahamite is exhausted. Figure 82 shows a view of the opening in 




FtiULTZQNE^ 

M/necf from /ot//f 



<\ ,VV\ U!DDERM1Y_ 



' ' - ._ ;#/W 

to the Ritchie 



rflfrfrr ,^,-0 




Elevation 



bewhtre 



A*WA 16'Wide 



f Fissure above fault 
I ?4"W/& 30'M& 3&W& 




* fissure be fort Faufr 



Plan 



FIG. 83. Sections through Grahamite Mine, Ritchie County, W. Va. 

the hillside from which the grahamite has been removed. Figure 83 
shows the nature and extent of the workings. Next to the sand- 
stone walls, the grahamite shows a coarsely granular structure, with 
a semi-dull fracture. The following layer is highly columnar in 
structure with a lustrous fracture. Finally, in the center of the 
vein, the grahamite is more compact and massive, with the col- 
umnar structure less developed and a semi-dull fracture. This 
variation in structure, fracture and lustre is characteristic of gra- 
hamite deposits. 

On analysis it tests as follows: 



X 



GRAHAMITE 



247 



(Test 6) 
(Test 7) 
(Test 90) 

(Test 150) 
(Test 19) 
(Test 21) 



Streak on porcelain Black 

Specific gravity at 77 F 1 . 18-1 . 185 

Hardness on Moh's scale 2 

Behavior on heating in flame Softens, burns and splits 

Fusing-point (K. and S. method) 520-540 F. 

Fixed carbon 42 . 1 5-42 , 48 per cent 

Soluble in carbon disulfide . . 97. 61 per cent 

Non-mineral matter insoluble 0.17 per cent 

Combined mineral matter o. 44 per cent 

Free mineral matter 1.71 per cent 



Total 99 . 93 per cent 

(Test 22) Insoluble in carbon tetrachloride 55- o per cent 

(Test 23) Soluble in 88 petroleum naphtha 3.0 percent 

(Test 25) Hydroscopic moisture 0.07 per cent 

(Test 26) Carbon 86. 56 per cent 

(Test 27) Hydrogen 8 . 68 per cent 

(Test 28) Sulfur i .79 per cent 

Difference 2. 97 per cent 

Texas. 

Fayette and Webb Counties. Clifford Richardson 22 reports a 
deposit of grahamite in Fayette County in the neighborhood of 
Lagrange, also an occurrence in Webb County, near Laredo, in the 
southern portion of the State. These test as follows: 







Fayette County 
Grahamite, 
Per Cent. 


Webb County 
Grahamite, 
Per Cent. 


(Test 10) 


Fixed carbon 


37.7 


52.8 


(Test 21 ) 


Mineral matter 


4.2 


2.O 


(Test 2c) 


Moisture. 


o. 3 


O-3 


(Test 26) 


Carbon 


76.2 


78.6 


(Test 27) 


Hydrogen 


6.6 


7.5 


(Test 28) 


Sulfur 


7.4 


5.4 


(Test 20) 


Nitrogen 


0.4 


1.2 




Undetermined 


<.2 


C.I 











Oklahoma. 23 

Pushmataha County. Two small occurrences are reported in 
the Potato Hills about 5 miles north of Tuskahoma, One is in SE 
y 4 , Sec. i, T 2 N R 19 E, and the other in NE #, Sec. 2, T a 
N, R 19 E. Neither of these is of importance. 

Jackford Creek Deposit. The largest known grahamite vein in 
the world occurs in Jackf ork Valley* 1 2 miles west of Tuskahoma in 



ASPHAITITES 



X 



the SE J4, NE M, Sec. 9, T 2 N, R 18 E, It is about i mile long, 
and varies in thickness from 19 to a maxipium of 25 ft At the 
surface, the vein dips at an angle of 37, and after continuing down- 
ward for 140 ft, turns suddenly at an angle between 45 and 50 deg. 
It is illustrated in Fig. 84. The grahamite fills a fault in shaly sand- 
stone. The upper wall of the vein is firm and requires no timbering. 
In mining the material, oive-ins are prevented by allowing pillars 
of grahamite to remain in place to support the upper "hanging" 
rock wall. When the author visited the mine in 1912, a track was 
laid along the bottom wall, and the grahamite hoisted out in skips on 




Courtesy of Central Commercial Co. 
FIG. 84. Vertical Section through Grahamite Mine Near Tuskahoma, Okla. 

a cable-way. There is evidence of large pieces of rock having be- 
come detached from the hanging wall and fallen into the deposit 
of grahamite before it became solid. 

As is tfopimon with most grahamite deposits, several distinct 
types of material are found in the vein. The grahamite which oc- 
curs atong the rock walls for a thickness of 2 to 6 ft. (type b) shows 
a hackly (known as a "pencillated") fracture, and a semi-dull to dull 
lustre/ whereas the grahamite taken from the center of the vein 
(type a) shows a conchoidal fracture and very bright lustre similar 
to gilsonite. This is probably due to the fact that the grahamite 
in contact with the wall cooled more rapidly than the central portion, 



X 



GRAHAMITE 



249 



and very likely has also been subjected to more or less strain from 
movements of the suijounding rock. Many thousand tons of gra- 
hamite have been mined from this vein which is now pretty nearly 
exhausted (from 6000 to 7000 carloads during the first four years 
of its operation, and at the time of the author's visit about 50 tons' 
per day). The cost of moving to the surface is comparatively 
small, but the material has to be carted 10 miles to Tuskahoma, HI* 
nearest shipping point. 

On analysis the two varieties (a) and (b) test as follows: 

(Test ;) Color in mass (types a and b) Black 

(Test 4) Fracture (type a) Conchoidal 

Fracture (type b) Hackly 

(Test 5) Lustre (type a) .,.., Bright 

Lustre (type b) Semi-bright to dull 

(Test 6) Streak (types a and b) Black 

(Test 7) Specific gravity at 77 F. (types a and b) . . i . 1 8-1 . 195 

(Test 9* ) Hardness, Moh's scale 2 

Behavior on heating in flame (type a) Intumesces violently 

Behavior on heating in flame (type b) Softens, splits and burns 

(Test 1 5* ) Fusing-point (K. and S. method) (types a and b) . . 530-604 F, 

NOTE. There is no appreciable difference in fusing-point between the two varieties 
(a and b)* 

(Test 16) Volatile matter 500 F., 5 hrs Less than i per cent 

(Test 19) Fixed carbon (types a and b) 52.76-55.00 per cent 

(Test 21) Solubility in carbon disulfide Greater than 99. 5 per cent 

' Non-mineral matter insoluble Less than o, 5 per cent 

Free mineral matter (types a and b) ...,., o. 21-0, 70 per cent 

32 77 115 



IW 

90 
80 
70 
60 
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ensile Strength* 

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Fusing Point *2QQF 
Susceptibility Index* 2t.$ 




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10 ZO W 40 50 eo 70 60 90 100 HO 120 130 140 150 160 
Tempera ture,Degrees Fahrenheit 

FIG. 85. Chart of Physical Characteristics of Fluxed Oklahoma Grahamite Mixture. 



250 ASPHALTITES X 

Figure 85 shows the consistometer hardness, tensile strength 
(multiplied by 10) and ductility curves of a mixture of the graham- 
ite and residual oil, fluxed together so as to have a hardness of 
exactly 25.0 at 77 F. (Test gc), equivalent to a penetration at 77 
F. of 20 (Test 9&). The mixture contains: grahamite, 60 per cent; 
and residual oil, 40 per cent. The resulting fusing-point (K. and S. 
method) was 277 F. The same residual oil was used in this test 
as for the gilsonite in Fig. 76, and the fusing-point of the grahamite 
used was 550 F. (K. and S. method). 24 

Another mixture containing 33 per cent of the grahamite and 
67 per cent of the same residual oil tested as follows: 

(Test 9^) Penetration at 115 F., 50 g., 5 sec 81 

Penetration at 77 F., 100 g., 5 sec 50 

Penetration at 32 F., zoo g., 60 sec 55 

Penetration at o F., 200 g., 60 sec 29 

(Test gc) Consistency at 1 15 F 5.8 

Consistency at 77 F 11.7 

Consistency at 32 F 21 . 5 

Consistency at o F 37. 6 

(Test 9*0 Susceptibility index 11.7 

(Test iob) Ductility at 115 F 15 

Ductility at 77 F 3 

Ductility at 32 F i J 

Ductility at o F , J 

(Test 150) Fusing-point (K. and S. method) 135 F. 

(Test 15*) Fusing-point (R. and B. method) 147 F. 

(Test 16) Volatile at 500 F., 5 hrs o. 6 per cent 

(Test 17^) Flash-point 535 F. 

This particular mixture is characterized by its extremely low 
susceptibility index and its high ductility, which manifests itself 
even at o F. 

Impson Valley Deposit. This occurs on a branch of the Ten- 
mile Creek on the SW J4, Sec. 21 and NW */ 4 , Sec. 28, T i S., 
R 14 E., about 1 6 miles northwest of Antlers. It is known under 
various names such as Jumbo Mine, Choctaw Mine, or Old Slope 
Mine, This is the second largest deposit in the State of Oklahoma. 

It occurs in a zone of faulting and fracture in shale rock, and the 
vein is lenticular in form, occurring as a series of pockets of the 
general form, illustrated in Fig. 32, varying in thickness from a 
fraction of an inch to 30 ft. as a maximum. As the dip of the vein 
is very steep, the material must be hoisted out in buckets with a 
windlass, and then hauled 15 miles to Moyer, the nearest shipping 



X GRAHAM1TE 251 

point. Heavy timbering is necessary on account of the character 
of the enclosing rock. The grahamite shows the same variation in 
fracture and lustre as the Jackford Creek deposit. On analysis it 
tests as follows: 

Color in mass, fracture, specific gravity, hardness and behavior 
on heating in flame, same as the preceding : 

(Test 15) Fusing-point (K. and S. method) 460-520 F. 

(Test 1 6) Volatile matter, 500 F., 5 hrs Less than I per cent 

(Test 19) Fixed carbon 48.5-53-0 per cent 

(Test 21) Solubility in carbon disulfide 90. 5-96. a per cent 

Non-mineral matter insoluble 0.0-6.0 per cent 

Free mineral matter 1 . 1-6. 7 per cent 

(Test 22) Carbenes 68 per cent 

(Test 23) Solubility in 88 petroleum naphtha 0.2-0.7 per cent 

(Test 25) Moisture at ioo-C 0.0-0.7 per cent 

(Test 26) Carbon 83.90 per cent 

(Test 27) Hydrogen 7.14 per cent 

(Test 28) Sulfur i .04-2.24 per cent 

Undetermined 6,72 per cent 

(Test 340) Saturated hydrocarbons 0.32 per cent 

Atoka County. McGee Creek Deposits. Two small veins, one 
4 in. and another about i ft in thickness, occur in the SW J4, Sec. 
23, T i N, R 14 E, about 15 miles northwest of Antlers. These 
constitute the so-called "William's Mine." Shafts have been sunk 
from 15 to 20 ft, but not sufficient grahamite has been found to 
warrant continuing operations. It tests as follows: 

(Test 19) Fixed carbon 43. 5-45.7 per cent 

(Test 21) Soluble in carbon disulfide 95-7~99-7 per cent 

Non-mineral matter insoluble 0.0-4.0 per cent 

Free mineral matter 0.3 per cent 

(Test 23) Soluble in 88 petroleum naphtha 4. 5- 6. 8 per cent 

A larger deposit also occurs in the vicinity of McGee Creek, in 
the NE }4, Sec. 25, T i S, R 13 E, and NW *4, Sec. 30, T i S, 
R 14 E, about 12 miles southeast of Stringtown. This is known 
as the Pumroy or Moulton Mine. The grahamite fills a fissure, 
caused by faulting, and is reported to be 14 to 15 ft. thick at the 
surface, tapering to about 4 ft at a depth of no ft. The mine 
is now abandoned, but when operated some years ago, about 2000 
tons were mined annually, being hauled 1 5 miles to Stringtown, the 
nearest shipping point A prospect occurs about % niile south of 



252 ASPHALTITES X 

the foregoing, consisting of a vein about 2 ft. thick. On analysis 
it tests as follows : 

(Test 151?) Fusing-point (K. and S. method) 473 F. 

(Test 19) Fixed carbon 38.42-41 .o per cent 

(Test 21) Solubility in carbon disulfide 83 . 7 -95 . o per cent 

Non-mineral matter insoluble 4.8-9,2 per cent 

Free mineral matter 0.98- 7.1 per cent 

Boggy Creek Deposit. This occurs about 6 miles northeast of 
Atoka, and i mile from the M. K. & T. R. R. in the SW %, Sec. 29, 
T i S, R 1 2 E. The vein occurs in shale varying in thickness from 
several inches to several feet. It has long been abandoned, and no 
analyses are available. 

Chickasaw Creek Deposit. An undeveloped vein in shale, 
carrying streaks of grahamite, about 9 ft. thick has been reported in 
Sec, 15, T i S, R 12 E about 2 l / 2 miles east of Stringtown on the 
M. K. & T. Railroad. 

Stephens County. This occurs in the NW >, Sec. 6, T 2 S, 
R 4 W, about 6 miles north of Loco, and 18 miles east of Coman- 
che. This vein has been prospected for about half a mile, and occurs 
as a fault in sandstone and shale. The vein is of a pronounced len- 
ticular type existing in a series of pockets, some as large as 10 ft. 
across, often connected with a thin vein-like crack less than an inch 
wide. At several points the deposit pinches out entirely. In the 
direction of the vein, the pockets measure 25 to 100 ft. horizon- 
tally and vertically. A characteristic feature of this deposit is the 
infiltration of pyrites, grains of which are clearly visible to the naked 
eye. The surrounding shale is porous, and carries minute particles 
of the grahamite, which are disseminated throughout the rock for 
some distance on both sides of the vein. 25 

The material tests as follows: 

(Test 4) Fracture Hackly 

(Test 5) Lustre Dull 

(Test 6) Streak Black 

(Test i$a) Fusing-point (K. and S. method) 401-466 F. 

(Test 19) Fixed carbon 34.4 -39.4 " pe r cent 

(Test ai) Soluble in carbon disulfide 81 . 85-97 . 70 per cent 

Non-mineral matter insoluble o . 10- 3 . 60 per cent 

Free mineral matter (mostly pyrites) i . 20-14 55 per cent 

Colorado. 

Grand County. Deposits of grahamite are found in Middle 
Park along the continental divide in the northern part of Grand 



X GRAHAMITE 253 

County. A large vein occurs in Sec. 24, T 4 N, R 77 W, on a fork 
of Willow Creek about 25 miles north of Grand River, in a region 
of clay, conglomerate and sandstone. Several veins and fissures 
have been prospected, the main vein varying in width from 2 in. up 
to 6 ft, and extending 100 to 125 ft. Comparatively small quan- 
tities of the grahamite have been mined, due to difficulties in trans- 
portation to the nearest railroad. The product tests: 

(Test 7) Specific gravity at 77 F i , 15-1 > 16 

(Test 19) Fixed carbon 47-4 -49-3 per cent 

(Test 21) Soluble in carbon disuifide 98 . 2 -99 . 3 per cent 

Non-mineral matter insoluble 0.6-1.7 per cent 

Free mineral matter o.o - o. i per cent 

(Test 22) Carbenes 80.6 per cent 

(Test 23) Solubility in 88 petroleum naphtha o. 8 - i .3 per cent 

(Test 26) Carbon 85.9 -86. i per cent 

(Test 27) Hydrogen 7.63- 7-75 per cent 

(Test 28) Sulfur 0.93- 0.99 per cent 

Undetermined 5-34- 5-45 per cent 

r TT r* MEXICO 

State of Vera Cruz. 

District of Papantla. Grahamite deposits occur about 20 miles 
south of Papantla, near the village of Espinal, forming a continua- 
tion of the glance pitch vein at the village of Talaxca (about 6 miles 
north of Papantla), previously referred to herein* A total of 5 
grahamite veins have been located, with outcroppings at the sur- 
face, the widest of which measures 1.5 meters, with an average 
length of 700 meters. The asphaltite varies from a true grahamite 
(A) to a metamorphized type (B) approaching impsonite, testing 
as follows: 

Type"A" Type"B" 

(Grahamite) (Impsonite) 

(Test i) Color in mass Black Black 

(Test 4) Fracture Hackly Hackly 

(Test 5) Lustre Bright Dull 

(Test 6) Streak Black Black 

(Test 7) Specific gravity at 77 F 1.15 1.19 

(Test 15*) Fusing-point (R. & B.) 375 F. Decomposes 

(Test 19) Fixed carbon 37 -o per cent 43-35 per cent 

(Test 2i) Soluble in carbon disulfide 99. 80 per cent 20.00 per cent 

Non-mineral matter insoluble o. ia per cent 79 .41 per cent 

Mineral matter o . 14 per cent o. 59 per cent 

Total 100.00 per cent 100.00 per cent 

(Test 22) Soluble in carbon tetrachloride 10,3 percent 

(Test 23) Soluble in 88 petroleum naphtha . 39 . 7 per cent 3.5 per cent 

(Test 28) Sulfur 6. 16 per cent 



254 ASPHALTITES X 

State of San Luis Potosi. 

District of Tamazunchale. A vein of grahamite has been found 
at Huasteca on the Panuco River 2e in a vertical fissure, occurring in 
shales as an overflow at the junction of the shale stratum with the 
overlying sandstone. On analysis the material tests as follows : 

(Test 4) Fracture Semi-conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Black 

(Test 7) Specific gravity, at 77 F 1.145 

(Test 19) Fixed carbon 35.3 per cent 

(Test 21) Soluble in carbon disulfide 93 . 8 per cent 

Non-mineral matter insoluble 3.4 per cent 

Free mineral matter 2.8 per cent 

(Test 23) Solubility in 88 petroleum naphtha 8.4 per cent 

(Test 26) Carbon 77.67 to 83. 14 per cent 

(Test 27) Hydrogen 8 .06 to 8 .09 per cent 

(Test 28) Sulfur 7.51 to 5. 47 per cent 

State of Tamaulipas. Another deposit has been reported near 
the City of Victoria, containing 3.4 per cent of non-mineral matter 
insoluble in carbon disulfide and 54 per cent of fixed carbon, 

CUBA 27 

Province Pinar del Rio. In the District of Mariel, near the City 
of Bahia Honda, there occurs a fairly large vein of grahamite, 
known as "La America Mine," or the "Rodas Conception Mine/' 
testing as follows : 

(Test 4) Fracture Shows distinct cleavage veins 

(Test 5) Lustre Semi-dull 

(Test 7) Specific gravity, at 77 F i . 1 57 

(Test 19) Fixed carbon 40.0-42 . 2 per cent 

(Test ai) Soluble in carbon disulfide 99.4-99.6 per cent 

Non-mineral matter insoluble o.o- o. i per cent 

Free mineral matter 0.4- o. 5 per cent 

(Test 22) Carbenes About 25 per cent 

(Test 23) Solubility in 88 petroleum naphtha.. 17.4-20.0 per cent 

A smaller deposit, known as "Santa Julia/' occurs near the 
stream of Don Hermanos, 7 miles southwest of Bahia Honda. 

Another deposit occurs near the City of Mariel, i mile south 
of Mariel Bay, known as the "Magdalena Mine/' which extends 
about 100 ft* in length and 40 ft. in width. The first concession was 
granted in 1859 involving 3705 acres. The veins consist of a series 
.of lenses from 2 to over 30 meters wide, in calcareous rock. The 



X GJMHAM1TE 255 

deposit has been worked to a depth of about 300 feet Large 
quantities of grahamite of a fairly uniform composition have been 
mined, characterized by the presence of about 40 per cent of asso- 
ciated mineral matter, which has been utilized principally as a com- 
ponent of paving compositions. 28 It tests as follows : 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Dull 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .45 to 1 ,49 

(Test 15^) Fusing-point (R. and B. method) 374-400 F. 

(Test 16) Volatile at 212 F About 5% 

(Test 17^) Flash-point (open cup) 41 5-425 F. 

(Test 19) Fixed carbon 30.0-38 .o per cent 

(Test 21) Soluble in carbon disulfide 51 -58 per cent 

Non-mineral matter insoluble 3 -7 per cent 

Free mineral matter 38 -42 per cent 

(Test 22) Carbenes i . 5- 6.3 per cent 

, (Test 23) Solubility in 88 petroleum naphtha 37 -48 per cent 

(Test 26) Carbon 7*-5-77.8 per cent 

(Test 27) Hydrogen 8.5- 8 .7 per cent 

(Test 28) Sulfur ! 6.9- 7.7 per cent 

Difference 6.6-11 .4 per cent 

Another vein occurs in this same locality, probably a continuation 
of the preceding, known as the "Mercedes Mine," testing similarly. 

Province of Havana. In the neighborhood of Campo Florida, 
grahamite has been obtained from a mine known as "La Habana," 
which tests : 

(Test 4) Fracture Semi-conchoidal 

(Test 5) Lustre Dull 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i , 175 

(Test 19) Fixed carbon 45.0 per cent 

(Test 21) Soluble in carbon disulfide 98 . 9 per cent 

Non-mineral matter insoluble o. 7 per cent 

Free mineral matter 0.4 per cent 

(Test 23) Solubility in 88 petroleum naphtha 6.0 per cent 

(Test 26) Carbon 82, 5 per cent 

(Test 27) Hydrogen 7- 5 per cent 

(Test 28) Sulfur 6.4 per cent 

Undetermined 3 . 6 per cent 

A similar deposit has been reported about 12 miles east of 
Havana and another one, known as the "Casitalidad Mine," situ- 
ated about 9-10 miles east of Havana, and 2 miles south of the 
coast, in a vein 600-900 ft. long and 1-30 ft thick, testing sub- 
stantially the same as the preceding. 



256 ASPHALT1TES X 

Province of Santa Clara* Nine miles northeast of the City of 
Santa Clara near Loma Cruz, there occurs the deposit known as 
"Santa Eloisa," in a bed of serpentine. It tests as follows: 

(Test 4) Fracture Semi-conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F 1.29 

(Test 19) Fixed carbon 34~35 P<* cent 

(Test 21) Soluble in carbon disulfide 7 8 ~79 per cent 

Non-mineral matter insoluble i . 8-2 . 2 per cent 

Free mineral matter 19-20 per cent 

(Test 22) Carbenes 2-3 per cent 

(Test 23) Solubility in 88 petroleum naphtha. , 31-33 per cent 

Another mine occurs a short distance from Placetas del Sur, in 
an irregular vein of lenticular form, occurring in several branches. 
This mine is known as the "Esperanza," and the product is charac- 
terized by its comparatively low fuslng-point The average ma- 
terial as mined tests as follows : 

(Test 4) Fracture Hackly 

(Test 5) Lustre Moderately bright 

(Test 6) Streak Black 

(Test 7) Specific gravity, at 77 F 1.22 

(Test go) Hardness, Moh's scale 2 

In flame Softens, splits and burns 

(Test 150) Fusing-point (K. and S. method) 400-433 F. 

(Test 19) Fixed carbon 52, 95 per cent 

(Test 21) Soluble in carbon disulfide 97 9~98 . 8 per cent 

Non-mineral matter insoluble 0.05-0. 92 per cent 

Free mineral matter i .15-2.75 per cent 

Mineral matter combined with non-mineral 
constituents 0,37 per cent 



SOUTH AMERICA 

TRINIDAD 

Two deposits of grahamite 29 occur near San Fernando on the 
west coast of the island on the shore of the Gulf of Paria, known as 
the Vistabella and Marbella Mines. The grahamite has been mar- 
keted under the name of "manjak," presumably taking advantage 
bf the popularity of the Barbados glance pitch, although from a 
geological standpoint the two minerals are entirely different The 
veins occur in soft shale and sandstone, in a region carrying petro- 
leum in considerable quantities. 



X GRAHAMITE 257 

A nufnber of veins of grahamite have been uncovered, the lar- 
gest known as the Vistabella mine, which measures 360 ft horizon- 
tally and has been mined to a depth of about 250 ft Its thickness 
is 1 1 ft, at the outcrop, and increases steadily to 33 ft at a depth 
of 200 ft Three distinct types have been found in the vein, viz: 

1 I ) An amorphous coaly type which has a hackly fracture, and 
usually occurs at the margin of the vein. It is dull in lustre and 
exhibits no regular jointings, 

(2) A columnar type, of dull lustre, having a columnar jointing 
running at right angles to the margins of the vein. The jointing is 
often well formed, dividing the material into hexagonal or pentag- 
onal prisms. 

(3) A lustrous variety identical in appearance to gilsonite and 
Barbados glance pitch (manjak). This has a bright lustre, and a 
conchoidal fracture, being found in the deeper workings of the mine, 
at the center of the vein. 

There is no chemical difference in the varieties, although it ap- 
pears that at the center of*the vein, at a depth of about 120 ft 
the grahamite has a lower fusing-point, closely resembling the Bar- 
bados glance pitch, thus serving as a link between the grahamite 
and the glance pitch, clearly proving that both are derived by 
metamorphosis from a common source. 

A stratum of oil-bearing sandstone is known to exist beneath the 
grahamite, which appears more than likely to have been derived 
from an asphaltic petroleum which intruded under pressure through 
a fault in the shale. 

The mining of the grahamite is comparatively simple, but the 
shafts have to be carefully timbered, and precautions have to be 
taken to avoid igniting the gases generated in the workings, as these 
are highly explosive. Formerly between 2000 and 2500 tons were 
mined per annum. 

On analysis it tests as follows: 

(Test i) Color in mass Black 

(Test 2) Homogeneity 3 distinct types recog- 
nizable (see above) 

(Test 4) Fracture Types I and 2, hackly; 

Type 3 conchoidal. 

(Test 5) Lustre Types I and 2 dull; 

Type 3 bright 

(Test 6) Streak,.... Black 

(Test 7) Specific gravity, at 77 F 1.170-1.175 



258 



ASPHALT1TES 



X 



(Test ga) Hardness, Moh's scale 2 

(Test 9^) Hardness, penetrometer o 

On heating in flame Softens, splits and burns 

(Test ija) Fusing-point (K. and S. method) 350-438 F. 

NOTE. The material resembling glance pitch obtained from the centre of the vein at 
the 2oo-ft. level fused at 280 F. (K. and S. method)* 

(Test 15^) Fusing-point (B. and R. method) 370-460 F. 

(Test 19) Fixed carbon 31 .5-35.0 per cent 

(Test 21) Solubility in carbon disulfide 91 .7-96.0 per cent 

Non-mineral matter insoluble 0.9- 1.2 per cent 

Free mineral matter 4.0- 6.4, averaging 

about 5 . 7 per cent 
Mineral matter combined with non-mineral 

constituents 1.15 per cent 

(Test 22) Carbenes About 40 per cent 

(Test 23) Solubility in 88 petroleum naphtha: 

At loo-ft. level 12 . 8 per cent 

At I40-ft. level 15. 2 per cent 

At 200-ft. level 18. 5 per cent 

At 2OO-ft. level, softer material in center . 56 . o per cent 

(Test 25) Moisture 0.2-1 .o per cent 

(Test 26) Carbon 84 .o per cent 

(Test 27) Hydrogen 5.7 per cent 

(Test 28) Sulfur ! 3-0-3.8 per cent 

(Test 29) Nitrogen 2. 2 per cent 

Figure 86 shows the hardness, tensile strength (multiplied by 
10) and ductility curves of a mixture of the grahamite fusing at 
400 F (K, and S. method) and residual oil (the same as utilized 
in mixture shown in Fig 85,) fluxed together in such proportions 

770 , ,, 5 o 



too 

90 
60 
70 
60 
50 




' Hardness 

Tensile Strength* 10 



<S> Fusing Point 277yf 
Susceptibility fndex*/2A 



.0 10 > 30 40 50 60 70 60 90 100 110 120 130 140 150 160 
Temperature.Oegrees Fahrenheit 

FIG. $6. Chart of Physical Characteristics of Fluxed Trinidad Grahamite Mixture. 



X GRAHAM1TE 259 

that the hardness at 77 F. is exactly 25.0 (Test gc), correspond- 
ing to a penetration at 77 F. of 20 (Test gb). The resulting mix- 
ture contained grahamite, 32 per cent and residual oil, 68 per cent, 
and had a fusing-point of 200 F, (K. and S. method). 

The Marbella vein is smaller than the Vistabella, attaining a 
thickness of 7 ft. near its center. It is lenticular in form and splits 
up into two smaller veins at one end. The grahamite mined from 
the Marbella vein has substantially the same characteristics as the 
preceding. At the 5o-foot level, 8.8 per cent is soluble in 88 
petroleum naphtha (Test 23) ; at the 125-ft. level, 9.6 per cent; and 
at the 200- ft. level 12 per cent. 

ARGENTINA 

Province of Mendoza. Asphaltite (presumably grahamite?) 
occurs in several localities, containing up to 0.6 per cent ash carrying 
38 per cent vanadium oxide (V 2 O 5 ). 30 

Province of Neuquen. An unusual variety of grahamite occurs 
on the eastern slope of the Andes Mountains, in the form of a ver- 
tical vein about 8 km. long and 2 to 3 m. wide. It must be hauled 
to the Great Southern Railroad, whence it may be transported to 
the nearest port, Bahia Blanca. An average sample tests as follows : 

(Test i) Color in mass Black 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i . 135 

(Test 15^) Fusing-point (K. and S. method) About 625 F. 

Behavior on heating in flame Decrepitates violently 

(Test 21) Soluble in carbon disulfide 53-35 per cent 

Non-mineral matter insoluble 46.40 per cent 

Mineral matter o. 25 per cent 

Total 100.00 per cent 

This asphaltite fluxes with great difficulty with residual oils de- 
rived from asphaltic and semi-asphaltic petroleums, which necessi- 
tates the mixture being heated to 500 F. for several hours. During 
this treatment, the "non-mineral matter insoluble" undergoes depoly- 
merization, until it all eventually goes into solution. On the other 
hand, it fluxes quite readily with linseed oil on heating to 500 F, 
This grahamite is unusual, in that although half is insoluble in 



ASPHALTJTES X 

carbon disulfide, yet it may be fluxed completely as described. It is 
apparently on the border line between true grahamite and impsonite. 

PERU 
Province of Tarma. 

Department of Junin. Deposits of grahamite occur near Huari, 
a small town in the Department of Junin, a few miles west of the 
southern branch of the Central Railway of Peru, at altitudes of 
15,000 to 16,000 ft. in the Andes Mountains. They occur as len- 
ticular veins in limestone, and are characterized by the mineral con- 




FIG. 87. Map of Grahamite Region in Peru. 



stituents carrying vanadium compounds, probably in the form of 
sulfide. The region is illustrated in Fig. 87, and includes the fol- 
lowing mines: The Chiucho mine consists of a vein 6 in. to 35 ft. 
wide, 15 miles from the railway, averaging: moisture 2.35 per cent, 
volatiles 40.45 per cent, fixed carbon 55,0 per cent, and ash 2.20 
per cent containing i.o to 2.25 per cent vanadic oxide (V a O). La 



X GRAHAM1TE 261 

Lucha mine is connected with the railroad by a small tramway 5 
miles long. The output has been utilized extensively as a fuel by 
the neighboring smelters, and contains: moisture 1.15 per cent, fixed 
carbon 44.48 per cent, volatiles 48.65 per cent, and ash 5.72 per 
cent carrying less than i per cent vanadic oxide. It is assumed that 
the vanadium must have been present originally in the asphaltic 
petroleum from which the grahamite was derived, since it is not 
found in the associated rocks. In substantiation of this hypothesis, 
it is pointed out that vanadium is similarly associated (up to i per 
cent) with certain black carbonaceous shales in the province of 
Jauja, some distance from the foregoing deposits. 31 

Other occurrences have been reported at Minasragra, near 
Cerro de Pasco, also at Lacsacocha (Yauli), both of which con- 
tain vanadium. 



CHAPTER XI 



ASPHALTIC PYROBITUMENS * 

The asphaltic pyrobitumens are natural substances composed 
of hydrocarbons, characterized by their infusibility and comparative 
freedom from oxygenated substances. They are grouped into five 
classes, viz. : elaterite, wurtzilite, albertite, impsonite, and asphaltic 
pyrobituminous shales. The first four are comparatively free from 
associated mineral matter (usually under 10 per cent). If the min- 
eral matter predominates, the material is known as an asphaltic 
pyrobituminous shale, which term is applied indiscriminately to 
shales containing wurtzilite, albertite or impsonite. 

Much confusion exists regarding the classification of asphaltic 
pyrobitumens. Every now and then it is alleged that some new 
type is discovered, which on closer investigation proves to be an old 
substance christened under a different name. Thus the so-called 
"nigrite" described by G. H. Eldridge 2 is nothing more than 
albertite. 

Elaterite, wurtzilite, albertite and impsonite when they occur 
associated with less than 10 per cent of mineral matter, are distin- 
guished from one another as follows: 





Streak 


Specific Gravity 
at 77 P. 


Fixed Carbon, 
Per Cent 


Elaterite 


Light brown 


O.QO I .(X 


2-< 


Wurtzilite 


Light brown 


I (X I O7 


* j 
C 2C 


Albertite 


Brown to black 


i 071 10 


> *j 

2C <O 


Impsonite 


Black 


i. 10-1 .25 


*j j w 
CO-QO 











All four are derived from the metamorphosis of petroleum, and 
it is probable that the impsonite represents the final stage of trans- 
formation of elaterite, wurtzilite and albertite, as well as the as- 
phaltites (gilsonite, glance pitch and grahamite). 

262 



XI ELATER1TE 263 

ELATERITE 

This asphaltic pyrobitumen is the prototype of wurtzilite. It is 
found in a few localities, in small amounts and is of scientific in- 
terest only* 

ENGLAND 

Derbyshire County. Elaterite was originally discovered at the 
Odin Mine in Castleton by M. Lister in i673-4. s It was again 
described by C. Hatchett, 4 who found it to be moderately soft and 
elastic, like India rubber, having a specific gravity of 0.953 0.9 8. 
It is slightly soluble in ether (18 per cent) and swells up in petro- 
leum naphtha. H. J. Klaproth 5 examined this same material, stat- 
ing that it " fuses at a high heat, and after this may be drawn into 
threads between the fingers," also that it contains between 6 and 7 
per cent of ash. 6 

AUSTRALIA 
State of South Australia. 

Coorong District. A variety of elaterite is found on the coast 
south of Adelaide, Australia, known under the name of "coorong- 
ite." 7 It is a rubbery product, known as "Australian caoutchouc, " 
which shows: fixed carbon i per cent, volatiles 97 per cent, and ash 
2 per cent. It was deposited on the ground after the subsidence of 
the floods in 1865 and again in 1920. It is contended that coorong- 
ite is derived from algae-like organisms, similar to those which are 
still to be found in certain salt lakes in South Australia. These or- 
ganisms appear on the lakes in winter and are blown ashore, where 
they are supposed to consolidate into coorongite. 

ASIATIC RUSSIA 

State of Turkestan. A deposit occurs at the mouth of the Hi 
River, in the neighborhood of Lake Balkash, 8 and tests as follows : 

(Test 7) Specific gravity 0.995 

(Test 21) Solubility in carbon disulfide Very slight 

Free mineral matter 3-5 per cent 

(Test 370) Acid value 4.9 

(Test 37^) Saponification value 56 . 9 

(Test 37*) Saponifiable matter 1 1 . t per cent 

Unsaponifiable matter 88 .9 per cent 

It is characterized by the presence of saponifiable matter, and 
in this respect differs from the foregoing. A similar deposit occurs 



264 



ASPHALT1C PYROBITUMENS 



XI 



along Lake Ala-Kool (Ala-Kul), east of the foregoing, in masses 
2-10 ft. wide and up to 2 in. thick, associated with algae. 9 



WURTZILITE 
This has been found in but one region, 10 as follows : 



Utah. 



UNITED STATES 



Uinta County. This region embraces about 100 square miles in 
the neighborhood of Indian, Lake, Avintequin and Sams Canyons, 
tributaries of Strawberry Creek, which in turn leads into the Uinta 

River. The veins occur about 50 miles 
southwest of Fort Duchesne, varying 
in length from several hundred feet 
to about 3 miles, and from i to 22 in. 
wide, filling vertical faults in shaly 
limestone. Altogether about 30 veins 
have been discovered, closely resem- 
bling those of gilsonite. Many of 
them split into a number of smaller 
branches, either in a vertical or hori- 
zontal direction. The largest veins 
occur between the Left-Hand and the 
Right-Hand forks of Indian Canyon. 
Wurtzilite has been exploited under 
various names, including elaterite 
(improper use of this name), aeger- 
ite, aconite, etc. 

A view of one of the veins is 
shown in Fig. 88; a section through 
the mine, in Fig. 89; and the tram- 
way for conveying the product from 
the hillside mine to the valley below, 
in Fig. 90. 

Wurtzilite is characterized by being sectile and cutting like horn 
or whalebone. Thin flakes are somewhat elastic, comparable in a 
way to that of glass or mica, rather than to the yielding elasticity 
of rubber. If a shaving is bent too far or suddenly, it snaps off like 




Courtesy of Raven Mining Co. 

FIG. 88. View of Wurtzrlite 
Mine, Uinta County, Utah. 



XI 



WURTZ1UTE 



265 




Courtesy of Raven Mining Co. 
FIG. 89. Vertical Section through Wurtzilite Vein, Uinta County, Utah. 




Courtesy of Kaven Mining Co, 
Fia 90. Transporting Wurtzilite from the Mine. 



266 ASPHALTIC PYROBITUMENS XI 

glass. This distinguishes it from other asphaltic pyrobitumens as 
well as the asphaltite^s. Attempts were made to find its fusing-point 
by heating it as high as 800 F. in sulfur, but without having any 
effect. 

It tests as follows : 

(Test i) Color in mass Black 

(Test 4) Fracture. Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Light brown 

NOTE. Extremely thin splinters are semi- 
transparent, showing a deep red col- 
or by transmitted light. 

(Test 7) Specific gravity at 77 F 1.05-1,07 

(Test 90) Hardness, Moh's scale Between 2 and 3 

(Test 9^) Hardness at 77 F. (penetrometer) o 

(Test 9<r) Hardness at 77 F. (consistometer) Over 150 

On heating in flame Softens and burns quietly 

(Test 15) Fusing-point Does not fuse without de- 
composition 

(Test 16) Volatile at 325 F., in 5 hrs i- 3 per cent 

(Test 19) Fixed carbon 5-25 per cent 

(Test 21 ) Soluble in carbon disulfide 5-10 per cent 

Non-mineral matter insoluble 85-95 per cent 

Mineral matter 0.2-2,5 per cent 

(Test 22) Carbenes o.o-i . 5 per cent 

(Test 23) Soluble in 88 petroleum naphtha 0-2 per cent 

(Test 26) Carbon 79. 5-80.0 per cent 

(Test 27) Hydrogen 10. 5-12. 5 per cent 

(Test 28) Sulfur 4.0-6.0 per cent 

(Test 29) Nitrogen 1 . 8-2. 2 per cent 

ALBERTITE 

Albertite is a generic term applied to a group of asphaltic pyro- 
bitumens similar to the type-substance which was formerly mined 
in Albert County, New Brunswick, Canada. The name "carboids" 
has also been suggested for this group of substances, 11 and the terms 
"kerotenes" and "kerites" to designate broadly those hydrocarbons 
that are insoluble in carbon disulfide. Albertites are characterized 
by their 

} Infusibility; 
2 ; Insolubility in carbon disulfide, etc. ; 

3) Specific gravity (1.07 to i.io at 77 F.) ; 

4) Percentage of fixed carbon (25 to 50 per cent) ; 

5) Small percentage of oxygen present in the non-numeral 
constituents (less than 3 per cent). 

It occurs in several localities, of which the typical deposit will 
be described first. 



XI ALBERTITE 267 

CANADA 
Province of New Brunswick. 

Albert County. In 1849 * local geologist, Dr. Abraham Ges- 
ner, discovered a substance originally termed "albert coal," subse- 
quently renamed "albertite," 12 on Frederick Brook, a branch of 
Weldon Creek, near Albert Mines, 20 miles south of Moncton. 
Shortly after this, litigation gave rise to a discussion whether or 
not the mineral was a true coal. The courts decided that it was, 
and not until many years later was its true status determined. 

The principal vein has been traced approximately 2800 ft. and 
varies in thickness from several inches to a maximum of 17 ft. It is 
connected with a number of smaller lateral veins which in turn break 
up into still smaller offshoots. The maximum depth reached by 
mining operations was approximately 1400 ft, and it is estimated 
that altogether 230,000 tons have been mined. The main use of 
the product was to enrich bituminous coal in the manufacture of 
illuminating gas, but it is no longer available, as the mine has been 
inactive for many years. 

This occurrence takes the form of a true fissure vein cutting 
across a series of beds of so-called u oil shales," which will be de- 
scribed in greater detail later. Mention should be made here that 
the surrounding shales abound in fossil remains of fish, which indi- 
cate that albertite and its associated shales are of animal origin. 

On analysis it tests as follows: 

(Test i) Color in mass Black 

(Test 2) Homogeneity Uniform 

(Test 4) Fracture Conchoidal to hackly 

(Test 5) Lustre Bright 

(Test 6) Streak Brown to black 

(Test 7) Specific gravity at 77 F 1.075-1.091 

(Test 90) Hardness, Moh's scale 2 

(Test 9^) Hardness, penetrometer, 77 F o 

(Test gc) Hardness, consistometer, 77 F Greater than 150 

On heating in flame Intumesces 

(Test 15) Fusing-point Infusible. Decomposes 

before it melts 

(Test 19) Fixed carbon 25 -50 per cent 

(Test 21) Soluble in carbon disulfide 2 -10 per cent 

Non-mineral matter insoluble 85 -98 per cent 

Mineral matter o. 1-0.2 per cent 

(Test 23) Soluble in 88 petroleum naphtha o. 5-2,0 per cent 

(Test 24) Solubility in pyridine (boiling) 25-35 per cent 



268 



ASPHALTIC PYROBITVMENS 



XI 



(Test 26) 


Carbon 


/ 
Per 
Cent 

8^.44. 


II 

Per 
Cent 

8< 4.O 


/// 

Per 
Cent 
8c <t 


/^ 

P<r 
Cent 

86 31 


r 

Per 

Cent 

87 2C 


(Test 27) 


Hydrogen. .......... 


10 08 


92o 


j jj 
11 20 


8 96 


96*1 


(Test 28) 


Sulfur 


o. 


. *w 

Trace 


i 20 


Trace 


. u,* 


(Test 29) 


Nitrogen 




l.IO 


O 42 


2 GO 


I 7C 


(Test 30) 


Oxygen 




j. AW 

2.22 


^ *!"* 


* 7 W 
I O7 


* / J 




Undetermined 


6 . o A. 


O 12 




O IO 


I 21 

















IOQ.OO 100.04 IO -35 100.24 99.83 

Province of Nova Scotia. 

Pictou County. An unusual deposit occurs immediately below 
the well-known McGregor seam at Stellarton. The approximate 
thickness of the bed is given as 5 ft, subdivided as follows: 

j I } A layer of coal I ft. 4 in, wide. 
2) A layer of albertite i ft 10 in, wide. 
(3) A layer of pyrobituminous shale i ft 10 in. wide. 

This species of albertite has been exploited under the name 
"stellarite." It seems to represent a state of transition between 
true albertite and the cannel coals, of which the Scotch mineral 
torbanite is a representative. The bed contains fossil animal and 
vegetable remains. A splinter of stellarite may be easily lighted 
with a match and will burn with a bright, smoky flame, throwing off 
sparks like stars (whence its name) . It was formerly used to enrich 
bituminous coal in the manufacture of illuminating gas. The layer 
of coal is an ordinary fat-coking coal, showing a laminated struc- 
ture, and containing 62.09 P er ce ^t of fixed carbon and 4.33 per 
cent of ash. 

The stellarite and associated pyrobituminous shale tests as 
follows : 



Stellarite 
(Albertite) 

(Test i) Color in mass Brown to black 

(Test 4) Fracture Hackly 

(Test 5) Lustre Semi-bright to dull 

(Test 6) Streak Reddish brown 

(Test 7) Specific gravity at 77 F, . 1.07-1.10 

(Test 15) Fusing-point Infusible 

(Test 19) Fixed carbon. 22.35-25. 23 per cent 

(Test ai) Soluble in carbon disulfide 2,0 per cent 

* Mineral matter 8 . 2-8 . 9 per cent 

(Test aj) Moisture.. 0.2-0.3 per cent 

(Test 26) Carbon 88.1 per cent 

(Test 27) Hydrogen, n . i per cent 

(Test 28) Sulfur o. i per Cent 

(Test 29) Nitrogen 0.2 per cent 

(Test 30) Oxygen o.j per cent 



Pyrobituminou* 
Shale 

Gray black 
Conchoidal 
Dull 
Brown 
1,56-1.78 
Infusible 

8.3-12.3 percent 
Trace 

52,0 -62.0 per cent 
0.6 - i.oper cent 



0.25- 0.74 per cent 



XI ALBERTITE 269 

The presence of the very small percentage of oxygen (0.5 per 
cent) differentiates the material from lignite and the other non- 
asphaltic pyrobitumens, thus corresponding with the ultimate analy- 
sis of the New Brunswick albertite. 

UNITED STATES 
Utah. 

Uinta County. A vein of albertite (christened "nigrite" by 
Eldridge), 120 ft long, showing a maximum width of 20 in., is 
found 8 miles from Helper, and 5 miles east of Soldier Summit, 
having the following characteristics : 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Semi-dull 

(Test 6) Streak Brownish black to black 

(Test 7) Specific gravity at 77 F 1.091-1.099 

(Test 90) Hardness, Moh's scale 2 

Behavior on heating in flame Splits and burns 

(Test 15) Fusingrpoint Infusible 

(Test 19) Fixed carbon 37~4Q per cent 

(Test 21) Soluble in carbon disulfide 3- 6 per cent 

Non-mineral matter insoluble 94- 2 ~"97- P er cent 

Mineral matter o. 2 per cent 

(Test 23) Soluble in 88 petroleum naphtha Trace 

(Test 28) Sulfur i .o per cent 

SOUTH AMERICA 
Falkland Islands. 

An asphaltite resembling albertite, having a specific gravity at 
77 F. of 1.04, containing 3.7 per cent of siliceous ash, and mostly 
insoluble in the usual solvents, has been reported. 18 

GERMANY 

Province of Hanover. A small deposit of albertite-like pyro- 
bitumen was discovered in 1870 south of the village of Bentheim, 
east of the city of Giidehaus. The material was mined years ago 
and utilized as fuel, under the name "Gagat-kohle." It occurs in a 
fault of a deposit of clayey schist, in a vein 0.50 to 0.65 m. wide. 
The material has a high lustre, a conchoidal fracture, a black streak, 
specific gravity at 77 F. 1.075, hardness 2.5, soluble in carbon 
disulfide 23.5 per cent, slightly soluble ip turpentine, ash 0.53 per 
cent. It softens and swells in a flame and distills without fusing. 
The mine is now idle, 14 



270 ASPHALT1C PYRQB1TUMENS XI 



AUSTRALIA 

Tasmania. A species of albertite described under the name of 
"tasmanite" 16 has been reported near the River Mersey in the 
northern portion of Tasmania. It is found disseminated in pyro- 
bituminous shale and complies with the following tests : 

(Test l) Color in mass Black 

(Test 2) Homogeneity Uniform 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Yellowish brown 

(Test 7) Specific gravity at 77 F i . 10 

(Test go) Hardness, Moh's scale 2 

(Test 15) Fusing-point Infusible 

(Test 21) Soluble in carbon disuifide Trace 

Mineral matter 8-14 per cent 

(Test 26) Carbon 79-^ "79-3 per cent 

(Test 27) Hydrogen 7.2 - 7.4 per cent 

(Test 28) Sulfur 5.28- 5.32 per cent 

(Tests 29 and 30) Nitrogen and oxygen 4. 93 per cent 

PORTUGUESE WEST AFRICA 

Province of Angola. 

District of Libollo. A species of albertite is reported at Calu- 
cala, 14 miles north of the railway station Zenza .do Itombe (which 
is 1 8 miles east of Luanda on the Luanda-Malange Railway line) 
under the name "libollite." 16 



IMPSONITE 

This represents the final stage in the metamorphosis of asphal- 
tites and asphaltic pyrobitumens. It is characterized by its : 

1 i ) Infusibility and insolubility in carbon disuifide ; 

(2) Specific gravity (i.io to 1.25) ; 

(3) High percentage of fixed carbon (50 to 85 per cent) ; 

(4) Comparatively small percentage of oxygen (less than 5 per 
cent) t which differentiates it from the non-asphaltic pyrobitumens. 

The weathered asphaltites taken from the exposed portions of 
the vein, where they have been subjected for centuries to the action 



XI IMPSONITE 271 

of the elements, closely resemble impsonite in their physical and 
chemical properties, and may therefore be classified as such. Out- 
crops of grahamite are especially prone to metamorphize into imp- 
sonite, and many prospectors have been misled on this account 
The following represent the most important deposits : 



, IT 



NORTH AMERICA 

UNITED STATES 
Oklahoma. 

La Flore County. One of the largest deposits of impsonite oc- 
curs 2 miles east of Page on the southern slope of Black Fork 
Mountain (S J4, Sec 24, T 3 N, R 26 E), filling a fissure caused 
by a fault. The vein is about 10 ft thick, and has been mined to 
some depth. It complies with the following tests: 

(Test i) Color in mass Black 

(Test 4) Fracture Hackly 

(Test 5) Lustre Semi-dull 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i . 235 

(Test 9*) Hardness, Moh's scale 2-3 

Heating in flame Decrepitates 

(Test 15) Fusing-point Infusible 

(Test 19) Fixed carbon 75.0-81 .6 per cent 

(Test 21) Soluble in carbon disulfide 4- 6 per cent 

Non-mineral matter insoluble 93-96 per cent 

Mineral matter o . 7-2 , 5 per cent 

(Test 24) Solubility in pyridine (boiling) 3. 88 per cent 

(Test 25) Moisture o. i-i . 5 per cent 

(Test 28) Sulfur i ,69 per cent 

Murray County. Impsonite has been reported 5 miles north- 
east of Dougherty (Sec. 33, T i S, R 3 E), in a vein about 18 in. 
thick at the top and 7 ft. at the bottom. Its characteristics are 
similar to the preceding. 

Arkansas. 

Scott County. Another deposit of impsonite, referred to as 
"arkosite," 18 occurs in the western part of Fourche Mountain, 
about 1 2 miles east of the Black Fork Mountain locality in Okla- 
homa. The exact locality is I mile east of Eagle Gap, and 2 miles 



272 ASPHALT1C PYROBITVMENS XI 

st of Harris, It occurs in a region of shale and sandstone, and 
tests as follows: 

; (Test i> Color in mass Black 

(Test 4) Fracture Hackly 

(Test 5) Lustre Semi-dull 

(Test 6) Stfeak Black 

(Test 7) Specific gravity at 77 F i .25 

(Test 94) Hardness, Moh's scale 3 

Heating in flame Decrepitates 

(Test 15) Fusing-point Infusible 

(Test 19) Fixed carbon 80, o per cent 

(Test ai) Soluble in carbon disulfide Trace 

Non-mineral matter insoluble 99. 3 per cent 

Mineral matter 0.6 per cent 

(Test 28) Sulfur 1.38 per cent 

Nevada. 

Eureka County. A deposit is reported 15 miles south of Pali- 
sade in Pine Creek valley, in a vein filling a fault about 300 ft. long 
and of unknown depth. Its physical and chemical characteristics 
are similar to the preceding. 1 



, 19 



Michigan. 

Keweenaw County. An interesting formation has been de- 
scribed in the vicinity of the Porcupine Mountains in the southwest 
part of Keweenaw Point, in which the impsonite acts as a cement in 
sandstone beds carrying grains of native copper. Much of the imp- 
sonite is surrounded by copper, giving rise to the assumption that 
the former was present prior to the deposition of the copper. The 
impsonite analyzes: 64.8 per cent fixed carbon and 33.3 per cent 
ash containing 2 per cent copper. 2 



, 20 



SOUTH AMERICA 
PERU 21 



Canta (Department of Lima) and Yauli (Depart- 
ment of Junin). More than a do^en veins have been found in the 
District of Yantac, about 28 miles from CasapiUica, on the Central 
Railway of Peru, near the city o } f Marcapomacocha (see Fig. 87), 
also at Cajatambo (Cojcitambo), having a specific gravity qf 1.25, a 



XI IMPSONIT& 273 

bright conchoidal fracture, a black streak and 1,6 per cent ash, 82 
They occur along both slopes of the western Cordillera of the 
Andes, at altitudes of 12,000 to 16,000 ft, and vary in thickness 
from a few inches to 5 ft. The average composition shows : mois- 
ture 5.2 per cent, fixed carbon 72.2 per cent, volatile 10.3 per cent, 
and ash 12.3 per cent (containing 5 to 16 per cent of vanadic oxides 
V 2 O 5 ). The presence of tiny fissures radiating from the main vein, 
and the inclusion of "horses" in the vein proper differentiate the 
material from a coal formation. It is, however, distinctly anthra- 
cite in character, burning with little to no flame. 

Llacsacocha Mine occurs 13 miles by trail south of the town of 
Yauli, extending for more than 1200 ft. in limestone formation, 
having numerous lenses and faults. It is black and lustrous, free 
from pyrites, and contains: fixed carbon 88.2 per cent, volatile 9.0 
per cent, and ash 2.8 per cent (carrying 15 per cent vanadic oxide). 

Rumichaca Mine at Minasragra, near Cerro de Pasco, yields 
about 80 per cent of the world's supply of vanadium and is the 
largest of all in the Yauli district. Being close to the railroad, it 
has been largely worked during the past ten years, and used as a 
fuel. The vein carries from a few inches to 40 ft in width and 
contains an average of 16 per cent ash (carrying 5.3 per cent vana- 
dic oxide) otherwise it is similar in composition to the foregoing. 

Negrita Mine is situated 15 miles from the railroad, near Hulla- 
cocha Lake, occurring as a true fissure vein, cutting across limestone 
and shale. Three lenses yielded 2000 tons. An average analysis 
showed 9.5 per cent ash (carrying 5 per cent vanadic oxide). 

Cacharata Mine is located about 1000 yd. from the previous 
vein and measures 2 ft. wide, being similar in composition. 

Province of Huarochiri (Department of Lima). Narrow and 
irregular veins occur at Sillapata, 15 miles from the railway station 
of Matucana, running high in ash (averaging slightly less than i per 
cent of vanadic oxide). 

BRAZIL 

State of Sao Paulo. Irnpsonite has been found in a dyke near 
Limeira, analyzing: fixed carbon 76 per cent, volatile matter 5 per 
cent, and ash 1 6 per cent/ 



.83 



274 ASPHALTIC PYROB1TVMENS XI 

AUSTRALIA 

West Australia. A deposit of impsonite has been reported in 
West Australia having a specific gravity of 1.154, moisture 0.37 
per cent, fixed carbon 56.27 per cent, volatiles 41.91 per cent, and 
ash 1.82. It does not melt up to 300 C* 4 



CHAPTER XII 
PYROBITUMINOUS SHALES 1 

Under this heading will be considered the oil-forming shales 
containing pyrobitumens associated with earthy matter, which will 
produce oily or tarry distillates upon being subjected to destructive 
distillation. Oil-bearing and asphalt-bearing shales from which pe- 
troleum or asphalts may be extracted w r ith solvents are not included. 
The well-known shales in France occurring at Autun (Saone-et- 
Loire) and Bruxieres-les-Mines (Allier) consisting of semi-liquid 
asphalt associated with shales shall accordingly be excluded, al- 
though these have been classified indiscriminately with the true pyro- 
bituminous shales by other writers. 

Pyrobituminous shales may be sub-divided into two classes : 

1 i ) Asphaltic pyrobituminous shales in which asphaltic pyro- 
bitumens (elaterite, w T urtzilite, albertite or impsonite) are associated 
with shales. 

(2 ) Non-asphaltic pyrobituminous shales in which non-asphaltic 
pyrobitumens (cannel coal, lignite or bituminous coal) are associated 
with shales. 

Little or no attempt has been made to differentiate between 
these two groups, on account of the difficulty in identifying the 
bituminous material present. This will become apparent when it is 
considered that pyrobitumens are more or less insoluble in solvents 
and are moreover masked by the associated mineral matter, which 
interferes with the usual distinguishing tests, such as the specific 
gravity, lustre, streak, etc. Up to the present time all pyrobitu- 
minous shales have been referred to under the general term "oil 
shales," which is really a misnomer. 

The following means are suggested to differentiate the two 
classes: 

( i ) By the pyrobitumens found locally. 

The presence of asphaltic bitumens in the vicinity would indicate 
an asphaltic pyrobituminous shale. Similarly, non-asphaltic pyro- 

275 



276 



PYROBITUMINOUS SHALES 



XII 



bitumens would tend to establish the identity of the shale as non- 
asphaltic. If both types are present, the eviaence is non-conclusive. 



(2) By the associated fossil remains. 



If vegetable (plant) fossil remains only are found associated 
with the shale, the indications are that it is non-asphaltic, since it 
is definitely established that the non-asphaltic pyrobitumens are of 
vegetable origin. On the other hand, if animal (fish or mollusc) 
fossil remains are present, the shale will more, than likely represent 
the Asphaltic pyrobituminous variety, 

(i) Effect of heat on the solubility. 

On heating in a closed retort to 300 to 400 C, asphaltic pyro- 
bituminous shales will depolymerize and become more soluble in 
carbon disulfide, whereas the non-asphaltic pyrobituminous shales 
remain unaffected. It is also interesting to note that the bituminous 
constituents of non-asphaltic pyrobituminous shales are rendered 
fusible and soluble by neating the finely powdered shale to 500 to 
600 F. in a closed retort with a residual oil derived from petro- 
leum, or with coal tar. 8 

(4) By the percentages of fixed carbon and oxygen (calculated 
on the basis of the non-mineral matter present). These two cri- 
teria, considered together, furnish the most reliable means of dis- 
tinguishing between the two classes of shale, as will be observed 
from the following figures, calculated on the basis of the non-min- 
eral constituents present : 





Fixed Carbon 
(Calculated on the 
Ash-free Basis) 
Per Cent 


Oxygen (Calculated 
on the Ash-free Basis) 
Per Cent 


Asphaltic Pyrobituminous Shaks; 
Wurtzilite shalefc 


i IO 


Less than 2. 


Albert! te shales. , 


c <5i? 




Non*asphaUie Pyrobituminous Shaks: 
Cannel coal shales 


5^*5 

'irt 


Less than 3 


Lignite shales 


5 -* 

1 C 1ft 


5-10 

**- - ** Q 


Bituminous coal shales 


*J J u 

iCCO 


15 25 

ff T O 




x j y-> 


3*s 



It will be noted that the percentage of fixed carbon calculated on 
the mineral-free basis, runs Ipwer than in the corresponding (pure) 
pyrobitumens, due to the presence of the mineral matter, which 
assists in the combustion of the xarbon during the test, decreasing 
the yield of "fixed carbon," and at the same time increasing the 
percentage of volatile constituents. This is important from * com- 



XII PYROBITUMINOUS SHALES 277 

mercial viewpoint The most valuable pyrobituminous shales are 
those which produce the largest amount of volatile matter when 
subjected to destructive distillation. This is true with the albertitic, 
cannel coal (torbanitic) and lignitic shales, whereas the bituminous 
coal shales yield but little volatile matter and have no commercial 
importance. 

Two types of bituminous constituents are present in non- 
asphaltic pyrobituminous shales, viz.: (i) macerated and carbon- 
ized plant remains similar to coal, and (2) yellow resinous bodies 
representing the last stage in the oxidation of the woody tissue, 
Elaterite, wurtzilite and impsonite shales are rarely found. 

Pyrobituminous shales generally contain more than 33 per cent 
of associated mineral constituents. The non-mineral constituents 
present in non-asphaltic pyrobituminous shales have been designated 
by the terms "kerogen" s or "petrologen." * 

From the foregoing it will be apparent that the subject of "pyro- 
bituminous shales" is an extremely complicated one, still requiring 
a vast amount of research work before all the deposits can be cor- 
rectly classified. 

Pyrobituminous shales are treated exclusively by subjecting 
them to a process of destructive distillation in suitable retorts to 
recover the tarry distillate and ammonium sulfate as will be de- 
scribed in Chapter XVI. The intrinsic value of the shale is de- 
pendent upon the amount of shale tar and ammonium sulfate 
obtained. 

A detailed description of the individual deposits of pyrobitumi- 
nous shales does not fall within the scope of this publication. 



PART III 
TARS, PITCHES, AND PYROGENOUS ASPHALTS 



CHAPTER XIII 
GENERAL METHODS OF PRODUCING TARS 

Tars constitute the volatile oily decomposition products ob- 
tained in the pyrogenous treatment of bituminous and other organic 
substances. The pyrogenous treatment embraces three processes, 
viz. : 

1 i ) Subjecting to heat alone without access of air, often termed 
"destructive distillation," and sometimes referred to as "pyrolysis." 

(2) Partial combustion, which may take place either in an at- 
mosphere of air and steam (in gas producers) or with a limited 
access of air. 

(3) Cracking oil vapors at high temperatures. 

Practically all organic substances which undergo decomposition 
produce tars upon being subjected to heat, provided they yield a 
substantial proportion of volatile decomposition products, the tem- 
perature is sufficiently high to bring about the decomposition, and 
air is entirely or partially excluded during the pyrogenous treat- 
ment If the organic substance does not contain volatile matter, as 
proves the case with anthracite coal or graphite, no tar will result. 
If air is present in too large a quantity, the products of decomposi- 
tion will undergo complete combustion, and the tar will be con- 
sumed. Materials which evaporate (i. e. } distil undecomposed), or 
sublime, will remain unchanged in composition, and products which 
explode are converted into permanent gases, without the formation 
of tars. 

At the present time tars are produced commercially from the 
following products : 

278 



XIII 



GENERAL METHODS OF PRODUCING TARS 



279 



(1) Bituminous substances including peat, lignite, bituminous 
coal, petroleum and pyrobituminous shales. 

(2) Certain other organic substances including wood, and 
bones. 

The following will give a synoptical outline of the raw materials 
used, the modes of treatment and the kinds of tar produced: 



Raw Materials Used 


Heat Alone 
(" Destructive 
Distillation") 


Partial Combustion 


"Cracking" 


Air and Steam 
("Producers") 


Limited Access 
of Air 


Bituminous substances: 
Petroleum products. . . . 
Peat 


Wax tailings 

Peat tar 
Lignite tar 
Shale tar 
Gas-works coal 
tar 
Coke-oven coal 
tar 

Wood tar 
Bone tar 






[Pressure tar 
I Oil-gas tar 
I Water-gas tar 


Peat tar 

Lignite tar 
Shale tar 

Producer-gas 
coal tar 




Lignite 






Pyrobituminous shales. 
Bituminous coals 

Other Organic Materials: 
Wood 






Blast furnace 
coal tar 






Bones 



















Petroleum products (e.g., "gas oils") upon being subjected to a 
high temperature under more or less pressure in a closed retort will 
result in the formation of oil-gas tar; and when sprayed on incan- 
descent anthracite coal or coke result in the production of water-gas 
tar. Peat, lignite and pyrobituminous shales result in the formation 
of peat-, lignite- and shale-tars respectively: (i) when subjected to 
destructive distillation, or (2) upon undergoing partial combustion 
in an atmosphere of air and steam in a so-called "gas producer." 
Tars resulting from these two processes are similar in composition 
and hence are designated by the same name. Destructive distilla- 
tion yields a larger percentage of tar than partial combustion in an 
atmosphere of air and steam. 

Bituminous coals form different kinds of tar, depending upon 
the nature of the process. Thus gas-works coal tar and coke-oven 
coal tar are produced by the destructive distillation of bituminous 
coal in gas-works retorts and coke-ovens respectively. Producer-gas 



280 GENERAL METHODS OF PRODUCING TARS XIII 

coal tar is derived from the partial combustion of bituminous coal 
in an atmosphere of air and steam in a gas producer. Blast-furnace 
coal tar results from the partial combustion of bituminous coal in a 
limited access of air in a so-called "blast furnace," Destructive 
distillation of wood results in the formation of wood tar, and of 
bones in the production of bone tar. 

In the order of their commercial importance, based on the quan- 
tities produced annually, tars may be grouped as follows, viz.: 
coal tar is produced in the largest quantity, water and oil-gas tars 
come next, and wood tar follows in sequence. Insignificant quan- 
tities of producer-gas coal tar, bone tar, blast-furnace tar, peat-, 
lignite- and shale-tars are produced in the United States. Lignite 
tar is produced in comparatively large quantities in Germany. The 
production of peat- and bone-tar has not assumed great importance 
anywhere. 

The following tars have been described in the literature, 1 pro- 
duced by the destructive distillation of the corresponding substance; 
but have but little commercial value : 

Montan-wax tar ; 2 beeswax-tar ; tars derived from the destruc- 
tive distillation of vegetable and animal oils; linoleum tar derived 
from linoleum waste; cork tar; leather tar; 3 tanning residues; sea- 
weed tar; sulfite cellulose tar (tall oil tar) produced from the de- 
structive distillation of sulfite cellulose liquor; 4 lignin tar; amber 
tar, also tars derived from other fossil resins; straw tar; tars de- 
rived from seed husks and hulls; 5 tobacco tar; bagasse tar; 6 mo- 
lasses tar; 7 tar from beet residues in sugar manufacture; tar from 
potato residues resulting from fermentation; 8 tars from fermenta- 
tion residues of various sorts; yinasse tar; anthracene-oil tar ob- 
tained as residue in anthracene oil distillation; fusel-oil tar obtained 
on distillation of fusel oil ; asphalt tar obtained on destructive distil- 
lation of natural rock asphalts (e.g., at Ragusa, Italy; Tyrol, Aus- 
tria; and at other localities), etc. 

The corresponding pitches are produced by distilling the respec- 
tive tars listed above ; i.e., montan-tar pitch, beeswax-tar pitch, vege- 
table- (or animal) oil-tar pitch, linoleum-tar pitch, cork-tar pitch, 
leather-tar pitch, tannin-tar pitch, seaweed-tar pitch, sulfite-cellulose- 
tar pitch (tall-oil pitch), lignin-tar pitch, amber-tar pitch, straw-tar 
pitch, seed-tar pitch, tobacco-tar pitch, bagasse-tar pitch, molasses- 
tar pitch, beet-residue-tar pitch, potato-residue-tar pitch, fermenta- 



XIII DESTRUCTIVE DISTILLATION 281 

tion-residue-tar pitch, vinasse-tar pitch, anthracene-oil-tar pitch, 
fusel-oil-tar pitch, naphthylamine pitch, cumarone pitch, cresol pitch 
(carbol pitch), asphalt-tar pitch, etc. 

We will now consider the various processes for producing tars 
in greater detail. 

DESTRUCTIVE DISTILLATION 

This process is used for destructively distilling infusible organic 
substances including non-asphaltic pyrobitumens, pyrobituminous 
shales, wood and bones. It consists in heating the substance to a 
high temperature in a still from which air is excluded, and the dis- 
tillation is continued until the volatile constituents are driven off and 
the residue carbonizes. The volatile constituents are grouped into 
two classes, viz,: non-condensable and condensable products, the 
former including the permanent gases, and the latter, the aqueous 
liquor and tar. 

The nature of the ingredients formed during the distillation de- 
pends largely upon the nature of raw material used and the tem- 
perature at which it undergoes decomposition. As a rule, the older 
the substance from a geological standpoint, the higher will be the 
temperature at which it decomposes. At low temperatures, we find 
aliphatic (straight chain) hydrocarbons in the tar, also varying 
amounts of phenolic bodies, of toluene and naphthalene, but no 
benzene or anthracene. This is true in the case of peat, lignite, 
cannel coal and pyrobituminous shales. Where the destructive dis- 
tillation takes place at a high temperature, aromatic hydrocarbons 
will predominate, including benzene and anthracene. This is true 
with bituminous coals. The aqueous liquor will show an acid reac- 
tion in the case of wood and peat, and an alkaline reaction with 
lignite, coals and pyrobituminous shales. 

In general, the yield of tar depends upon five factors, viz. : the 
composition of the substance, the temperature, the time of heating, 
the pressure, and upon the efficiency of the condensing system. 
These will be considered in greater detail. 

The Composition of the Substance, (a) The Percentage of 
Volatile Constituents. The greater the percentage of volatile con- 
stituents, and conversely the smaller the percentage of "fixed car- 
bon," the larger will be the yield of tan Figured on the basis of 



282 



GENERAL METHODS OF PRODUCING TARS 



XIII 



&\ja vrjLitju juzw*4rf *rj.jj.msjLsu I/JT i xti/Asi/ ujxv vj .x /3*Y4j ^VXAJL 

the dry weight of the non-mineral constituents, the yield of volatile 
matter will range as follows, commencing with the highest: wood, 
peat, lignite, bituminous coal. The yields of tar follow in the same 
sequence, viz. : 

Wood 10 -20 per cent 

Peat 7i~i5 per cent 

Lignite 5 -10 per cent 

Bituminous coal , 3 - 7 per cent 

(b) The Percentage of Oxygen in the Fuel. As a general rule, 
the greater the percentage of oxygen in the fuel, the greater will be 
the yield of tar. Georg Lunge 9 cites the following figures to show 
the relation between the percentages of oxygen, tar, and water, 
based on the dry weight of fuel: 



Fuel Contains 
Per Cent 


Yield Tar, 
Per Cent 


Yield Water, 
Per Cent 


Oxygen <-6i 


310 


A <8 


Oxygen 65-7^ 


4.6c 


<.86 


Oxygen 7J~9 


c.o8 


6,80 


Oxygen 9-1 1 


$.48 


8,60 


Oxygen 11-13 


r, ro 


7 86 









The Temperature, (a} The Temperature at which the Fuel 
Decomposes. As stated previously, each type of fuel has a definite 
temperature at which distillation commences. The older the fuel 
from a geological standpoint, the higher will be this temperature, 
and hence the greater will be the yield of coke, and the smaller that 
of tar. It would appear that a preliminary decomposition approach- 
ing a state of fusion occurs at this temperature, which remains fairly 
constant until the carbonization is complete. The coke-forming 
property of bituminous coals depends upon the presence of con- 
stituents melting at a lower temperature than that at which carboni- 
zation occurs. 

(b) The Temperature at Which the Distillation Is Performed. 
This is distinct from the preceding, and is determined by the quan- 
tity and intensity of the heat applied externally to the retort in 
which the destructive distillation takes place. It depends upon the 
nature of the heating medium, and the manner in which it is applied. 
The temperature may be close to that at which the fuel undergoes 



XIII DESTRUCTIVE DISTILLATION 283 

distillation, or it may be vastly in excess thereof. The higher the 
temperature above that necessary to cause incipient decomposition, 
the smaller will be the yield of tar, and the larger that of gas; more- 
over, a high temperature results in the formation of a larger per- 
centage of free carbon in the tar, due to greater decomposition 
("cracking") of the distillate. 

Aromatic hydrocarbons, upon being subjected to a gradually in- 
creasing temperature (650-800 C), are transformed as follows: 

Higher benzene homologues-*Lower benzene homologues-Di- 
phenyl-Naphthalene- Anthracene. 

At temperatures above 800 C., the anthracene is decomposed 
into carbon and gas. 10 

The Time of Heating, (a) Thickness of the Fuel Layer. The 
deeper the layer of fuel in the retort or furnace, the greater the 
super-heating, and consequently the smaller will be the yield of tar 
and the larger that of gas. When the layer is deep, the volatile 
portions are compelled to pass through a mass of incandescent fuel, 
so that the temperature of the gases is increased, due to the greater 
time of contact. This is the underlying principle in the manufacture 
of generator gas. 

It follows also that the greater the area of contact between the 
fuel and the heating surface, the shorter time it will take to raise the 
temperature of the former the requisite degree. Small charges of 
fuel may thus be heated more rapidly, which is conducive to the 
formation of a greater proportion of gas and tar and a smaller yield 
of coke. Slow heating, on the other hand, results in the production 
of a large proportion of coke, and smaller proportions of gas and 
tar respectively. It is for this reason that comparatively small and 
narrow retorts are used for the manufacture of illuminating gas, and 
very much larger chambers where coal is treated to obtain coke. 

(b) Size of the Fuel. The size of the lumps of fuel has an im- 
portant bearing on the time of heating. If the lumps are too fine, 
they will pack together to such an extent that insufficient space is left 
between them for the transfer of heat by the gaseous products. 
On the other hand, if the lumps are too large, it will take an abnor- 
mally long time for the carbonization process to reach the center of 
each lump, since the heat conduction of the fuel itself is poor. 



284 GENERAL METHODS OF PRODUCING TARS XIII 

(c) Construction of the Retort or Furnace. The thickness of 
the walls, the method of heating, the size as well as the nature of 
the material of which the retort is constructed, all tend to influence 
the time of heating. Small units, the use of preheated gases for 
supporting the combustion, and thin retort walls constructed of ma- 
terials which have a relatively high conductivity at elevated tem- 
peratures, serve to decrease the time of heating. 

The Pressure. The greater the pressure, the longer are the 
volatile products forced to remain in contact with the hot retort and 
incandescent fuel, and the greater, therefore, will be the carboniza- 
tion. The use of reduced pressure hastens the removal of the vola- 
tile constituents and serves to increase the outputs of gas and tar, 
and reduce the yield of coke* At the same time, the period of dis- 
tillation is increased. In manufacturing illuminating or fuel gas, 
modern practice consists in carrying out the distillation under a 
moderate vacuum. On the other hand, when the main object is to 
produce coke, the pressure of the gas inside the retort is purposely 
allowed to increase somewhat. 

The Efficiency of the Condensing System. As the vapors leave 
the retort, oven, blast-furnace, or producer at 500 to 800 C M all 
the constituents exist in the gaseous state, excepting the "free car- 
bon" derived from the decomposition of the gases in contact with 
the highly heated walls, and the particles of mineral matter which 
are carried over mechanically. The vapors are composed of a mix- 
ture of substances, .some congealing to solids, others condensing to 
liquids, and still others remaining as permanent gases at atmos- 
pheric temperature and pressure. As the vapors cool, the solids and 
liquids separate out, forming the tar. This separation is progressive, 
the higher boiling-point constituents condensing first, followed by 
substances of lower boiling-points, and finally liquids boiling slightly 
above atmospheric temperature. With this in view, the vapors may 
either be cooled slowly, or they may be cooled rapidly, so that all 
condensable constituents are caught together in the form of "tar," 
to be redistilled later into its components. It is a singular fact, that 
even when the vapors have been thoroughly cooled, the tar will not 
separate out completely, without further treatment. Part remains 
suspended in the gases as infinitesimally fine globules, known as a 
"tar fog." This term is most expressive, since its behavior is very 



XIII PARTIAL COMBUSTION WITH AIR AND STEAM 285 

similar to that of an ordinary fog, alluding to the weather. Mere 
cooling will not condense a "tar fog," accordingly other means must 
be employed. 

PARTIAL COMBUSTION WITH AIR AND STEAM 

This takes place in manufacturing producer gas. Several forms; 
of producers are in use, and peat, lignite, pyrobituminous shale, or 
bituminous coal are variously employed as fuel. The reaction which 
ensues may be expressed as follows, in which "C" represents the 
carbonaceous matter present in the form of fuel: 



The resulting gas, known as "producer gas," is composed of carbon 
monoxide with a smaller proportion of hydrogen. When anthracite 
coal or coke is used as fuel, no tar results ; with bituminous coal, tar 
is formed in certain types of producers but not in others; and with 
peat or lignite, tar is produced in all types, on account of the readi- 
ness with which they volatilize at low temperatures, and the com- 
paratively large proportion of volatile constituents present These 
tars correspond very closely in physical and chemical properties to 
the ones obtained from the corresponding processes of destructive 
distillation, but with the former the yield is smaller, since most of 
the tarry matter is consumed. 

Lignite carrying a moderate proportion of mineral matter (e.g., 
Messel lignite) is treated in a special form of producer to obtain a 
small amount of gas and the largest possible yield of tar (4 to 14 
per cent) . This is brought about by introducing a limited and care- 
fully regulated quantity of air and steam, sufficient only to support 
partial combustion. The same method is always followed in treat- 
ing pyrobituminous shales, on account of the greater intrinsic value 
of the tar, of which 5 to 25 per cent is recovered. These processes 
approach destructive distillation closely, the object being to bring 
about incipient combustion of the lignite or shale and the non-con- 
densable gases derived therefrom, thereby raising the temperature 
sufficiently to cause destructive distillation. 

When peat, bituminous coal or lignite containing a large propor- 
tion of mineral matter* is treated in a producer, it is always intended 



286 GENERAL METHODS OF PRODUCING TARS XIII 

to produce the largest possible yield of gas, and the smallest pro- 
portion of tar. 

PARTIAL COMBUSTION WITH A LIMITED ACCESS OF AIR 

This process takes place in manufacturing generator gas, also 
upon smelting ores in blast-furnaces. No tar is produced in manu- 
facturing generator gas, hence this process ceases to be of interest 
from the bituminologist's standpoint. In the case of blast-furnaces, 
no tar results when anthracite coal or coke is used as fuel, but when 
bituminous coal is used, as is sometimes the practice in England and 
on the Continent, 2 to 3*4 per cent of its weight of tar is produced. 
The air is forced into the blast-furnace from below, and travels 
upward through a comparatively thick layer of incandescent fuel. 
The oxygen on coming into contact with the fuel is first converted 
into carbon dioxide, which on rising through the incandescent layer 
combines with more carbon, forming carbon monoxide. The heat 
generated volatilizes a certain amount of the bituminous coal in the 
upper layers from which the tarry matters escape unconsumed. 

CRACKING OF OIL VAPORS 

In manufacturing oil-gas, crude petroleum or a heavy distillate 
known as "gas-oil" is sprayed under more or less pressure into a 
closed retort heated to redness. This causes the oil to decompose 
into a permanent gas and from 5 to 10 per cent by weight of oil-gas 
tar. The reaction, known as "cracking," results in the breaking 
down of the hydrocarbons present in the petroleum or gas oil into 
simpler substances. 

Water-gas is produced by the combustion of anthracite coal or 
coke in an atmosphere of steam according to the following reaction : 



The gas consists theoretically of equal volumes of carbon monox- 
ide and hydrogen. It burns with a non-luminous flame, and when 
intended for illuminating purposes must be enriched or "car- 
bureted." The highly heated water-gas as it is generated, is ac- 
cordingly mixed with a spray of crude petroleum or gas oil, then 



XIII CRACKING OF OIL VAPORS 287 

passed into a carburetor in which the oil becomes vaporized, and 
finally through a superheater maintained at a temperature suffi- 
ciently high to crack the oil vapors into permanent gases. From 2 
to 10 per cent of tar is produced, based on the weight of the petro- 
leum or gas-oil used. This tar is known as water-gas tar and is 
similar in its physical and chemical properties to oil-gas tar. 



CHAPTER XIV 
WOOD TAR, WOOD-TAR PITCH AND ROSIN PITCH 

WOOD TAR AND WOOD-TAR PITCH 

This chapter will deal with the treatment of wood, either by 
destructive distillation, or by a combination of steam and destruc- 
tive distillation. 1 The treatment of resinous woods by the steam 
distillation process alone, for the recovery of turpentine and other 
oils, does not fall within the scope of the present treatise. 

Varieties of Wood Used. From the standpoint of destructive 
distillation, woods may be divided into two classes, viz.: 

Hard Woods, including the maple, birch, beech, oak, poplar, 
elm, willow, aspen, alder, ash, hickory, chestnut and eucalyptus. 

Resinous or Soft Woods, including the pine, fir, cedar, cypress, 
spruce, hemlock, larch or tamarack. 

The trees from which hard woods are obtained are known as 
"broad-leaved" or u deciduous trees," and those producing resinous 
or soft woods are termed "coniferous trees" or "evergreens." Soft 
woods are distinguished from hard woods principally in that the 
former contain larger quantities of turpentine and resin. The dis- 
tillation of hard wood aims at the recovery of wood alcohol, ace- 
tates, tar and charcoal, whereas the distillation of resinous wood 
(soft wood) is directed to the recovery of turpentine, wood-tar 
oils, tar and charcoal. 

In the wood-distilling industry the basis of measurement is a 
cord, which is taken to equal 128 cu. ft. of the closely stacked wood 
containing 15 per cent of moisture. The weight of a cord varies 
with different kinds of wood, from about 1700 Ib, in the case of 
white pine and poplar, to about 4000 Ib. in the case of oak. 

For purposes of destructive distillation, the wood should be as 
dry as possible, since during the process all the moisture must be 
evaporated before the wood decomposes. The smaller the per- 
centage of moisture contained in the wood, the more rapid will be 
the distillation process and the smaller the quantity of fuel required. 

288 



XIV 



WOOD TAR AND WOOD-TAR PITCH 



289 



It is advisable therefore, to cut and stack the green wood containing 
20 to 50 per cent of moisture from six months to two years, during 
which the moisture content will fall to between 12 and 25 per cent 
Yields of Distillation. The following figures will give a general 
idea of the average yields upon distilling a cord of the respective 
classes of wood: 





Hard Woods 


Soft (Resinous) Woods 


Turpentine 


o 


5- 25 Gal.* 


Wood-tar oils 


o 


30- 75 GaL 


Crude -alcohol (containing acetone) 
Tar 


8- 12 Gal. 
8- 20 Gai 


2- 4 Gal. 
30- 60 GaL 


Charcoal 


40- 52 Bu. 


25- 40 Bu. 




ico-^co Lb. 


50-100 Lb. 









* Sawdust yields 5 to 10 gal. of turpentine and light wood 10 to 25 gal. per cord, 

The tar may be classified according to the type of carbonizing 
apparatus employed, as follows: mound tar, pit tar, oven tar, retort 
tar and generator tar. 

Hard- Wood Distillation. The following figures show the yields 
of tar and charcoal from the various hard woods in percentage, 
based on the dry weight of the material : 2 





Tar, 
Per Cent 


Charcoal, 
Per Cent 


Hickory 


13.0 


37,7 


Maple . . 


12.8 


40.6 


Birch 


12. 


40,6 


Beech 


9.4. 


41 ig 


Oak 


7.8 


4$. 7 


Chestnut 


4 .6 


47-6 




.A. 





In the United States, the principal centers for hard-wood dis- 
tillation are in the States of Pennsylvania, New York and Michigan. 
Soft-wood distillation is carried on largely in the States of Florida, 
Georgia, North and South Carolina and Alabama. 

The crude products of the distillation of hard wood may be 
grouped into four classes, viz. : 

(1) Non-condensable gases , 20-30 per cent 

(2) Aqueous distillate (crude pyroligneous acid) 30-50 per cent 

(3) Wood-tar oils, and wood tar 5-20 per cent 

(4) Charcoal > ; * *O-45 per cent 



290 



WOOD TAR, WOOD-TAR PITCH AND ROSIN PITCH 



XIV 



Method of Distilling. When hard wood is heated in a retort, 
water passes off below 150 C., after which decomposition sets in. 
With soft (resinous) wood, turpentine and water commence to 
distil between 90 and 100 C. and continue to 150 C., whereupon 
products of destructive distillation pass over. The distillation proc- 
ess is practically complete at 430 C. In the case of hard wood, 
the first group of products which pass over (between 150 to 
280 C.) include acetic acid, methyl alcohol and wood creosote; 
the second group (280 to 350 C.) consist of non-condensable gases 
(about 53 per cent of carbon dioxide, 38 per cent of carbon monox- 
ide, 6 per cent of methane, 3 per cent of nitrogen, etc.) ; the third 
group (350 to 400 C.) are composed of solid hydrocarbons and 
their derivatives. The yields of methyl alcohol and acetic acid in- 
crease with a rise of temperature up to 300 C. beyond which they 
decrease; moreover their yield is greater when the wood is heated 
slowly, than when the distillation is forced. 

The following fractions are obtained on distilling beech-wood 
tar (specific gravity at 15 C. 1.05-1.10) : 

Aqueous distillate (*) 15-20 per cent 

Light tar oils (to 110 C.) 5-10 per cent (sp. gr. o. 90-0. 98) 

Heavy tar oils (120-270 C.) 10-20 per cent (sp. gr. i .04-1 .05) 

Soft wood-tar pitch 40-60 per cent 

* Containing 10 per cent acetic acid and 3-5 per cent crude wood alcohol. 

In distilling hard woods, 
large rectangular iron retorts 
are used, measuring 6 ft in 
width, 7 ft. high and either 27 
or 50 ft. long, depending upon 
whether they are intended to 
hold 2 or 4 carloads. The re- 
torts are set in brickwork, and 
provided with large air-tight 
iron doors at the ends. The 
wood is loaded on small iron 
cars holding between I and 3 
cords each (Fig. 91) which 

are run on tracks directly into the retorts. 

The arrangement of a modern wood-distilling plant is shown in 

Fig. 92; where A represents a car; 5, the retort; C, first cooler; JD, 




FIG. 91. Iron Cars Used in the Distilla- 
tion of Hardwood. 



XIV 



HARD-WOOD DISTILLATION 



291 



second cooler; E 9 the acetate drying floor; a, condensers; b. liquor 
trough; c } gas main to boilers; i, fuel conveyor; w, fireplace; w, ash 
pit; o, hinged spout to deliver fuel from i to m. After the retort 
is charged, the doors are closed and heat applied slowly, either by 




FIG. 92. Modern Wood Distilling Plant. 




FIG, 93. Plant for Refining Wood Tan 



burning the non-condensable gases resulting from the distillation 
process, or by atomizing the tar underneath the retort with a jet of 
steam. Unless the gases are stored in a gas-holder, the process is 
started by burning a small amount of wood on an auxiliary grate 
beneath the retort. 



292 



WOOD TAR, WQOto-fAR PlTCti AND ROSIN PITCH 



XIV 



The vapor from the retort is passed through condensers, where 
the pyroligneous acid, alcohol and other condensable constituents 
are recovered. These are conveyed to large settling tanks, and al- 
lowed to rest quietly until the tar settles out 

The distillation process continues from twenty to thirty hours, 
whereupon the fires are extinguished and the retort allowed to cool. 
The small iron cars now carrying charcoal are quickly run from the 
retort into large iron coolers, similar in size and shape to the retort 
itself, and the doors are closed to prevent access of air. 

Refining Processes. The general arrangement of a refining 
plant is shown in Fig. 93, where A 12 represents the raw liquor 
vats, B 15 represent the raw liquor settling tanks, C i the tar 
still, C 23 the raw liquor still, D 1-2 the neutralizing vats, 
E 13 the lime-lee stills, F 13 the alcohol stills, G the weak alcohol 
storage tank and H the strong alcohol storage tank. Table XVII 
shows a diagrammatic outline of the products obtained upon distill- 
ing hard wood, and refining its distillates. 

TABLE XVII 

HARD WOOD 

Distilled Destructively 



Non-condensable Gases 
(Burned under retort) 



Condensable Distillate 
Separated by settling into: 



Charcoal Residue 



Crude Aqueous Portion 
Separated by distillation into: 


i 

Raw Tar 
Distilled into: 
1 


i' I 
Distillate, known as Tarry Residue 


Distillate of 


I 
Residue of 
Boiled Tar 
^ Redistilled 


KfoiitrnliTiwl with Hm* nnrl rliVfillorl ^^li _ *. 





1 




1 


illate composed of Residue composed of crude 
Tude dilute wood acetate of lime. Converted 


i i i 

Light oil Heavy oil Residue of 
Wood-tar pitch 



alcohol containing 
acetone. Rectified 
into: 



by roasting into gray acetate 
of lime. Then treated by 
one of the following methods 



11 A 

Acetone Wood alcohol Distilled with G 
Sulf uric acid o 


mverted into 
ther acetates 



Distilled at a high 
temperature alone 


. i, 


1 


1 i 


I i 


Distiflate of 


Residue of 


Other 


Acetone Light 


Heavy Residue of 


Acetone 


Calcium 


Acetates 


Acetone 


Acetone Calcium 




Sulfate 




Oils 


Oils Carbonate 



XIV HARD-WOOD DISTILLATION 293 

After the pyroligneous acid and tar have been separated by set- 
tling, the crude products are distilled independently to recover any 
pyroligneous acid from the crude tar, and conversely, any tar re- 
tained by the crude pyroligneous acid (dissolved in the alcohol and 
acetone present). The method consists in heating the tar with 
steam in closed coils until the water is driven off, and then blowing 
live steam thrpugh the charge. 3 

A continuous process, known as the "Badger-Stafford Process," 4 
has been devised for treating scrap wood obtained in other manu- 
facturing operations. The hogged scrap wood (averaging 70 per 
cent maple, 25 per cent birch and 5 per cent ash, elm and oak) is 
first passed through six rotary driers heated by flue gases entering 
at 600 F. The scrap wood is discharged from the driers at 302 F. 
and then fed into retorts 40 feet high and 10 feet in diameter. Air- 
tight valves at the top and bottom allow the introduction of the 
wood and the removal of the charcoal, respectively, without escape 
of gas, which passes off at the top of each retort to four condensers 
mounted around it. The average temperature in the central zone is 
950 F., and at the bottom 490 F. 

The products from the retorts are charcoal, which is passed to 
coolers and conditioners; pyroligneous acid or "green liquor," which 
is pumped from the condensers to the primary separators; and non- 
condensable gas, which is used for heating the retorts and burned 
under the boilers. 

Each ton of wood produces 1 1 1 gal. of pyroligneous acid con- 
taining approximately 4.5 per cent methanol and 12.5 per cent acetic 
acid, also allyl alcohol, acetone, methyl acetate, suspended and dis- 
solved tar, various oils and water. The pyroligneous acid is first 
delivered to settling tanks where the suspended tar is largely re- 
moved, and then pumped to the primary tar stills. The acid distil- 
late from these stills is returned to the settling tanks, while the dis- 
tilled heavy tar is sent to the pitch still, where creosote oil and pitch 
are recovered by distillation under a vacuum of 27 inches with the 
use of steam at 125 Ib. pressure. 

The pyroligneous acid free of settled tar is distilled in six large 
batch primary stills operating on a 30 hour cycle. The soluble tar 
remaining as a residue in these stills is pumped under the boilers 
where it is burned. The acid distillate passes to a separator where 



294 



WOOD TAR, WOOD-TAR PITCH AND ROSIN PITCH 



XIV 



the acid oils are removed, then through a sand filter, and finally to 
the continuous stills, which yield crude 95 per cent methanol at the 
top of thg column and 15 per cent acetic acid at the bottom. The 
crude methanol, which contains allyl alcohol, acetone, methyl acetate 
and alcohol oils, is first fractioned in two discontinuous stills, which 
yield refined allyl alcohol and alcohol oils as final products, while 
a 50 per cent methyl acetone, an intermediate methyl acetate, and a 
99 per cent methanol are sent to the four-column continuous stills, 
which in turn yield 75 per cent methyl acetone, 75 per cent methyl 
acetate and C.P. methanol. 

The 15 per cent acetic acid obtained from the first continuous 
de-alcoholizing distillation is used directly in the production of 
ethyl acetate from ethyl alcohol in the presence of sulfuric acid. 

A flow-sheet of the process is illustrated in Table XVIII. 

TABLE XVIII 

FROM CARBONIZATION BUILDING 




\ 






> 


;L 


H 


CRUDE METHANOL 


L 


ETHYL ALCOHOL 


I | PLUS LIME | 


H 


ETHYL FORMATE 


H 






*j WEAK ACETIC ACID 


PLUS CALCIUM CLORIDE ' 


H 


IPLUS SULPHURIC ACID 1 | CRUDE ETHYL ACETATE | ^{ 


| PLUS LIME 


| DRY ETHYL ACETATE f*^ 


H 


J" 


HEAVY ACID OIL 




L 


r 



ALLYL ALCOHOL 



FINISHED KETONES 



1WASHED ALCOHOL OIL 



HIGH BOILING ESTERS 



85% ETHYL ACETATE 



| HEAVY NEUTRAL 01 L" 



LIGHT ACID OIL 



The following table gives the yields of the various intermediate 
and{inal products per ton of dried wood treated: 



INTERMEDIATE PRODUCTS 



Total 100% spirits, gallons. . 



FINAL PRODUCTS 

Charcoal, Ibs 600 

Non-condensable gas, cubic feet (290 

B.t.u. per cubic foot) 5000 

5,0 C, P. methanol, gallons 3.118 

Methyl acetone, gallons o. 653 

Allyl alcohol, gallons o. 048 

Ketones, gallons 0.126 

Methyl acetate, gallons o. 945 

Soluble tar, gallons 22.0 



XIV 



SOFT-WOOD DISTILLATION 



295 



Settled tar, gallons n .o 

Acetic acid (as 100%), Ibs 101 .0 



Pitch, Ibs 66.0 

Creosote oil, gallons 3.25 

Ethyl acetate, gallons. 14-65 

Ethyl formate, gallons i . 27 



Various other processes have been devised for distilling wood 
waste in the production of wood tar involving the treatment of 
sawdust, shavings, splittings, wood bark, roots, refuse of one kind 
or another. 5 

The dehydrated tar, known as "boiled tar" or "retort tar," 
amounting to between 3 and 10 per cent of the weight of the wood, 
may be utilized in one of the following ways: 

( i ) It may be sold as such, and used for preserving wood. 

? 2 ) It may be burned under the retorts as fuel. 

(3) It may be subjected to fractional distillation to recover the 
light oils boiling below 150 C, heavy oils boiling between 150 
and 240 C., and the residual pitch constituting between 50 and 65 
per cent by weight of the tar. The light oils are used as solvents in 
manufacturing varnish, and the heavy oils after further refining are 
marketed as commercial wood creosote which finds a sphere of use- 
fulness as a disinfectant, wood preservative, and flotation oil. 

Soft (Resinous) Wood Distillation. Method of Distilling. In 
treating soft wood (resinous wood )a different method is followed. 
Iron or steel retorts varying 
in capacity from one to four 
cords are used, constructed 
either vertically or horizon- 
tally, as shown in Fig. 94. 
Low - pressure superheated 
steam, or saturated steam un- 
der high pressure, is intro- 
duced into the retort to re- 
move the turpentine, and then 
the volatile oils (known as 
"heavy oils") leaving a resi- 
due of coke behind. Three classes of resinous wood are used for 
the purpose: 

( I ) "Light wood" containing comparatively large quantities of 
turpentine. 




FlG. 94. Retorts for Distilling Soft Wood. 



296 WOOD TAR, tPOOD-TAR PITCH AND ROSIN PITCH XlV 

"Stumps/' which also contain more or less turpentine 
Saw-mill waste, which is rather poor in turpentine. 

The wood is first "hogged/* or in other words, cut into chips 
before it is introduced into the retort. The temperature is raised 
gradually to 200 C. as the steam passes through the retort Water 
and crude turpentine distil over first and are separated by settling. 
As the temperature rises above 200 to 220 C. the wood commences 
to decompose into tarry substances, and at about 250 C. the resins 
present break up into "rosin spirits" and "rosin oils," Both the 
crude turpentine and the heavy oils are redistilled separately, the 
former producing purified wood turpentine and the latter pine oil, 
rosin oil and pitch. Rosin spirits boils between 80 and 200 C, 
wood turpentine between 150 and 180 C., pine oil between 190 
and 240 C, and rosin oil between 225 and 400 C. This process 
is illustrated diagrammatically in Table XIX. 

TABLE XIX 

LIGHT WOOD (PINE OR. RESINOUS WOODS) 
Steam distilled up to 200 C., and then distilled destructively 

Water Below 200 C, Above aoo C. 

Condensable Distillate. Redistilled into: Destructive distillation occurs 



I I | I i 

Light oils Heavy oils Non-condensable Condensable Charcoal 

(Fractioned) (Fractioned) gases Distillate Residue 



| J ^ J J I Treated the same as in 

Rosin Wood Part of Balance of Rosin Pine-tar Hard wood distillation 

Spirits Turpentine Pine oil Pine oil oils pitch (See Table XVII) 

In some cases the "light wood" is subjected to a process of 
destructive distillation without using steam. The temperature is 
raised slowly and the distillate under 200 C, caught separately to 
avoid contamination with tarry matters. After the temperature 
rises above 200 C., the process follows the same course as for hard- 
wood distillation. 

Refining Processes. The distillate under 200 C. is fractioned 
into light and heavy oils respectively. The light oil is in turn redis- 
tilled to recover the rosin spirits, wood turpentine and a part of the 



XIV SOFT -WOOD DISTILLATION 2&7 

pine oil. The heavy oil is similarly redistilled to separate the pine 
oil, rosin oil and a part of the pitch. The crude tar obtained above 
200 C, is distilled to recover any acetic acid, and the residue either 
marketed as "pine tar" or distilled to separate the light and heavy 
oils from the pine-tar pitch obtained as residue. A pitch-like prod- 
uct may be obtained upon blowing rosin oil with air and superheated 
steam. 8 

Another treatment of soft wood consists in subjecting it to an 
extraction process with solvents, which are recovered and used over 
again. In this process, the wood is first ground into small frag- 
ments, which may either be treated as such, or else subjected to a 
treatment with live steam to remove the volatile f oils, including the 
turpentine and pine oil. The rosin is extracted with hot petroleum 
naphtha or benzol. The extract is thereupon distilled to remove 
the solvent (also the turpentine and pine oil, where the wood was 
extracted directly, without steaming). The rosin is extracted from 
the residue by means of a petroleum solvent (sometimes after first 
purifying by dissolving In furfural and subsequent evaporation), 
leaving a form of wood pitch which tests as follows : 

(Test 15^) Fusing-point (R, and B. method) 195-240 F. 

(Test 23) Soluble in 88 petroleum naphtha 10-20 per cent. 

(Test 370) Acid value 11-115 

(Test $jd) Saponification value 140-170 

(Test 37*) Saponifiable constituents 9*-95 per cent. 

The wood, after treatment in this manner, may either be distilled 
destructively, or used as a fuel, or used as a filler in other manufac- 
turing operations, 

Wood Tars, The bituminous products derived from the de- 
structive distillation of wood are designated commercially as hard- 
wood tar and pine tar ; hard-wood-tar pitch and pine-tar pitch. 

Wood tar has also been termed "Stockholm tar" and "Arch- 
angel tar." 

Hard-wood Tar and Pine Tar. The physical and chemical 
characteristics of the tars and corresponding pitches vary, depend- 
ing upon the kind of wood used, as well as the exact method of 
treatment The following figures will give a general idea of the 



208 WOOD TAR, WOOD-TAR PITCH AND ROSIN PITCH XIV 

characteristics of the dehydrated hard-wood tar and pine tar ordi- 
narily encountered in the American market : 

HARDWOOD PINE TAR (FROM 
TAR RESINOUS WOODS) 

.(Test i) Color in mass ..Black Brownish 

(Test 7) Specific gravity at 77 F i . 10-1 , 30 i , 05-1 . 10 

(Test 8) Viscosity Fairly liquid Viscous 

(Test 9) Consistency at 77 F Liquid Liquid 

(Test 15) Fusing-point. U Below 20 F. Below 50 F. 

(Test 1 6) Volatile matter at 500 F., 5 hrs. . , 35-60 per cent 40-7 5 per cent 

(Test 170) Flash-point 5-75 F- 60-90 F. 

(Test 19) Fixed carbon 5- ao per cent 5- 15 per cent 

(Test ai) Solubility in carbon disulfide 95-100 per cent 98-100 per cent 

Non-mineral matter insoluble o- 5 per cent o- 2 per cent 

Mineral matter o- i per cent o- x per cent 

(Test 22) Carbines o- 2 per cent o- 2 per cent 

(Test 23) Solubility in 88 petroleum naphtha 50- 90 per cent 65- 95 per cent 

(Test 28) Sulfur o.o per cent o.o per cent 

(Test 30) Oxygen 2-10 per cent 5-10 per cent 

(Test 32) Naphthalene None None 

(Test 33) Solid paraffins None None 

(Test 34*) Sulfonation residue Trace to 5% Trace to $% 

(Test 37*) Saponifiable constituents 25-85% 20-60% 

(Test 37jr) Resin acids Up to 15% Up to 30% 

(Test 39) Diazo reaction Yes Yes 

(Test 40) Anthraquinone reaction No No 

(Test 41) Liebermann-Storch reaction Yes Yes 

According to David Holde, on shaking wood tar with water, 
the aqueous extract will react acid (due to the acetic acid present), 
and upon adding a few drops of ferric chloride, will at first form a 
green and then a bluish- to brownish-green coloration. Birch-bark 
tar gives a green color with ferric chloride, which on addition of 
ammonia changes to an intense blue ; whereas birch tar gives a brown 
color. Both hard-wood tar and pine tar are almost completely 
soluble in absolute alcohol, glacial acetic acid and acetic anhydride. 
On subjecting wood tar to distillation, the first portion passing over 
shows 3, separation of water which will react acid. On continuing 
the 4* s tiM at i n > oily matters are obtained which dissolve readily in 
alcohol, and on treatment with concentrated sulfuric acid become 
converted into wate^-soluble substances. Pine tar has a high acid 
value, since it often contains as much as 30 per cent by weight of 
res}n acids, and is characterized by the absence of sulfur, paraffins, 
naphthalene and anthracene; and by the presence of phenol (Test 
39) and resin acids (Test 41) which causes it to have a high acid 
value (Test 374) and give an acid reaction to litmus. 



XIV WOOD-TAR PITCHES 299 

The following constituents have been identified in German tars : T 

BEECHWOOD PINE 

TAR TAR 

Per Cent Per Cent 

Unsaponifiable matter 18.0 53.5 

Saponifiable matter: 

Hydroxy acid anhydrides 9.5 o.o 

Hydroxy acids 52.3 14.0 

Resin acids 7.7 17.0 

Reported as fatty acids* 3.2 6.0 

Phenols 9.3 9.5 



Total 100,0 loo. o 

* Separated by TwitchelTs method, but not true fatty acids. 

Wood-tar Pitches. Hard-wood-tar pitch and f>ine-tar pitch vary 
in their physical properties, depending upon the following cir- 
cumstances : 

1 i ) The variety of wood used. 

(2) The method by which the wood is distilled, including the 
temperature, its duration, the kind of retort, etc, 

(3) The extent to which the tar is distilled in producing the 
pitch. The further it is distilled, the harder will be the pitch and the 
higher its fusing-point. 

Hardwood-tar Pitch and Pine-tar Pitch. These comply with 
the following characteristics : 

PINE-TAR PITCH 

HARDWOOD-TAR (FROM RESINOUS 
PITCH WOOD) 

(Test i) Color in mass Black Brownish black 

(Test 2) Homogeneity Uniform Uniform 

(Test 4) Fracture Conchoidal Conchoidal 

(Test 5) Lustre Bright to dull Bright to dull 

(Test 6) Streak Brown to black Brown 

(Test 7) Specific gravity at 77 F i , 20-1 .30 1 , 10-1 . 15 

(Test gb) Penetration at 77 F 0-60 0-60 

(Test gc) Consistency at 77 F 10-100 10-100 

(Test 9</) Susceptibility index > ico > 100 

(Test 10) Ductility Variable Variable 

(Test 1 50) Fusing-point (K. and S. method).. 100-000 F, 100-000 F, 

(Test 15^) Fusing-point (R. and B. method). . 1 15-005 P. 115-005 F, 

(Test 1 6) Volatile matter Variable v Variable 

(Test 19) Fixed carbon I5~35 PC* cent 10-05 per cent 

(Test 01) Soluble in carbon disulfide 3-95 per cent 40-95 per cent 

Non-mineral matter insoluble 5-70 per cent 0-60 per cent 

Mineral matter , o-i per cent 0*1 per cent 



800 WOOD TAR, WOODTAR PITCH AND ROSIN PITCH XIV 

PINE-TAR PITCH 

HARDWOOD-TAR (FROM RESINOUS 
PITCH WOOD) 

(Test aa) Carbenes 2-10 per cent 0-5 per cent 

(Test 23) Solubility in 88 petroleum naphtha 1 5-50 per cent 25-80 per cent 

(Test 28) Sulfur o per cent o per cent 

(Test 30) Oxygen in non-mineral matter 1-5 per cent 2-8 per cent 

(Test 32) Naphthalene None None 

(Test 33) Solid paraffins. None None 

(Test 340) Sulfonation residue 0-5 per cent 0-3 per cent 

(Test 37*) Saponifiable constituents 60-95 per cent 45-75 per cent 

(T$st37) Resin acids Up to 20 per cent Up to 40 per cent 

(Test 39) Diazo reaction Yes Yes 

(Test 40) Anthraquinone reaction No No 

(Test 41) Liebermann-Storch reaction Yes Yes 

The following constituents have been identified in German 
pitches : 8 

HARD BEECHWOOD- MEDIUM HARD 

TAR PITCH, PINE-TAR PITCH, 

Per Cent Per Cent 

Unsaponifiable matter 6.0- 6.3 19.7 

Saponifiable matter: 

Hydroxy acids and anhydrides 77o- 65 .3 31 . 8 

Resin acids o.o- o.o 35.2 

Neutral tar resins 14.0- 25.4 1.5 

Reported as fatty acids * 1.5- 1.5 a. 8 

Phenols 1.5- 1.5 8.0 

Mineral matter o.o- o.o I .o 

Total 100. o 100,0 100,0 

* Separated by TwitchelTs method, but not true fatty adds. 

V 

Soft and medium hard wood-tar pitches are fairly soluble in 
ethyl alcohol, and as the hardness increases the solubility decreases. 
Hard pitches are only sparingly soluble. 

According to Benson and Davis, 9 wood-tar pitches are more 
soluble in acetone than in carbon disulfide. Thus, hardwood-tar 
pitches were found to be 15.631.9 per cent more soluble in acetone 
than in carbon disulfide, and pine-tar pitches (obtained from the 
Douglas fir) 8.0 to 57.8 per cent more soluble in the former solvent. 

Wood-tar pitches are characterized by their extreme suscepti- 
bility to changes in temperature, by the fact that they appear hard 
and at the same time show a surprisingly low fusing-point, 10 and are 
characterized by the absence of sulfur, paraffins, naphthalene and 
anthracene. Wood-tar pitches are notoriously non-weatherproof. 
They are extremely susceptible to oxidation on exposure to the 
weather and are soon converted into a lifeless and pulverulent mass. 



XIV ROSIN PITCH 301 

However, their physical properties and weather-resistance may be 
improved by fluxing with cashew-nut-shell oil, 11 or by blending with 
fatty-acid pitch, which latter may be accomplished by heating to- 
gether pitches of the same fusing-points, respectively, 12 

Wood tar may be hardened and made more suitable for use in 
black paints by treating with concentrated sulfuric acid removing 
the water-soluble substances, 13 and the product may be dissolved 
in acetone or methyl alcohol for use as lacquers. 14 Artificial 
resins may also be produced by treating wood tar with formaldehyde 
in the presence of a catalyst, 15 or by heating wood tar with 10 per 
cent zinc oxide at 110 C., 16 or by treatment with chlorine in the 
presence of A1C1 3 as catalyst, 17 in which latter case the product is 
soluble in methyl alcohol. Wood tars may be hardened by heating 
with sulfur, 18 or by blowing with air in the presence of a small 
amount of sulfur, 19 or by blowing with air, ozonized air or oxygen 
at 120-150 C 20 

Wood tars have been utilized for the production of tar soaps, 
lubricants, flotation agents, pharmaceutical products, etc. 21 

ROSIN PITCH 

Raw Materials Used. The sap of the long-leaf pine, known 
chemically as an oleo-resin, is composed of a mixture of spirits of 
turpentine and rosin. It is gathered by incising the bark one-half to 
one inch, whereupon the oleo-resin slowly exudes and is collected in 
small cups. 

The oleo-resin is then distilled to separate the spirits of turpen- 
tine from the rosin. The apparatus ordinarily used in the United 
States for this purpose is shown in Fig. 95, consisting of a simple 
type of copper still with a "worm" condenser. The capacity of the 
still varies from 10 to 40 barrels, and usually between 15 and 20, 
After the still is charged, the fire is started, and a mixture of spirits 
of turpentine and water (since the oleo-resin contains between 5 
and 10 per cent of water) appears in the condenser. When all the 
water has boiled over, additional quantities are added in a small 
stream during the distillation, since the introduction of water causes 
the turpentine to boil at a lower temperature and prevents over- 
heating, improving both the color and yield of the turpentine and 
rosin. Towards the end of the distillation the stream of water is 



302 



WOOD TAR, WOOD-TAR PITCH AND ROSIN PITCH 



XIV 



shut off, and the rosin heated until all the moisture is expelled, 
usually between 300 and 400 F. Before cooling, any foreign mat- 
ter is skimmed off the surface of the rosin, after which it is strained 
through a fine mesh screen and barreled, 22 

Method of Distilling. Rosin, deprived of its turpentine, when 
heated in a closed retort undergoes destructive distillation, yielding 
a gas, an aqueous liquor 'and an oily distillate which may be sepa- 
rated into several fractions. If the process is carried to completion, 
coke will be left as residue. If the distillation is terminated before 
the formation of coke, a pitchy residue will remain, known com- 
mercially as "rosin pitch." 

The rosin may be distilled either with or without superheated 
steam. If the latter is employed, the quality of the distillate is im- 




FIG. 95. Retort for Distilling Rosin. 



proved, and a much better temperature control obtained. Distilla- 
tion under vacuum is also used in many cases. The rosin may ac- 
cordingly be distilled by any of the following processes : 

( i ) At atmospheric pressure without steam. 
(2)* With superheated steam. 
(3) Under vacuum. 

When the temperature of the rosin reaches 150 C. a liquid 
distillate appears which separates into two layers, the lower con- 
taining acetic acid, also other organic acids dissolved in water, and 
the upper composed of oily substances known as u rosin spirits" or 
"pinoline." When the temperature reaches 200 C. the receiver is 
changed, and the distillate which ensues is either collected together 
or separated into fractions. The temperature of the residue in the 
retort is permitted to reach 350 to 360 C. but never to exceed the 
latter. The distillate between 200 and 360 C. known as "rosin 
oil.* 1 mav be separated into various fractions termed "yellow rosin 



XIV ROSIN PITCH 303 

oil," "blue rosin oil," "green rosin oil," etc., depending upon their 
respective colors. 

Products Obtained. In distilling rosin destructively at atmos- 
pheric pressure, the following products are separated: 

Non-condensable gases 9.0 per cent 

Acid liquor 3.5 per cent 

Rosin spirits or pinoline 3.5 per cent 

Rosin oil 67.0 per cent 

Rosin pitch 16.0 per cent 

Loss (rosin adhering to walls of still, etc.) i .o per cent 

According to Victor Schweizer, 23 when rosin is distilled with 
superheated steam, the following yields are obtained: 

Acid liquor 5.5- 5. 8 per cent 

Rosin spirits 1 1 . 25-12 . o per cent 

Blue rosin oil 49 ,o -50. 5 per cent 

Brown rosin oil 10 . 25-10. 65 per cent 

Rosin pitch 18.0 -19.0 per cent 

The rosin pitch is run from the still while it is hot, and allowed 
to cool in a suitable receiver, 

Properties of Rosin Pitch. It is fairly uniform in composition 
and conforms with the following characteristics : 

(Test i) Color in mass Black 

(Test 2) Homogeneity Uniform 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Dull 

(Test 6) Streak Light yellow to brown 

(Test 7) Specific gravity at 77 F i .08-1 .15 

(Test 9^) Penetration at 77 F 0.5 ^ 

(Test 9^) Consistency at 77 F 50-100 

(Test gd) Susceptibility index Greater than 100 

(Test iof) Ductility at 77 F o 

(Test i$a) Fusing-point (K. and S. method) 120-200 F. 

(Test 15^) Fusing-point (R. and B. method) 135-225 F. 

(Test 16) Volatile matter, 500 F., 5 hrs 10-18 per cent 

(Test 17) Flash-point Above 250 F. 

(Test 19) Fixed carbon 10- 20 per cent 

(Test 21) Soluble in carbon disulfide 98-100 per cent 

Non-mineral matter insoluble * o- 2 per cent 

Mineral matter o- i per cent 

(Test 22) Carbenes o- 5 per cent 

(Test 23) Solubility in 88 petroleum naphtha 90-100 per cent 

(Test 28) Sulfur o.o per cent 

(Test 30) Oxygen in non-mineral matter 5-10 per cent 

(Test 33) Solid paraffins o.o per cent 

(Test 340) Sulfonation residue 0-5 per cent 

(Test 37*) Saponifiable constituents 25-95 per cent 

(Test 39) Diazo reaction Yes 

(Test 40) Anthraquinone reaction No 

(Test 41) Liebermann-S torch reaction Yes 



304 WOOD TAR, WOOD-TAR PITCH AND ROSIN PITCH XIV 

Rosin pitch is very much like rosin in its physical properties. It 
is extremely susceptible to temperature changes, and as ordinarily 
produced, is hard and friable at 77 F. It is characterized by the 
presence of considerable quantities of unaltered resin acids (10 to 
45 percent), and is free from fatty acids, glycerol, sulfur and paraf- 
fin. It withstands weathering very poorly, and has therefore but a 
limited use, including the lining of barrels and casks ("brewers' 
pitch") . Upon being heated, it passes rapidly from the solid to the 
liquid state, forming a melt of low viscosity. A product similar to 
rosin pitch may be produced by heating rosin with sulfur at 250 C. 24 
Burgundy pitch" is the name applied to the oleo-resin which 
exudes from the Norway spruce (Abies excelsa}, found in the 
Vosges Mountains and in the Alps; also from a species of pine ob- 
tained in the United States (Pinus australis). The crude oleo-resin 
is melted by boiling with water, and strained to remove any par- 
ticles of bark or other impurities. It then constitutes the so-called 
"Burgundy pitch" (Fix abietina], sometimes marketed under the 
name "Vosges pitch/' These terms are misnomers, since the ma- 
terial is not a true "pitch," but in reality an oleo-resin. It contains 
more or less spirits of turpentine, which escaped expulsion during 
the boiling process, also a quantity of emulsified water imparting to 
it an opaque, yellowish-brown color. In consistency it is a more or 
less brittle solid, largely susceptible to temperature changes. In 
summer it softens and gradually flows, and in winter it appears very 
hard and brittle. It melts easily, decrepitating because of the water 
present, and has a strong odor because of the associated spirits of 
turpentine. On aging it loses its opacity, due to evaporation of the 
emulsified water, and turns first to a translucent, and then to a trans- 
parent brown color, similar to that of rosin. Its composition is 
substantially the same as rosin, containing in addition, spirits of 
turpentine and emulsified water. 



CHAPTER XV 

PEAT AND LIGNITE TARS AND PITCHES 

PEAT TAR AND PEAT-TAR PITCH 

Formation of Peat. Peat * is derived from the decomposition 
of vegetable matter in swampy places, such as marshes and bogs. 
On the surface we find the growing aquatic plants; somewhat deeper 
we find their decayed remains; and still deeper a dark colored pasty 
substance containing a substantial percentage of moisture and con- 
stituting the crude peat. The plants which result in the formation 
of these deposits are mainly aquatic, including marine grasses, reeds, 
rushes, hedges and various mosses. The transformation is caused 
partly by oxidation in the presence of moisture, and also to some 
extent by the action of certain forms of bacteria, molds and fungi. 
As the mass of peat builds up in thickness, the lower layers are first 
compacted by the resulting pressure, and then gradually carbonized. 
The essential condition to peat formation is that the vegetable re- 
mains shall be deposited at a rate exceeding that of their decompo- 
sition. This does not prove to be the case in very warm climates, 
where the remains are entirely decomposed. The organic matter 
should only be partly decomposed, and since the products of partial 
decomposition act as a preservative to inhibit further decay, we can 
readily understand why the building up of peat beds is cumulative. 
It progresses most rapidly at a mean atmospheric temperature of 
45 F M which accounts for the fact that no peat bogs occur between 
the latitudes of 45 N., and 45 S. It is estimated that there exist 
in the United States 20 million acres of peat bogs, 30 million acres 
in Canada, 50 million on the continent of Europe, also approxi- 
mately 3 million in Ireland. 

Varieties of Peat. The following constitute the most important 
varieties of peat, based on the locality in which they are found : 

(i) "Hill peat, n found at mountain tops and derived from 
plants consisting of sphagnum and andromeda mosses, likewise 
heath, 

305 



306 PEAT AND LIGNITE TARS AND PITCHES XV 

(2) "Bottom peat," found near rivers, lakes, etc., in the low- 
lands, including: (a) dark peat, approaching lignite in composition, 
occurring at the lower parts of the deposit; (b) middle peat, which 
is lighter in color and in weight than the preceding; (c) the top 
stratum, which has a fibrous structure. 

Peat varies in color from light yellowish, through various tints 
of brown, to brownish black or black, all of which appear deeper 
when the peat is moist The lighter shades generally darken to 
brownish black or black upon exposure to air ; due largely to oxida- 
tion* In texture, peat varies from light porous matter having a 
fibrous or woody structure, to substances which are amorphous and 
clay-like when wet, but appearing quite hard and dense upon drying. 
When recently formed, the peat beds are but loosely compacted, but 
as they accumulate, the under layers become compressed, so what 
once was a foot thick may be concentrated to several inches. In 
other cases the beds become covered with sedimentary rocks, which 
augment the pressure, and gradually transform the peat into lignite. 

The chemical composition of peat is but little understood. It is 
regarded as a mixture of water, inorganic matter (calcium and iron 
compounds), vegetable fibers and humus acids (such as humic, 
ulmic, crenic, apocrenic, etc.). According to H. Borntrager 2 the 
black varieties contain between 25 and 60 per cent of humic acids, 
30 to 60 per cent of fiber, and 3 to 5 per cent of ash. Nitrogenous 
compounds are also present, varying from I to 3 per cent of the 
dry weight, resulting partly from the associated animal matter, and 
also due partly to the humic acids combining with atmospheric nitro- 
gen, forming what are known as azo-humic acids. Sulfur is also 
present in amounts between o.i and 5,3 per cent based on the dry 
weight. 

Resinous substances are found in certain varieties of peat, to 
which various names have been assigned, also bodies of a waxy 
nature derived from the associated gelatinous algae, known as 
"sapropel." In time, sapropel is converted into a coal-like sub- 
stance, known as sapropelite, or sapropelite coal, which has been 
regarded as the progenitor of cannel coal and boghead coal. 

Methods of Collecting Peat. Peat is generally collected by 
cutting trenches through the bog with a spade, and removing it in 
sods about 3 to 4 ft. long. The deposits are worked in steps or 



XV PEAT TAR AND PEAT-TAR PITCH 307 

tiers. Mechanical excavators and dredges have also been used for 
the purpose. The sods are allowed to drain, then air-dried and 
finally heated to a high temperature in either stationary or revolv- 
ing ovens, to remove the water. Peat as freshly mined contains 75 
and 90 per cent by weight of water, which must of necessity be 
removed before the product can be used as a fuel. Air-dried peat 
carries 10 to 15 per cent of moisture, and the artificially dried 
peat between a trace and 80 per cent of mineral ash, consisting 
principally of sand and clay with smaller quantities of iron oxide, 
calcium and magnesium salts. The maximum quantity of ash usually 
considered allowable when used as a fuel is 25 per cent of the dry 
weight. Peat with less than 5 per cent ash is considered good, be- 
tween 5 and 10 per cent as fair, and over 10 per cent as poor, 
with peat containing less than 10 per cent of ash in the moisture- 
free state, the fixed carbon varies between 15 and 35 per cent, 
averaging about 30 per cent. 

Dehydrating Processes. It is customary to briquette the partly 
dried peat, carrying 10 to 15 per cent of water, and then continu- 
ing the drying until practically all the moisture is removed, and the 
residual peat compacted into tough briquettes suitable for use as 
fuel. It is briquetted under a pressure of 18,000 to 30,000 Ib. per 
square inch, which generates sufficient heat to liberate some of the 
tarry compounds of the peat, causing the sides of the briquettes to 
assume a highly polished glaze. The product is claimed to have 
a calorific value almost equal to that of coal. Various mechanical 
contrivances have been devised for removing the water and mois- 
ture from peat. 

In Europe and Canada, attempts have been made to utilize air- 
dried peat for generating producer gas. Various types of apparatus 
have been devised for the purpose, which result in the recovery of 
i to 2 per cent of peat tar, based on the dry weight of the peat 8 
In generators (e.g., Mond gas generators) from '8 to 9 per cent of 
tar is recovered, and in low temperature distillation processes from 
8 to 25 per cent is recovered. 

Methods of Distilling. Various methods have been used for 
distilling peat, similar to those employed for treating coal. Dried 
peat may be destructively distilled in closed retorts, obtaining a gas 
suitable for use as a fuel, likewise tar, ammonia, and a good grade 



308 , PEAT AND UGNITE TARS AND PITCHES XV 

of coke, but in the United States this process has only been carried 
on in a small experimental way. There are two classes of peat tar, 
lamely retort peat tar and producer peat tar, both of which are 
low-temperature products generated at not exceeding 600 C At 
the present time the cost of drying and briquetting peat brings its 
price higher than that of bituminous coal. For these reasons neither 
peat tar nor peat-tar pitch are produced in commercial quantities. 
The following represent the percentages by weight of by-prod- 
ucts obtained per ton of the air-dried peat: 

Gases and loss Ia -ao per cent 

Aqueous liquor 30-40 per Cent 

Peat tar 2-10 per cent 

Coke 30-40 per cent 

100 per cent 

The composition of an average specimen of peat tar is as 
follows : 

Insoluble in ether (i.e., oxy-acids and their esters, also iron and cal- 
cium derivatives) 3 per cent 

Soluble in ether: 



5 per cent 

Unsaponifiable substances: 

Solid portion 8 per cent 

Liquid portion 55 p cr cent 

Saponifiabie substances: 
Oxy-^cids 

Insoluble in ether 3 per cent 

Soluble in ether 8 per cen t 

Fatty acids 10 per cent 

Phenols , 3i per cent 

4i per cent 

Total 100 per cent 

The following yields are obtained from German peat: 

Water-free peat tar 4 , 9 to 9,9 per cent 

Light oils (sp. gr, o. 820-0. 835) 7-3 to 34. 6 per cent 

Heavy oils (sp. gr, 0.830-0.885) 19.6 to 36.0 per cent 

Paraffin '. 3.3 to 46.0 per cent 

Peat-tar pitch 12.8 to w. 6 per cent 

Creosote oil and loss 6.2 to 40.5 percent 

Refining Processes. The tar is separated from the aqueous 
liquor by heating the mixture with steam to the melting-point of the 
tar, which then rises to the surface. It is a black, viscid liquid 
with a disagreeable acrid odor, representing a to 20 per cent of 



XV 



PEAT TAR AND PEAT-TAR PITCH 



309 



the dry weight of the peat used. The aqueous liquor contains am- 
monia salts, acetic and other organic acids, wood alcohol, and pyri- 
dine bases. The tar is slowly distilled, and after the water ceases 
to pass over, the receiver is changed and the distillation continued 
until 45 per cent of oily distillate has been collected. The receiver 
is again changed, and heavy oils containing paraffin wax, totalling 
about 30 per cent by weight of the tar, are caught separately, 
leaving 15 to 20 per cent of peat-tar pitch in the retort, which is 
finally drawn off. The oily distillate first obtained is redistilled 
into light naphtha (density under 0.83), and heavy naphtha (den- 
sity 0.85). The heavy oil is cooled and pressed to separate lubri- 
cating oil from the paraffin wax. The products are treated first 
with concentrated sulfuric acid and then with caustic soda to re- 
move tarry impurities and creosote oil respectively, the latter being 
recovered in the form of creosote or carbolic acid. 
The dry peat tar yields the following : 





Crude, 
Per Cent 


After Purification, 
Per Cent 


Light naphtha 


16 


11 


Heavy naphtha 


1Q 


1C 


Lubricating oil 


o^ 
1C 


^j 

1 O 


Paraffin wax 


1 j 
12 


X 3 




Peat-tar pitch 


16 


16 


Creosote 




frt 


Loss 


1 1 


on 










100 


100 



A diagrammatical outline of the various products obtained on 
the dry-distillation of peat is given in Table XX. 







TABLE XX 










PEAT 










(Dry distilled) 








Gas (57%) 


Aqueous liquor (46%) 
Distilled: 




Peat tar (4%) 
Distilled: 

1 


Coke (ag%) 


1 i 
Wood Ammonia 
alcohol (o.i6%> 
(0,34%) 


i i i 

Acetic Losses and Light 
acid water oil 
(0.44%) (%) 


1 I 
Heavy Paraffin 
oU (0.3%) 


1 1 
Phen- Pitch 
olatc (0.2%) 



310 PEAT AND LIGNITE TARS AND PITCHES XV 

Properties of Peat Tar. Dehydrated peat tars in general, test 
as follows: 

(Test i) Color in mass Black 

(Test 7) Specific gravity at 77 F 0.90-1 .05 

(Test 9) Hardness or consistency Liquid 

(Test i fa) Fusing-point (K. and S. method) 40-60 F. 

(Test 16) Volatile matter at 500 F., in 5 hrs 50-85 per cent 

(Test 17*) Flash-point 60-95 F. 

(Test 19) Fixed carbon 5-15 per cent 

(Test at) Soluble in carbon disulfide 98-100 per cent 

Non-mineral matter insoluble o- 2 per cent 

Mineral matter o- i per cent 

(Test 22) Carbenes o- 2 per cent 

(Test 23) Solubility in 88 petroleum naphtha 95-100 per cent 

(Test 28) Sulfur Less than i per cent 

(Test 30) Oxygen in non-mineral matter 5-15 per cent 

(Test 33) Solid paraffins 5-15 per cent 

(Test 34^) Sulfonation residue 5-15 per cent 

(Test 37*) Saponifiable constituents 5-15 per cent 

(Test 39) Diazo reaction Yes 

(Test 40) Anthraquinone reaction No 

(Test 41) Liebermann-S torch reaction No 

Properties of Peat-tar Pitch. Peat-tar pitch is obtained by the 
evaporation or steam distillation of peat tar. It is not an article 
of commerce in the United States. Its hardness or consistency, 
as well as its f using-point, depend upon the extent to which the dis- 
tillation has been conducted. Ordinarily, peat-tar pitch tests much 
the same as lignite-tar pitch, the results being included in Table 
LXXXIV. It is highly susceptible to temperature changes, and 
withstands exposure to the weather very poorly. 



LIGNITE TAR AND LIGNITE-TAR PITCH * 

Varieties of Lignite. The U. S. Geological Survey estimates 
that 1,087,514,400,000 tons of lignite are available in the United 
States, but it is used only in a limited way, due to the abundance 
of other types of fuel. Large deposits occur also in Alberta, Sas- 
katchewan and Manitoba, Canada. A zone covering about 1700 
square miles has been located in Australia, and one small deposit 
has been reported in England (at Bovey-Tracey in Devonshire). 
In Germany, however, the lignite industry has made much more 
rapid advances, owing partly to the scarcity of high-grade coals, and 
partly to the fact that the deposits are located close to large cities, 



XV LIGNITE TAR AND UGN1TE-TAR PITCH 311 

making the cost of transportation low. The lignite is accordingly 
used as a fuel for steam plants f for manufacturing producer gas, 
and for distillation purposes to recover its valuable by-products. 
The descriptions of the methods which follow are based on 

German practice as carried out in the following localities, viz. : 

? 

1 i ) Near Horrem, a short distance west of Cologne in Rhine Prov- 

ince; 

(2) In the neighborhood of Halle on the Saale, in the Proyinces 

of Saxony and Thuringia; and 

(3) At Messel, near Darmstadt in Hessen Province. 

The so-called browncoal (variety of lignite) is mined at the first 
two localities. It is estimated that 20,000 to 25,000 tons are bri- 
quetted daily in the Cologne mining district alone, where the beds 
run from 30 to 350 ft. thick, averaging 75 ft; Browncoal differs 
somewhat from American lignite in carrying a higher percentage 
of moisture (about 60 per cent instead of 25 to 50 per cent). 
American lignites generally resemble bituminous coal in hardness 
and appearance, whereas browncoal is distinctly earthy in appearance 
and is soft and friable enough to be dug with a spade. Moreover, 
browncoal contains up to 13 per cent waxy constituents which are 
of great value as a binder in briquetting, whereas American lignites 
contain less than 1.5 per cent of binder, and are unsuitable for 
briquetting when used alone. As mined, browncoal is soft and either 
unconsolidated or but slightly consolidated. The Messel deposit 
carries about 30 per cent clay and 45 per cent water, the organic 
constituents apparently being combined chemically with the clay. 
It is greasy in consistency, having a black color with a greenish cast. 
The bed covers about 240 acres in hemispherical depression, and 
measures 480 ft. in thickness, under a cover 13 ft. thick composed 
of gravel and clay. 

Mining Methods. Browncoal in the Cologne and Halle re- 
gions is found in stratified beds in which the layers alternately ap- 
pear lighter and darker in color. The lighter layers form a 
brownish-black plastic and greasy mass when freshly mined, and a 
yellowish to light brown pulverulent substance when dry. They are 
characterized by the presence of waxy constituents (soluble in car- 
bon disuifide, benzol, etc.) The darker layers form a black plastic 



312 PEAT AND LIGNITE TA&S AND PITCHES XV 

mass when fresh, and a dark-brown to black earthy substance after 
drying. They differ from the light-colored layers, in being sub- 
stantially free from waxy constituents. The two varieties are 
sorted during the process of mining. The light-colored product 
resembles the mineral pyropissite. 

The lighted variety of lignite has been incorrectly termed 
"bituminous lignite," and the darker, "non-bituminous lignite." For 
purposes of differentiation, we will refer to them as "retort lignite" 
and "fuel lignite" respectively.* Retort lignite ranges in specific 
gravity from 0.9 to i.i and melts at ignition, whereas fuel lignite 
has a gravity of 1.2 to 1.4, and does not melt, 

It is assumed that these two varieties of lignite, since they occur 
in the same deposit, result from differing conditions surrounding 
their formation, as for example a variation in water level. Thus 
if the original vegetable matter containing a large amount of waxy 
constituents was protected from the action of atmospheric oxygen 
by being surrounded with vfater until the transformation into lignite 
had been completed, then the woody tissue was more or less pre- 
served, and fuel lignite resulted. If, however, the water receded 
and exposed the deposit to the action of air, then the woody tissue 
became partly or wholly oxidized, leaving the more resistant ma- 
terials behind, and resulting in the formation of retort lignite. If the 
process of atmospheric oxidation had been carried to the greatest 
pdssible extent, then the waxes only remain behind, in the form of 
the mineral pyropissite, which, however, is no longer mined, since its 
total available supply has been exhausted. Lignite as freshly mined 
is more or less rapidly acted upon by atmospheric oxygen, the dark 
variety being more susceptible than the light one. A typical lignite 
vein carries about twice as much fuel lignite as retort lignite. 

Lignite is mined by the open-cut method where the over-burden 
is not very thick, or by driving shafts and tunnels when the bed is 
situated sortie distance below the surface. In the case of open-cut 
mJfiirig, the overburden is first removed with steam shovels, and the 
ligijite excavated by mechanically operated chain and buckets, which 
load the material into small skips. 

la Gerpany they are termed "Distillation Coal 1 ' (SchwelkoUe) and "Fire Coal" 



XV LIGNITE TAR AND LIGNITE-TAR PITCH 313 

Shaft mining presents a number of difficulties owing to the soft- 
ness and unstability of the crude lignite. The shafts must be well 
timbered, and in many cases it is first necessary to freeze the lignite 
before it can be handled. 

Methods of Distilling. Retort lignite is treated in one of two 
ways, viz. : 

(1) It is subjected directly to low-temperature destructive dis- 
tillation 6 or 

(2) It is first extracted with a solvent to remove the montan 
wax and the residue either distilled destructively or briquetted and 
sold as fuel. 

Fuel lignite is also treated in one of two ways, viz. : 

(1) If it is comparatively free from ash, it is briquetted and 
used as fuel ; or 

(2) If it contains a large proportion of ash, as with Messel 
lignite, it is used for manufacturing producer gas by combustion in 
an atmosphere of air and steam, so that practically all the carbon- 
aceous matter is consumed, leaving almost pure ash behind. Smce 
Messel lignite in its crude state contains but 25 per cent of com- 
bustible material, it is unsuitable for use as fuel, or for purposes 
of destructive distillation. 



When the lignite is to be used for fuel, it is converted into 
briquettes by subjecting the granulated material to great pressure. 
The heat generated during this operation softens the waxy sub- 
stances present, and binds the particles into a solid mass. It is 
unnecessary, therefore, to add any extraneous binding medium. 

In manufacturing briquettes, the lignite is first crushed to about 
the size of peas, then passed through a drier to reduce the moisture 
to approximately 15 per cent. A tubular drier, heated with steam, 
has been found most satisfactory for the purpose. 6 The lignite 
powder is fed into a briquetting press, where it is subjected to a 
pressure between 18,000 and 22,500 Ib. per square inch. 

Retort lignite is unsuitable for fuel or manufacturing briquettes, 
as the large quantity of waxy constituents present will soften when 
heated, causing the briquettes to melt and drop through the grate 



314 



PEAT AND LIGNITE TARS AND PITCHES 



XV 



bars. When the retort lignite has been extracted with solvents to 
remove the "montan wax/' the residue retains enough waxy con- 
stituents to enable it to be briquetted. 

When the retort lignite is to be subjected to destructive distilla- 
tion, it is used directly as 
it comes from the mine, 
without drying. In fact, 
the presence of the water 
materially assists the dis- 
tillation process by pre- 
venting the volatile prod- 
ucts from decomposing 
too extensively. The 
water is converted into 
steam which quickly re- 
moves the vapors from 
the hot retort and pre- 
vents cracking, thus in- 
creasing the yield of tar. 
Taking the yield of tar 
from freshly mined lignite 
as loo, the yield from air- 
dried lignite is about 74, 
and from lignite dried at 
105 C. approximately 56-. 
Practice has shown 
that the moisture content 
should not be less than 30 
per cent. In distilling lig- 
nite, the humic acids pres- 
ent are converted into the 

so-called "neutral bodies," the cellulose derivatives into phenolic 
bodies and unsaturated hydrocarbons, and the waxy constituents into 
saturated hydrocarbons and paraffin wax. 

It is claimed that the Rolle retort shown diagrammatically in 
Fig, 96 has been found most satisfactory for treating 3-5 tons lignite 
per day. It is 5 to 6 ft* in diameter by 20 to 25 ft. high, and works 
continuously, the operation progressing in two stages, viz.: 




FIG. 96. Retort for Distilling Lignite. 



XV LIGNITE TAR AND UGNITE-TAR PITCH 315 

1 i ) Drying the lignite. 

(2) Decomposing the lignite into gas, water, tar and coke. 

The contrivance is composed essentially of two concentric cylin- 
ders, an outer one of fire brick and an inner one consisting of a stack 
of conical rings assembled in louvre fashion, constructed of iron or 
fire clay. The lignite after being crushed into lumps about i l /2, to 
2 l /2 in. in diameter is introduced into the space between the con- 
centric cylinders. The products of distillation pass out through the 
flues A and B. The openings C represent the fire-flues; D ; the 
stack of conical rings; E, the cap covering the rings; F, an inverted 
cone of metal into which the coke falls after the lignite has been 
thoroughly carbonized; G, a device for intermittently drawing off 
the coke ; H, the combustion chamber ; /, vents for introducing the 
gases; K y the pipes through which the gases enter; and L, the fire 
place which comes into play when the retort is first started up. Coal 
or lignite is burnt on the grate, until the process of destructive dis- 
tillation commences, whereupon the resulting non-condensable gases 
are introduced through K and /, and caused to burn in the flues C. 
The space over the cap E is kept filled with lignite, and the rate of 
travel through the retort is controlled by the frequency with which 
the coke is removed from the chamber G. 

The temperature at which the distillation takes place varies 
between 500 and 900 F., and the vapors issue from the retort at 
250 to 300 F. The products of decomposition are drawn from the 
retort by a slight suction, and passed through a series of air con- 
densers, which removes most of the tar, the high boiling-point oils, 
and part of the water. The condensation is completed by passing 
the gases through pipes surrounded by water. 

The tar is separated from the condensed water by warming it 
and allowing it to stand quietly in a suitable receptacle. The tar 
being lighter than the water, rises to the surface, and is drawn off 
when the separation is complete. 

Products Obtained. A bituminous lignite containing 20-30 per 
cent moisture and 15-16 per cent soluble in carbon disulfide, 
yielded 24 per cent tar having a specific gravity of 0.885 at 50 C., 
a solidifying point of 37 C., and containing 16 per cent creosote 
oils. Similarly, a non-bituminous lignite containing 15 per cent 



316 



PEAT AND LIGNITE TARS AND PITCHES 



XV 



moisture and 3-4 per cent soluble in carbon disulfide, yielded 7.6 
per cent tar having a specific gravity of 0.955 at 5 C., a solidi- 
fying point 33 C, and containing 37 per cent creosote oils. On 
fractional distillation with superheated steam, the former yielded 
3.2 per cent pitch and the latter 8.5 per cent 
The following yields are obtained : 

Lignite tar (vertical retorts) up to 7 per cent 

" " (low temperature) 7 to 12 per cent 

Brown-coal tar (Rolle retort) 4 to 8 per cent 

" " " (low-temperature) 8 to 24 per cent 

A commercial product known as "kaumazite" is made from 
Bohemian lignite by a process of low-temperature distillation. 

In recent years the following 
products have been recovered : 

Water 50-60 per cent 

Tar 5-10 per cent 

Coke 25-35 per cent 

Gas Balance 

Treating Impure Lignite. The 
Messel lignite carrying a large per- 
centage of mineral matter is treated 
in a special form of retort built in 
batteries, as illustrated in Fig, 97, 
The process takes place in three 
stages, viz. : 

1 i ) Drying of the lignite and ac- 
companying generation of steam, tak- 
ing place in the zones c. 

(2) Distillation of the dried ma- 
terial, taking place in zones b. 

(3) Combustion of the residual 
coke by means of air and the steam 
generated in (i), taking place in 
zones a. The steam liberated in 
zones c is passed through the flues 
G-tf, /-/, and G-^ ; respectively, into 
zones a j as illustrated. 




Fie. 97. Retort for Distilling 
Impure Lignite. 



In other words, the steam generated by the lignite itself, is used 
to decompose the coke into producer gas, The gas is caused to burn 



XV LIGNITE TAR AND LIGNITE-TAR PITCH 317 

in the chambers A, B and C respectively, the products of combus- 
tion passing through the openings o ) o. Pipe d represents the out- 
let for the products of decomposition, and s represents the supply 
pipe for the heated gas. The paths of the products are indicated by 
the arrows. The yield of tar varies between 4 and 14 per cent, 
averaging about ^ l / 2 per cent (19 gallons per ton), that of gas 6 
per cent, water 44 per cent and coke 36 per cent. The residue dis- 
charged from the bottom of the retort is composed of mineral mat- 
ter carrying 8 per cent of undecomposed carbon. More gas is gen- 
erated during the process than is required for heating the retort, 
hence the excess is used for other purposes. 

Lignite in either the air-dried or briquetted form is gradually 
being used more and more, especially in Europe, for manufacturing 
producer gas. About 60 cu. ft. of gas are produced from each 
pound of the dry lignite, also l / to l / 2 per cent by weight of lignite 
tar, which is separated from the producer gas in the usual manner. 

In certain localities (e. g. northern Bohemia) lignite is carbon- 
ized in a variety of coke-oven, similar to that used for treating 
coal, to produce coke, during which process a tar is obtained known 
as coke-oven lignite-tar. The carbonization takes place at 1100 C. 
and the resulting tar has a specific gravity at 60 C. of 0.970. 

Properties of Lignite Tar. Lignite tar has a buttery consist- 
ency at ordinary temperatures and a dark brown to black color. It 
is composed of liquid and solid members of the paraffin and olefine 
series, together with a small quantity of the benzol series, also the 
higher phenols and their derivatives ( fo to 25 per cent) . It is char- 
acterized by the presence of a substantial proportion of solid paraf- 
fin (10 to 25 per cent) and from 0.5 to 1.5 per cent of sulfur. 

Four different varieties of lignite tar are recognized, viz. : 

(i) Retort tar (e. g. from Rolle retorts). 

(2} Low-temperature lignite-tar (produced below 6po C.), 

) Producer-gas lignite-tar (e. g. from Messel lignite). 

) Coke-oven lignite-tar (e. g. northern Bohemia). 

Lignite tars are usually emulsified with water, which separates 
with difficulty, and when derived from gas-producers they carry a 
certain amount of free carbon (up to 3 per cent). Both may be 
removed by centrifuging. Thus a tar carrying 1 1.7 per cent water 
and 2.28 per cent free carbon, upon centrifuging at 4000 to 6000 



318 PEAT AND LIGNITE TARS AND PITCHES XV 

r,p.m. at 60-85 C., yielded a product carrying 0.7 per cent water 
and 0.06 per cent free carbon. 

In general, dehydrated lignite tar conforms with the following 
characteristics : 

(Test i) Color in mass Yellowish brown to 

greenish brown to 
brownish black 

(Test 7) Specific gravity at 77 F o. 85-1 ,05 

(Test 9) Hardness or consistency at 77 F Salve-like to buttery 

(Test 10) Ductility at 77 F None 

(Test 150) Fusing-point (K. and S. method) 60-90 F. 

(Test 15^) Fusing-point (R. and B. method) 75-100 F. 

(Test 1 6) Volatile matter at 500 F., 5 hrs 70-85 per cent 

(Test 170) Flash-point (Pensky-Martens tester) 7 5-90 F. 

(Test 19) Fixed carbon 5-20 per cent 

(Test 200) Distillation test The boiling-point ranges 

between 80 and 400 
C., the greater por- 
tion distilling between 
250 and 350 C 

(Test 2i) Soluble in carbon disulphide 96-100 per cent 

Non-mineral matter insoluble o- a per cent 

Mineral matter o- i per cent 

(Test 22) Carbenes o- 2 per cent 

(Test 23) Solubility in 88 petroleum naphtha 98-100 per cent 

(Test 28) Sulfur o. 5-2 . 5 per cent 

(Test 29) Nitrogen Less than o. i per cent 

(Test 30) Oxygen 5-10 per cent 

(Test 31) Free carbon o-i per cent 

(Test 32) Naphthalene -1 per cent 

(Test 33) Solid paraffins 10-25 per cent 

(Test 34^) Sulfonation residue 10-20 per cent 

(Test 37*) Saponifiable constituents 5-20 per cent 

(Test 39) Diazo reaction Yes 

(Test 40) Anthraquinone reaction No 

(Test 41) Liebermann-S torch reaction No 

Marcusson and Picard 7 have reported the following percent- 
ages of saponifiable constituents present in normal tar from Saxon- 
Thuringian lignite : saponifiable constituents 7.4 per cent, consisting 
of oxy-acids soluble in ether 2.4 per cent; reported as fatty acids 
3,0 per cent; and phenols 2.0 per cent Generator tar from Saxon- 
Thuringian lignite: saponifiable constituents 14.0 per cent, com- 
posed of oxy-acids soluble in ether 0.5 per cent; oxy-acids insoluble 
in ether 4.0 per cent; reported as fatty acids 4.5 per cent; and 
phenols 5.0 per cent. 

Refining Processes. In practice, lignite tar is distilled to sep- 
arate various oils and paraffin wax. The distillates are purified by 



XV LIGNITE TAR AND LIGNITE-TAR PITCH 319 

treatment with acids and alkali, and the paraffin by re-crystalliz- 
ation. 

The distillation is conducted in one of three ways, viz. : 



1 i ) At atmospheric pressure, without steam. 

(2 ) By means of steam, sometimes after treating with alkal 

(3) Under vacuum, sometimes supplemented with steam. 



Vacuum distillation is generally used, as it saves fuel, reduces 
the time and prevents cracking of the distillates. The best prac- 
tice consists in using a slight vacuum at the beginning of the distilla- 
tion, and gradually increasing it until the paraffin begins to distil, 
when it is maintained at 1 6 to 28 in. of mercury by a steam injector, 
or vacuum pump. 

With steam distillation, either plain or superheated steam may 
be used and direct heating of the retort may be dispensed with in 
the latter case. 

The distillation may be intermittent or continuous. European 
practice provides for the continuous distillation of the dehydrated 
tar in a battery of vertical cylindrical stills with hemispherical bot- 
toms, having dome-shaped tops. Each still is connected with a con- 
denser composed of a circular coil of metal piping immersed in a 
water tank. Between 10 and 20 stills are erected side by side on a 
common brick setting. 

Lignite tar is first distilled to % its original bulk, and the com- 
bined residues of several stills are run into a separate retort. In 
some cases the residues are distilled to produce lignite-tar pitch, but 
in the majority they are distilled until nothing but coke remains. 
By thus treating the residues in separate retorts, the lives of the first 
retorts are lengthened materially, and the wear and tear concen- 
trated on a few. The retorts in which the preliminary distillation 
takes place are of course subjected to a much lower temperature 
than those in which the residues are treated. 

When lignite tar is distilled to coke, a certain amount of crack- 
ing occurs and consequent formation of tarry matter in the distill- 
ates, which is removed by treating with sulfuric acid. The result- 
ing sludge is worked up into lignite-tar pitch as will be described 
later. 

Obviously the pitches derived in these two ways differ in their 



320 PEAT AND LIGNITE TARS AND PITCHES XV 

physical properties, and particularly in the quantity of associated 
paraffin, which is smaller in lignite-tar-sludge pitch. 

Products Obtained. The tar is fractioned into crude oil (about 
33 per cent), a paraffinaceous distillate (about 60 per cent), red 
oil (about 3 per cent), and yields permanent gases (about 2 per 
cent), and coke (about 2 per cent). 

The crude oil is re-distilled into naphtha, illuminating oil, clean- 
ing oil, gas oil and light paraffin oil (vaseline oil). The paraffin- 
aceous mass is cooled and pressed, which removes the heavy paraf- 
fin oil from the paraffin wax. The paraffin wax is then re-crystal- 
lized and separated into the soft paraffin wax and hard paraffin 
wax respectively. 

According to Waldemar Scheithauer, an average grade of lig- 
nite tar will yield the following products, viz. : benzine 5 per cent, 
lubricating oil 5 to 10 per cent, light paraffin* oils 10 per cent, 
heavy paraffin oils 30 to 50 per cent, hard paraffin 10 to 15 per cent, 
soft paraffin 3 to 6 per cent, dark-colored products 3 to 5 per cent/ 
coke, gas and water 20 to 30 per cent. If the distillation of lignite 
tar is not continued to coke, lignite-tar pitch is obtained, amounting 
to about 5 per cent by weight of the tar. 

The diagram in Table XXI shows the essential steps in treating 
lignite tar by fractional distillation, including the two alternatives of 
running to pitch and coke respectively. 

The fractions are purified by treating successively with weak and 
strong sulfuric acid, followed by caustic soda, which improve the 
color and odor, and enable the products to command a higher price. 
The preliminary treatment with weak sulfuric acid removes a por- 
tion of the basic constituents, including the pyridirie. The stronger 
sulfuric acid extracts the remaining basic substances, the tarry mat- 
ters which impart a dark color, a portion of the unsaturated hydro- 
carbons and the resinous constituents. The alkali serves to neu- 
tralize the acid, and to remove the creosote oils which would impart 
a disagreeable odor and darken on exposure to light 

After the chemical treatment, the acid and soda sludges are 
settled off. The acid sludge is boiled with steam in lead-lined ves- 
sels, which decomposes it into pitch and sulfuric acid (30 to 40 
Baume). This acid is used for decomposing the soda sludge into 
creosote oil and sodium sulfate (Glauber salt). The impure creo- 



XV 



LIGNITE TAR AND LIGNITE-TAR PITCH 



321 



9 

a 



||H 
1 



y 



is 

"i 



"- 

ai 



o 

^s 
o 

I 



8 



J 



i- 



. 

1 



322 PEAT AND LIGNITE TARS AND PITCHES XV 

sote containing tarry matters is mixed with the pitch separated from 
the acid sludge, and after washing with water to remove all traces 
of acid and alkali, the mixture is distilled with superheated steam. 
The purified lignite creosote is recovered as distillate (having a 
specific gravity of 0.940 to 0,980, and yielding 50 to 70 per cent 
soluble in caustic soda) and the lignite-tar pitch remains as residue. 
The extent to which the distillation is continued regulates the hard- 
ness and fusing-point of the pitch, which is much harder in consist- 
ency than that obtained from the direct distillation of lignite tar. 
A black, glossy pitch of good quality may be produced by treating 
lignite tar with 4 per cent sulfuric acid (60 Baume) at 160 C. 
and the lower pitch-like layer heated with 20 per cent anthracene 
oil at 250 C. 9 

Properties of Lignite-tar Pitch. Lignite-tar pitches conform 
with the following tests : 

(Test i) Color in mass Hack 

(Test 2) Homogeneity. Uniform 

(Test 3) Appearance surface aged indoors one week. . Dull 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Very bright when fresh 

(Test 6) Streak Black 

(Test 7) Specific gravity at 77 F i .05-1 . 20 

(Test 9^) Penetration at 77 F 0-60 

(Test 9f) Hardness at 77 F., consistometer 10-100 

(Test gd) Susceptibility index Greater than too 

(Test 10) Ductility Variable 

(Test 150) Fusing-point (K. and S. method) 90-250 F. 

(Test 15^) Fusing-point (R. and B. method) 100-275 F. 

(Test 16) Volatile matter Variable 

(Test ija) Flash-point Usually above 250 F. 

(Test 19) Fixed carbon 10-40 per cent 

(Test 21) Solubility in carbon disulfide 95-99 per cent 

Non-mineral matter insoluble * 0-2 per cent 

Mineral matter o- i per cent 

(Test 22) Carbenes 0-5 per cent 

(Test 23) Solubility in 88 petroleum naphtha. ..... 60-85 per cent 

(Test 25) Solubility in benzol 75-90 per cent 

(Test 28) Sulfur i . 5-2. 5 per cent 

(Test 30) Oxygen in non-mineral matter 2- 5 per cent 

(Test 31) Free carbon Trace 

(Test 32) Naphthalene Absent 

(Test 33) Solid paraffins i- 5 per cent 

(Test 34^) Sulfonation residue 5-15 per cent 

(Test 37*) Saponifiable constituents o- 8 per cent 

(Test 39) Diazo reaction Yes 

(Test 40) Anthraquinone reaction No 

(Test 41) Liebermann-Storch reaction No 



XV LIGNITE TAR AND LIGNITE-TAR PITCH 323 

The following figures are reported by Julius Marcusson : 10 



(Test 9) Hardness 


STRAIGHT- 
DISTILLED 
LIGNITE-TAR 
PITCH 

. . . . . M oderatelv hard 


LIGNITE-TAR 
PITCH 
DERIVED FROM 
ACID-SLUDGE 

Hard and brittle 
i 9 oi F. 
20 per cent 
> 2 per cent 
4-4 
13-4 
6.0 per cent 
36 per cent 
8 per cent 
26 per cent 


(Test 150) Fusing-point (K. and S. method)88 F. 
(Test 24) Free carbon , * . , . - 1 1 t5*r cent 


(Test 28) Sulfur 


< 2 per cent 


(Test 374) Acid value 


o, c 


(Test 37^) Saponification value . . 


2.8 


(Test 37^) Saponifiable constituem 
(Test 38^) Asphaltenes 


ts .... 1.8 per cent 


24 per cent 


(Test 38^) Asphaltic resins 


ii per cent 


(Test 38*) Oily constituents*. . . . 


48 per cent 


* Salve-like; 


light brown color. 



Soft lignite-tar pitch is almost completely soluble in benzol and 
turpentine, and less soluble in petroleum benzine or naphtha. The 
solubility of hard pitches decreases in proportion to the extent they 
have been distilled. Lignite-tar pitch derived from acid sludge may 
be distinguished from straight-distilled pitches by the presence of 
sulf uric-acid oxonium derivatives insoluble in 88 petroleum naph- 
tha, as is the case with sludge asphalts derived from petroleum. Lig- 
nite-tar pitches are distinguished from coal-tar pitches by the ab- 
sence of anthracene, the presence of small quantities of paraffin wax, 
and the formation of water-insoluble sulfo-derivatives upon treat- 
ment with concentrated sulf uric acid (whereas coal-tar pitches form 
soluble derivatives). Furthermore, the free-carbon separated 
from lignite-tar pitches differs from that obtained from coal-tar 
pitches by the fact that the former is completely converted into 
soluble nitro-derivatives upon heating with fuming nitric acid. Lig- 
nite-tar pitches are distingished from wood-tar pitches by the asso- 
ciated sulfur and paraffin wax; also from asphalts, rosin pitch and 
fatty-acid pitch by the diazo reaction. 11 

A process of blowing lignite tar with air in, the presence of 
mineral substances has been patented. 12 It has also been proposed 
to blow a mixture of lignite-tar pitch and refined Trinidad asphalt. 18 
Lignite tars may be hardened by heating with sulfur, 14 or by heat- 
ing with spent iron oxide containing sulfur (obtained in the puri- 
fication of coal gas) in the presence of FeQ 3 , MnSO 4 , or the like. 18 
In Germany, where practically all of the lignite-tar pitch is pro- 
duced, it is used extensively for manufacturing cheap paints. 



CHAPTER XVI 
SHALE TAR AND SHALE-TAR PITCH 

Shale Mining. Scotland is the home of the "shale oil" indus- 
try. The present chapter is based on the operations practiced in 
Scotland, since in other countries the treatment of shales has not 
been developed to what may be regarded as an industry scale. In 
the United States, for example, the distillation of shales is more 
or less in a process of development, and at the present writing is 
still in an experimental stage. 

At the present time, Scotch refineries are located at Pumphers- 
ton, Broxburn, Oakbank, Addiewell and Uphall ; crude-oil works at 
Addiewell, Broxburn, Dalmeny, Deans, Hopetoun, Niddry Castle, 
Oakbank, Philipstoun, Pumpherston, Roman Camp, Seafield, Tar- 
brax and Uphall; and candle works at Addiewell and Broxburn. 

Shale is mined in the same manner as bituminous coal, by driving 
shafts, and then extending drifts radially. Considerable timbering 
is necessary, on account of the softness of the shale. When the 
seams are over 4 ft. in thickness, they are mined by the "pillar-and- 
stall" method, and when less than 4 ft. thick, by the "longwall" 
method. 

The mineral as mined is hauled to the surface by power, and 
then run through a breaker, where the masses are broken into lumps 
measuring 4 to 6 in. in diameter. The breakers consist of a number 
of toothed iron discs mounted on two shafts revolving in opposite 
directions. The shale, upon being crushed to the proper size, is next 
conveyed up an iacline to the top of the retort. 

Retorts Used for Distillation. The retorts used have been modi- 
fied from time to time to increase their efficiency, add to their dura- 
bility, hasten the speed of treatment, or to improve the quality of 
the output. In all instances the distillation takes place in the upper 
part of the retort where the shale is heated to 900 F. It is then 
subjected to a higher temperature (1300 to 1800 F.) in the lower 
portion, which is in reality a gas producer, steam and air being 

824 



XVI 



SHALE DISTILLATION 



325 



admitted to convert the carbonaceous residue into carbon dioxide 
and carbon monoxide. This generates sufficient heat to effect the 
distillation in the upper portion of the retort. The admission of air 
is carefully regulated to maintain the required temperature, with- 
out causing excessive combustion of the by-products. The steam 
serves to convert the nitrogen into ammonia, increases the value of 
the shale tar, dilutes the gas vapors, increases the velocity of the 
discharge, reduces the secondary decomposition of the vapors, in- 
creases the yield of paraffin products, and equalizes the temperature. 



' 1 ' 




FIG. 98. ^View of Pumpherston Works, Showing Mine-head, Retorts and Refinery. 

The charge gradually passes downward in the retort at a speed 
regulated by the removal of the spent shale at the bottom. 

At present, the tendency seems to gravitate towards the use of 
two types of retorts, viz.: the Pumpherston and the Henderson 
retorts, of which the former is considered to be the more efficient. 
Both types will now be described. 

Pumpherston Retort. A view of the Pumpherston works, 
showing the retorts and refinery is given in Fig. 98. A bank of the 
retorts is illustrated in Fig. 99, and the equipment for condensing 
the oils and ammoniacal liquors from the gases emanating from the 
retorts is shown in Fig. 100. Similarly, a cross-section of a Pum- 
pherston retort is given in Fig. 101. The shale is prevented from 



326 



SHALE TAR AND SHALE-TAR PITCH 



XVI 




Fia 99. Bank of Scottish Shale Retorts (Pumpherston Type). 




FIG. loo. Plant for Condensing Shale Tar and Ammonia Water Emanating from the 

Shale. 



XVI 



SHALE DISTILLATION 



fluxing and choking up the retort 
by keeping it moving continuously, 
which is accomplished by support- 
ing the column of shale on a disc 
e, from which a revolving scraper 
/ discharges the spent shale into 
the hopper below. The shale is 
introduced into an iron-charging 
hopper c, whence it passes into 
the upper cylindrical cast-iron por- 
tion of the retort a, measuring 
1 1 ft. high, 2 ft. in diameter at 
the top and 2 ft. 4 in. at the bot- 
tom. In this, the actual distilla- 
tion takes place at 900 F., with 
the formation of oil and gas. The 
shale slowly works its way into 
the lower portion b constructed 
of firebrick, of circular cross-sec- 
tion, measuring 20 ft in height 
and enlarged at the bottom to 3 
ft. in diameter, and finally into 
the lower hopper d extending un- 
derneath several retorts, converg- 
ing in such a manner that a single 
line of rails running below the 
center will permit the spent shale 
to discharge into small cars. 
Steam is introduced into the 
lower portion of the retort, a 
short distance above the disc e, 
and the gaseous products of dis- 
tillation are burned with air in the 
external flues at 1800 F. in the 
zone b where the ammonia is 
formed. The daily capacity of 
the retort is 4 to 4^4 tons, de- 
pending upon the richness of the 
shale. Four retorts constitute an 




FIG. 101. Pumpherston Type of Retort 
for Distilling Shale. 



828 



SHALE TAR AND SHALE-TAR PITCH 



XVI 



DD 




FIG. 102. Broxburn Type of Retort for Distilling Shale* 



XVI METHODS OF RECOVERING SHALE TAR 329 

"oven," and 16 ovens a "bench.* 1 The maximum output of shale 
oil amounts to 96 gal. per retort per day under the best operating 
conditions. 

Henderson or Broxburn Retort. This is illustrated in Fig. 102, 
and consists of iron hoppers a on top, into which the crushed shale 
is fed, next a rectangular cast-iron section b measuring 2 f t. 9 1 /2 in* 
by i f t 2 y% in. at the top, and 3 ft J4 * n - by I f t. 5 % in. at the 
bottom. This is 14 ft. long, and is joined by a fire-clay joint to a 
fire-brick section c, 20 ft. long, of rectangular cross-section, measur- 
ing 4 ft. 8 in. by i ft. 10 in. at the bottom. A pair of toothed iron 
rollers d continuously discharge the spent shale from the bottom 
into hoppers e, which are periodically emptied into cars under- 
neath. The vapors pass out at the top through the ducts /, into 
headers g. A slight vacuum is maintained in the retort and steam 
is admitted into the bottom of the fire-brick portion. The tempera- 
ture reaches 900 F. in the upper cast-iron section, where practically 
all the oil is distilled, and the shale is subjected to an increasing 
temperature, reaching a maximum of 1500 F, at the lower portion 
of the fire-brick section, whereupon it is cooled by the incoming 
steam before it is discharged. The retorts are heated by the fixed 
gases evolved from the shale, supplanted by a proportion of pro- 
ducer gas. The arrangement of the retorts in benches and ovens, 
also the output, is the same for the Pumpherston type. 1 

Methods of Recovering Shale Tar. The vapors which leave the 
retorts are passed through air-cooled pipes (Fig. 100) which sep- 
arate most of the tar and ammoniacal liquor. Sometimes an econ- 
omizer is used, consisting of a tower filler with pipes, around which 
cold water is circulated, and thus preheated for use in the steam 
plant The vapors are next passed through a scrubber (filled with 
coke or a checker-work of wood), and finally through a naphtha 
scrubber where they are washed with the " intermediate oil" ob- 
tained in distilling the shale tar (having a high boiling-point and 
a specific gravity of 0.84 to 0.86) which extracts any light naphtha 
not previously condensed (about 2 gal. per ton of shale). The 
naphtha is separated from the scrubbing oil by heating the mixture 
moderately in a still, and condensing the distillate (having a specific 
gravity of 0.73)* 



380 SHALE TAR AND SHALE-TAR PITCH XVI 

The crude tar and ammoniacal liquor are allowed to flow from 
the condensers to separating tanks, where upon standing, the tar 
rises to the surface and is drawn off and piped to the refinery* The 
crude tar is generally termed "shale oil/' but this name is just as 
inappropriate as the expression "oil shale," often used to designate 
the shale* 

Products Obtained. Upon destructively distilling the Kim- 
meridge Shales of England and the Lothian Shales of Scotland, 
the following products are obtained : 

(1) Non-condensable gases, averaging 9800 cu. ft per ton 
(2000 Ib.). 

( 2 ) Ammoniacal liquor yielding an average of 40 Ib. ammonium 
sulfate per ton. 

(3) Shale tar, Averaging 22 gal. per ton. 

(4) Scrubber naphtha, averaging 0.4 gal. per ton. 

(5) Spent shale, averaging between 75 and 85 per cent of the 
raw shale (i.e., 1500 to 1600 Ib. per ton), and containing approxi- 
mately 2j^ per cent unconsumed carbon. 

The non-condensable gases are burned under the retorts, and 
the spent shale discarded, as it has no further value. The valuable 
products are the light naphtha, the shale tar and ammonium 
sulfate. 

The ammoniacal liquor separated from the tar is treated with 
steam under a pressure of 20 to 30 Ib. in a tower filled with baffle- 
plates. The liquor is run in at the top and the steam introduced at 
the bottom. The ammonia is expelled in the gaseous state and re- 
covered by passing it into sulfuric acid contained in a vessel known 
as a "cracker box." The acid used for this purpose is usually the 
waste product from the refining process. Crystals of ammonium 
sulfate separate when the liquor becomes sufficiently concentrated, 
and after being dried are marketed as such. In this manner the 
ammonia is separated from the other nitrogenous bases, including 
pyridine, contained in the aqueous liquor. 

The following table gives the minimum and the maximum 
yields of dehydrated shale tar in gallons, and ammonium sulfate in 
pounds per ton of shale, obtained from the most important shate 
deposits in different parts of the world, 2 



XVI 



PROPERTIES OF SHALE TAR 



331 



Yield of Shale Tar 
(Gallons) 



Yield of Ammonium 
Sulfate (Pounds) 



Lothian shale (Scotland) 

Kimmeridge shale (England) 

Coorongitic shale (New South Wales) . 

Orepuki shale (New Zealand) 

Albert shale (New Brunswick) 

Arcadian shale (Nova Scotia) 

Shales (Eastern United States) 

Utah shales 

Colorado and Wyoming shales 

Kukkersite (Esthonia) 



ro-55 

10-40 

14-150 

20-40 

30-51 



4-45 

6-10 

10-68 

70-80 



6-70 
10-50 
20-30 

67-1 1 1 
9-40 
o-io 

40-50 

22-34 

5-15 



Properties of Shale Tar. Shale tar usually appears black in mass 
with a greenish fluorescence. It is similar in composition to lignite 
tar, although differing from the latter in containing a larger per- 
centage of nitrogen (i.i to 1.5 per cent). -Members of the paraf- 
fin and olefine series constitute 80 to 90 per cent by weight of the 
tar, and small quantities of cresols and phenols are present 

Dehydrated shale tar tests as follows: 

(Test i) Color in mass , Brownish black with a 

greenish fluorescence 

(Test 7) Specific gravity at 77 F o. 85-0.95 

(Test 9) Hardness or consistency Salve-like to buttery 

(Test 150) Fusing-point (K. and S. method) 60-90 F. 

(Test 15^) Fusing-point (R. and B. method) 75~n 5 F. 

(Test 1 6) Volatile matter at 500 F., 5 hrs 80-90 per cent 

(Test ija) Flash-point (Pensky-Martens tester) 20-60 F. 

(Test 19) Fixed carbon 5-10 per cent 

(Test 21) Soluble in carbon disulfide 98-100 per cent 

Non-mineral matter insoluble 0-2 per cent 

Mineral matter o-i per cent 

(Test 22) Carbenes 0-2 per cent 

(Test 23) Soluble in 88 petroleum naphtha 95-100 per cent 

(Test 24) Free carbon 0-2 per cent 

(Test 28) Sulfur i . 5-2. 5 per cent 

(Test 29) Nitrogen o. 25-1 .o per cent 

(Test 30) Oxygen 1-5 per cent 

(Test 33) Solid paraffins 5-15 per cent 

(Test 34^) Sulfonation residue I5~35 per cent 

(Test 37?) Saponifiable constituents 0-2 per cent 

(Test 39) Diazo reaction Yes 

(Test 40) Anthraquinone reaction No 

(Test 41) Liebermann-Storch reaction No 

The percentage of phenols contained in the shale tar is very 
much smaller proportionately than that present in peat or lignite 



332 SHALE TAR AND SHALE-TAR PITCH XVI 

tars. Shale tar is distinguished from the latter by containing larger 
percentages of nitrogen and sulfur, and smaller percentages of 
oxygen, paraffin and phenols respectively. 

Refining of Shale Tar. Shale tar may be distilled either inter- 
mittently or continuously. In either case the process consists in 
heating the tar in a still to expel the moisture, whereupon either 
plain or superheated stam is introduced through a perforated pipe 
under a pressure of between 10 and 40 Ib. The tar is distilled to 
coke and the following products separated: 

1 i ) Non-condensable gases ranging from i to 2 cu. ft. for each 
gallon of shale tar. 

(2) Crude naphtha having a specific gravity of 0.74 to 0.76. 

(3) So-called "crude distillate," or "once-run oil/' or "green 
oil" representing the fraction between the crude naphtha and coke. 

(4) A residue of coke approximating 3 per cent by weight of 
the shale tar. 

The steam is shut off towards the end of the distillation, after the 
"once-run oil" has passed over. 

The stills used in Scotland are of the vertical type from 2000 to 
2500 gal. capacity, constructed of a hemispherical cast-iron bottom, 
and a soft malleable-iron cylindrical body to which is attached a 
dome-shaped top bearing the exit pipe. Each still is connected with 
its own condenser. 

In the continuous distillation process, termed the "Henderson 
Process," a battery of three horizontal stills and one or more ver- 
tical pot-stills are used. The tar is first led into the middle hori- 
zontal still where the naphtha is distilled off, and the residue caused 
to flow continuously into the two side stills. These are heated 
higher than the center still, causing the one-run oil to distil over 
continuously. The residues from these second stills are led into the 
pot-still, where they are evaporated to dryness, the distillate being 
condensed and united with the once-run oil. Several pot-stills are 
used, since the red-hot coke must be allowed to cool before it can be 
removed, which prevents this part of the process being continuous. 

The once-run oil is refined by agitating it with sqlfuric acid at 
100 F. by compressed air. The acid sludge is run off, the oil 
washed with water, and then treated in another agitator with caus- 
tic soda in a similar manner* 



XVI REFINING OF SHALE TAR 333 

The refined once-run oil is fractioned either by an intermittent 
or continuous steam distillation process, the following products be- 
ing recovered : 

1 i ) Heavy naphtha varying in gravity between 0.75 and 0.77. 

(2) ^ Illuminating oils varying in gravity between 0.78 and 0.85, 
and having a flash-point of 125 F, 

(3) Gas-oil and fuel-oils varying in gravity between 0.85 and 
0.87, and having a flash-point higher than 150 F. These are used 
as fuel, or for manufacturing water-gas, or enriching illuminating 
gas. 

(4) Lubricating oils having a gravity from 0.87 to 0.91. 

(5) Paraffin wax which is purified by re-crystallization or 
"sweating, 1 * having a fusing-point between 110 and 130 F. 

(6) Still grease, which represents the distillate passing over at 
the close of the distillation. 

(7) Still coke, which remains in the still at the close of the 
operation. 

The various distillates, with the exception of the still grease are 
refined further with sulfuric acid and caustic soda, similar to the 
method used for treating the once-run oil. The crude paraffin wax 
is refined by the sweating process. 

The various steps of the distillation and refining processes are 
illustrated in Table XXII. 

The following yields are obtained from dehydrated Scotch shale 
tar: 

Heavy and light naphthas 3-6 per cent 

Illuminating oil 20-30 per cent 

Gas-oil or fuel-oil 10-25 per cent 

Lubricating oil > 1 5-20 per cent 

Soft paraffin scale 3-5 per cent 

Hard paraffin wax 7-9 per cent 

Non-condensable gases 3-5 per cent 

Acid and soda sludges and losses t . . . 20-25 per cent 

Still coke 2-3 per cent 

The acid and soda tars obtained from the various refining 
processes are mixed together in such proportions that the free acid 
and alkali will exactly neutralize each other. The resulting sludge 
is ordinarily used as fuel for the stills, but experiments have been 
made to convert it into pitch suitable for use as a wood preserva- 
tive, pipe-dip, or the base of bituminous paints. Comparatively 



334 



SHALE TAR AND SHALE-TAR PITCH 



XVI 



TABLE XXII 

FLOW SHEET ILLUSTRATING THE METHOD OF MANUFACTURE OF OILS, PARAFFIN WAX AND 
SULFATE OF AMMONIA FROM SHALE. THE NAMES OF FINISHED PRODUCTS ARE UNDER- 
LINED 

SHALE 



Liq 



Scrubber 
Naphtha 

Treated & Distd. 



Shale 
Tar 



Shale 



Swfate 

otArrimoriia 


Motor 

3E# 




Wed 


Cfude 
Naphtha 

TreatedWisrd 


Cn 

Treated 

t 
IS 


de Shale CoJ* 
Hate Rasm 

tOtstd. 


Ctoaners* 


So/Wf 


Crbdc 
Burning 


HeavyOtl \ 
contain/no CoAe 
Solid paraffin 



la/no fbber Signal tJtoise Crude 
~ "O/L M 



Cooled, filtered 3 pressed 



B/ue-Ofl 

Treattd&Distd 



J$$d 
faMffin 

Cooled, Filtered 



Baiching Lao. Oil 

OH&Sonet QSolid 

Paraffin Paraffin' 

Cooted,rtHer*d Cookd.fi fared 
$ 



UMll Solid 
VnM Paraffin 

'" \ -' 




Residuum 
Oil 



XVI REFINING OF SHALE TAR 335 

little has been accomplished in this direction, probably due to the 
fact that other products are available for these purposes, costing 
but little more and possessing superior weather-resisting properties. 
Shale-tar pitch is similar in its physical properties and composition 
to lignite-tar pitch, 

A residue derived from Esthonian shale oil (obtained by the 
destructive distillation of Esthonian "kukkersite" ) has been termed 
"esto-bitumen" or "esto-asphalt," which unlike paraffin petroleum 
asphalts is completely miscible with coal tar in all proportions. 8 



CHAPTER XVII 
COAL TAR AND COAL-TAR PITCH 

Under the headings "Coal tar" and "Coal-tar pitch/' will be 
included t^e tars and corresponding pitches recovered as by-products 
from bituminous coal * in : 

i) Gas works; 

2} Coke ovens; 

3) Blast furnaces; 

4; Gas producers; 

5) Low-temperature processes. 

* 

Water-gas tar and water-gas-tar pitch have been included by 
some writers within the scope of the terms coal tar and coal-tar pitch 
respectively, but in this treatise they will be considered separately, 
since they differ in their composition and properties, due to the use 
of petroleum products in their manufacture. 

Bituminous Coals Used. Bituminous coals only are suitable for 
the production of coal tar. Cannel, bog-head and anthracite coals 
will not answer, since the former distils at too low a temperature, 
and the latter contains insufficient volatile matter. Upon subject- 
ing cannel coal to low-temperature distillation, there is obtained 20 
to 40 per cent of cannel-coal tar having a specific gravity at 50 C. 
of 0.9, containing much paraffin and 5 to 10 per cent phenols. At 
20 C. cannel-coal tar has the consistency of butter. Upon subject- 
ing bog-head coal to low-temperature distillation, 30 to 60 per cent 
of tar is produced, having a thick, salve-like consistency and con- 
taining solid paraffins, phenols and naphthenes, but no naphthalene 
or anthracene. It is known as bog-head-coal tar. Torbanite on 
distillation yields 20 to 35 per cent of torbanite tar having a spe- 
cific gravity at 35 - C. of 0.90 to 0.95, and containing phenols and 
a small amount of solid paraffin. 

Bituminous coals are known as "gas coals'* when used for manu- 
facturing illuminating gas, and "coking coals" when used for coking. 
Western Pennsylvania, West Virginia, Virginia, eastern Kentucky 

836 



XVII TEMPERATURE OF TREATMENT 337 

and Tennessee produce most of the bituminous coals used for these 
purposes, and they comply with the following characteristics: 

Air-dry loss of coarse material i -5 per cent 

Moisture at 105 C. (powdered material) i . 5-7.0 per cent 

Volatile matter on ignition 20 -40 per cent 

Fixed carbon 50 -75 per cent 

Ash Less than 1 5 per cent 

Sulfur . . , . Less than a per cent 

Hydrogen 4. 5-5. 5 per cent 

Carbon 65-85 per cent 

Nitrogen i~2 per cent 

' Oxygen 5-1 5 per cent 

Very little is known regarding the chemical composition of the 
bituminous coal itself, due to the difficulty in converting the coal 
into recognizable derivatives, and because of its slight solubility in 
the usual solvents for bituminous materials. On subjecting coal to 
high temperatures, the bodies present decompose into simpler sub- 
stances which fail to give any clue as to their original structure and 
composition. Recent researches lead to the conclusion that coal is 
essentially a conglomerate of cellulose decomposition products, ad- 
mixed with altered resins and gums originally present in the plants 
from which the coal was derived. 

Temperature of Treatment. D. T. Jones examined the tars 
derived from the destructive distillation of bituminous coal in vacuo 
at very low temperatures (below 450 C.). These were then sub- 
jected at atmospheric pressure to successively increased tempera- 
tures up to 800 C. Unsaturated hydrocarbons, naphthenes, paraf- 
fins, phenols, aromatic hydrocarbons and pyridines were found to 
be present in the low-temperature tar, whereas benzol and its homo- 
logues, naphthalene, anthracene, phenanthrene and the solid aro* 
matic bodies were absent. As the temperature was increased, the 
naphthenes, paraffins, and unsaturated hydrocarbons were trans- 
formed into olefines. As the temperature was further increased, 
the olefines were in turn transformed into benzene and its homo- 
logues. The percentage of olefines appears to reach a maximum 
at 550 C., and a minimum at 750 C., at fahich latter temperature 
hydrogen and naphthalene are rapidly evolved^ as well as methane. 
The conclusion reached is that ordinary coal tar obtained from 
bituminous coal at high temperatures results chiefly from tlie de- 
composition of the tar previously formed at lower temperatures. 



338 



COAL TAR AND COAL-TAR PITCH 



XVII 



The following figures will give a rough idea of the effect of the 
temperature on the yield and characteristics of the tar produced 
from an average grade of British coal : 





Tempera- 
ture 


Tar 

(Gals: 
per Ton) 


Sp. Gr. 
Tar at 
77 F, 


Free 
Carbon 
in Tar, 
Per Cent 


Distillate to 315 C. 


Pitch 
(Per 
Cent by 
Weight) 


Naph- 
thalene, 
Per Cent 


Paraffin, 
Per Cent 


Coke-ovens (narrow) 


1300 C. 
1100-1350 C. 
900-1200 C. 
1000-1100 C. 
1000-1200 C. 
400-700 C. 


8.0 
9-5 

11. 
12. 
15-5 
18.3 


1.210 
I. 200 
I.I90 

1. 155 
1. 100 
1. 035 


20 
IS 

14 

12 

5.5 
I 


30-35 

20-30 
15-20 
5-12 

<5 

o 


o 
o 
Trace 

5 
13 
25 


72 
' 66 
65 
58 
48 
40 




Horizontal retort 


Inclined retort 


Vertical retort ,.,..,..* 


Low-temperature carbonization 



By low-temperature carbonization of coal is meant its destruc- 
tive distillation under ^700 to 800 C. Below this temperature 
range there are evolved mostly condensable tars and oils, with a 
minimum of fixed gases; whereas above this range, mostly fixed 
gases are produced, due to secondary reactions. This is illustrated 
.by the following figures applicable to i ton of average coal con- 
taining 25 to 30 per cent volatile matter: 





Low-temperature 
(Coalite Process) 


High-temperature Processes 


Gas Works 


Coke Ovens 


Temperature of vapors. ..... 
Yield gas 


550 C 
6,000-6,500 cu. ft. 
rich gas (700-750 
B.t.u.) 
lo gal. tar (*) 
15 Ib. 
14 cwt. 


1,000 C. 
12,000 cu.ft. medium 
gas (550 B.t.u.) 

10 gal. tar 
25 Ib. 
13$ cwt. 


1,200 C. 

11,500 cu. ft. lean 
gas (450 B.t.u.) 

8 gal. tar 
28 Ib. 
14-14$ cwt. 


Yield liquid products. ....... 


Ammonium sulfate 


Yield coke 




* Absence of naphthalene and anthracene distinguish this tar from high-temperature tars. 



The percentage yield of tar, figured on the weight of coal 
treated) will approximate the following: 

Gas works (horizontal retort) 5-7 per cent 

Gas works (vertical retort) 4-6 per cent 

Cokevovens 2-6 per cent 

Low-temperature carbonization 8-13 per cent 

ation *.,..* 5" IQ P cr cent 



XVII 



PRODUCTION OF GAS- WORKS COAL TAR 



339 



The commercial processes for obtaining coal tar will now be 
considered. 

Production of Gas-works Coal Tar. In manufacturing illumi- 
nating gas, bituminous coal is heated in comparatively small fire- 




I 

t/5 

rt 

o 

2 
c 

s 



clay retorts, of D-shaped, oval or round cross-section about 16 to 
24 in. in diameter. The D-shaped retort is ordinarily used in 



840 COAL TAR AND COAL-TAR PITCH XVII 

modern gas-works because it is least liable to distortion under the 
>action of heat, and moreover presents the greatest area at its base, 
enabling the contents to be heated more rapidly. In some cases the 
retorts are ''single-ended," measuring 8 to 9 ft. in length, but mod- 
ern practice favors the use of "double-ended" retorts composed of 
three Sections joined together, measuring 15 to 25 ft over all. In 
the single-ended retort a metal mouthpiece is bolted to one end, to 
which in turn the gas outlet pipe is fastened. With the double- 
ended retort, metal mouth-pieces are bolted fast to both ends, From 
6 to 9 retorts are set together in a common brick setting, consti- 
tuting a "bench" which is heated by a single furnace. 

Retorts Used. The retorts are supported in either a horizon- 
tal, inclinfed of vertical position. The inclined or vertical retorts 
seem to meet with greater favor since they avoid overheating, pre- 
vent the formation of "free carbon" in the tar, and at the same 
time permit the coke to be handled by gravity. The vapors leave 
horizontal retorts at 1600 to 1800 F. and the vertical and inclined 
retorts at 1300 to 1400 F. 

The retorts are heated with water-gas obtained by passing air 
and steam through incandescent coke beneath the "bench." The 
coke used for this purpose is derived as a residue from a previous 
charge of bituminous coal, amounting to 15 to 25 per cent of the 
total coke produced. The water-gas is burnt in flues surrounding the 
retorts and the process of combustion controlled by the introduction 
of air. This method of firing results in a higher and more uniform 
terfiperature with the minimum consumption of fuel. The tempera- 
ture in the combustion chamber ranges from 2800 to 3200 F., and 
in the flues surrounding the retorts from 1900 to 2200 F. An im- 
proved installation of horizontal retorts is shown in Fig. 103, in- 
clined retorts in Fig. 104, and vertical retorts in Fig. 105. Con- 
tinuously operating. vertical retorts are now being adopted exten- 
sively, in which the coal is fed through the retort in a constant 
stream, the coke being withdrawn continuously at the bottom. 

Formerly, the retorts were charged and discharged by hand, 
using a shovel and rake respectively. Mechanical devices are now 
used for the purpose, the double-ended horizontal retorts being 
charged ;* both^tids with a scoop, fed from an overhead hopper, 
operated ei thereby, compressed air or electricity. About 600 Ib, of 



XVII 



PRODUCTION OF GAS-WORKS COAL TAR 



341 



coal are introduced into the double-ended retort, and subjected to 
heat from 3 to 6 hours. The inclined and vertical retorts are 
charged through the top and discharged by gravity from the lower 
end. Horizontal retorts are discharged by a pneumatic or an elec- 
trically driven ram, which 
forces out the coke at the far- 
ther end. Inclined retorts are 
set at an angle between 25 and 
35, which is sufficient to en- 
able the coal to feed into the 
low r er end, where it is held in 
place by a metal cover. In 
the inclined and vertical types 
the volatile constituents are 
withdrawn from the upper 
end. 

The vapors are subjected 
to the highest temperatures in 
the horizontal retort, due to 
the longer contact with the 
heated internal surfaces, 
which results in a larger per- 
centage of free carbon, and a 
tar of higher specific gravity. 

Methods of Recovering 
Gas-works Coal Tar. The 
volatile products pass from 
the retort into the hydraulic 
main, which forms a water- 
seal, permitting any retort to 
be charged, and at the same 
time preventing the gas gen- 
erated in the other retorts es- 
caping through the open one. 
The hydraulic main reduces the temperature of the vapors to 130- 
160 F. 

After leaving the hydraulic main the vapors are subjected to 
the following treatment in modern gas-works : 




From "Coal and Coke," by F. H. Wagner 
FIG. 104. Inclined Gas- Works Retort. 



342 



COAL TAR AND COAL- TAR PITCH 



XVII 



(1) The gases are passed through a "primary condenser" 
which may either be air-cooled or water-cooled, or both. 

(2) The gases are then passed through a tar-extractor. 

(3) Then they are passed through an exhauster to relieve the 
pressure on the retorts and force the gases through the ensuing 
train of apparatus. 

(4) The gases are next passed through two "scrubbers," pref- 
erably of the rotary type. In the first scrubber the gases are washed 
with a heavy tar oil, such as anthracene oil, to remove the naphtha- 




FlG, 105. Vertical Gas- Works Retort. 

lene, and in the second with an alkaline solution of ferrous sulfate 
to remove the cyanogen. 

(5 ) The gases are then cooled to about 60 F. by passing them 
through a "secondary condenser," similar to the first one. 

(6) The ammonia is next removed by passing the gases through 
a third scrubber through which a stream of water is allowed to 
trickle. Formerly a tower scrubber filled with a checker-work of 
wooden boards was used for this purpose, but this is being replaced 
by a rotary scrubber similar to tnat used for extracting the naph- 
thalene and cyanogen. 



XVII PRODUCTION OF GASWORKS COAL TAR 343 

(7) The last step consists in passing the gases through a series 
of "purifiers," consisting of low cylindrical chambers llled with 
trays or sieves. Some of the purifiers are filled with slaked lime to 
remove carbon dioxide and a portion of the sulfur compounds, and 
others with iron oxide to remove the remainder of the sulfur com- 
pounds (mostly hydrogen sulfide). 

Products Obtained. The following percentages of tar are col- 
lected from the hydraulic main, condenser, washer and scrubber, 
also the tar extractor respectively: 

Hydraulic main 61 per cent 

Condensers 12 per cent 

Washer and scrubbers i per cent 

Tar extractor 12 per cent 

Total 100 per cent 

The operations which take place in the final handling of illuminat- 
ing gas before it enters the mains, cease to be of interest in relation 
to the production of tar, and will accordingly be omitted. 

In the United States, temperatures to which the retorts are 
heated vary from 900 to 1500 C. In England the average tem- 
perature is 1 1 00 C. In Germany horizontal retorts are heated 
between 1000 and 1 100 C., and inclined retorts between 1 100 and 
1200 C. The quantity and yield of the tar depend largely upon 
the temperature. In the low-temperature production of illuminating 
gas, an average of 16 gal. of tar is produced per ton of coal, and in 
high temperature processes an average of 8. The maximum varia- 
tion ranges between 4 and 20 gal. of tar per ton. High-tempera- 
ture processes are preferable, as they increase the yield of gas, but 
have the disadvantage of reducing its illuminating power. 

The following represent the yields from an average grade of 
bituminous coal in manufacturing illuminating gas: 

Gas 17 per cent (10,000 cu. ft.) 

Aqueous liquor 8 per cent 

Tar 5 F r cent 

Coke 70 per cent 

Total loo per cent 

Of course, these figures are subject to variation, and depend 
upon the quality of bituminous coal used, the temperature at which 
it is distilled, etc. Thus the yield of gas per ton of rich coal will 
vary from 5000 to 15,000 cu. t M and the residual coke from 55 to 
75 per cent. 



344 COAL TAR AND COAL-TAR PITCH XVII 

The tar collected from the hydraulic main, condenser, washers 
and scrubbers is run into wells constructed of metal or masonry, 
sometimes heated with steam-coils and allowed to settle as long as 
possible, to permit the aqueous liquor, which is lighter than the tar, 
to rise to the surface, where it is drawn off and treated separately 
to recover the ammonium compounds. The well-settled gas-works 
tar carries between 4 and 10 per cent of water. In exceptional 
cases the water may run a$ high as 40 per cent, although this is not 
regarded with favor. 

Production of Coke-Oven Coal Tar. 2 As stated previously, 
about 78 per cent of the coal tar produced annually in the United 
States is obtained from coke-ovens equipped to recover by-products. 
This only represents between 60 and 70 per cent of the total quan- 
tity of bituminous coal converted into coke. The remaining 30 to 
40 per cent is coked in brick "beehive" ovens, constructed in the 
form of a beehive, and not adapted to recover the gas, ammonia or 
tar, which are allowed to burn away through an opening iri the top 
of the oven, thus constituting a reckless waste of our national re- 
sources, running into many millions of dollars annually. For years 
this wasteful practice remained unchecked, but happily the present 
tendency is to replace the beehive ovens with types adapted to 
recover by-products, and it is probably only a matter of a few years 
more before all the coke-ovens will be equipped to recover the gas, 
ammonia and tar. This same wasteful tendency is reflected in a 
patent granted in the United States and describing the production 
qf coal-tar pitch by the simple expedient of igniting coal tar and per- 
mitting the more volatile constituents to burn off (sic!). 8 

In European countries, on the other hand, where the tendency 
has always been towards a greater economy, coke-ovens have long 
been perfected to recover these by-products. In this connection it 
must be borne in mind, whereas it is absolutely necessary to remove 
the tar in manufacturing coal gas for illuminating purposes, this 
does not prove to be the case where the coal is converted into coke 
for metallurgical industries. This, and the comparative cheapness 
of bituminous coal in the United States, also the low price com- 
manded by the by-products until recently, will account for the laxity 
4% conserving them. 

The temperature of coking varies between 1000 and 1100 C, 



XVII PRODUCTION OF COKE-OVEN COAL TAR 345 

and rarely above the latter inside the retort. The external tempera- 
ture of the retort may run as high as 1700 C. The adaptability of 
coal for coking purposes is indicated with a fair degree of certainty 
by the ratio of hydrogen to oxygen, together with the. percentage 
of fixed carbon calculated on the moisture-free basis. Practically 
all coals with an H : O ratio of 59 per cent or over, and less than 79 
per cent of fixed carbon, possess that quality of fusion and swelling 
necessary to good coking. Bituminous coals with a ratio down to 
55 will produce a more or less satisfactory coke, whereas coals with 
a ratio as low as 50 are unsuitable for coking purposes. 

Retorts Used. The present systems of by-product oven con- 
struction resolve themselves into two types depending upon whether 
the flue construction is horizontal or vertical. In either type the 
coking takes place in a narrow, retort-shaped chamber about 33 ft 
long, from 17 to 22 in. wide, and about 6 l / 2 ft. high. The width 
of the chamber averages 19 ft, which has proven suitable for com- 
pleting the coking within twenty-four hours. The retort holds be- 
tween 12 and 14 tons of coal. 

The ends of the retort are closed by means of iron doors lined 
with fire brick, which after being closed as tightly as possible are 
luted with clay to prevent the entrance of air. The coal is charged 
into the top of the oven, then pushed into place and leveled by me- 
chanical devices. At the end of the coking, the doors are opened 
and the coke removed by a ram, the red-hot coke being immediately 
quenched with water. 

The number of ovens in a battery varies between 40 and 100, 
depending upon the type of construction. The oven walls are con- 
structed of fire brick containing about 95 per cent of silica, which 
on account of its very high fusing-point enables the ovens to be 
worked at high temperatures, and at the same time proves to be an 
excellent conductor of heat. 

For a detailed description of the various types of coke-ovens 
in use, the reader is referred elsewhere. 

The coking in the by-product oven is in reality a destructive 
distillation process, the heat required being supplied by burning a 
portion of the gases evolved. A large excess of gas is produced 
amounting to between 40 and 60 per cent of the total 

Products Obtained. The following yields per ton are recovered : 



346 COAL TAR AND COAL-TAR PITCH XVII 

Gas. ....... t 15.0-16.0 per cent (8,500-10,500 cu. ft.) 

Ammonium sulfate 0.8- 1.3 per cent 

Tar 3.0- 6.4 per cent 

Coke 70.0-75.0 per ent 

Approximately 20 per cent of the nitrogen present in the coal is 
converted into ammonium compounds, part of which is found in 
the tar as pyridine, quinoline, etc. About half of the nitrogen re- 
mains in the coke, and may be regarded as lost. 

The vapors emanating from the coke-ovens are passed through 
various forms of condensers and scrubbers to separate the am- 
moniacal liquor and tar, which are sirhilar to those used in gas 
works. The yield of tar recovered from coke-ovens varies from 4 
to 15 gal. per ton, depending upon the kind of coal used, as well as 
the type of coke-oven. Over 90 per cent of the tar (anhydrous) 
condenses in the collector main and primary coolers, 2 per cent in 
the exhausters, and 7 per cent in the tax-extractor. 

The following constituents have been identified in coke-oven 
coal tar produced in the United States : 4 

Light oil: Per Cent 

Crude benzene and toluol 0.3 

Coumarone, mdene, etc ' 0.6 

Xylenes, cumenes and isomers . i . i 

Middle and heavy oils: 

Naphthalene . 10.9 

Unidentified oils in range of naphthalene and methylnaphthalenes i . 7 

a-Monomethylnaphthalene I . o 

j8-Monomethylnaphthalene 1.5 

Dimethylnaphthalenes ^ 3.4 

Acenaphthene 1.4 

Unidentified oils in range of acenaphthene i .o 

Fiuorene 1.6 

Unidentified oils in range of fluorene 1,2, 

Anthracene oil: 

Phenanthrene 4.0 

Anthracene i . i 

Carbazol and kindred nonbasic nitrogen-containing bodies 2.3 

Unidentified oils in range of anthracene 5.4 

Phenol 0.7 

Phenol homologues (largely cresols and xylenols) 1.5 

Tar bases (mostly pyridine, picolines, lutidines, quinolines and acri- 

dine) 2,3 

Yellow solids of pitch oils 0.6 

Pitch greases * 6.4 

Resinous bodies 5,3 

Pitch (460 F. fusing-point) f 44. 7 

Total 100. o 



XVII PRODUCTION OF BLAST-FURNACE COAL TAR 347 

Production of Blast-furnace Coal Tar. 6 Most blast-furnaces in 
the United States employ coke as fuel and a few use anthracite 
coal. Since all the volatile constituents have been removed from 
coke, and as anthracite coal contains only a very small percentage, 
no tar is obtained when either of these is used for smelting ores in 
blast-furnaces. In such cases the gases evolved are subjected to a 
purification process merely to remove the entrained dust, before 
using them for heating purposes. 

Owing to the scarcity of anthracite and the high cost of bitumi- 
nous coal in Europe and Great Britain, there is a tendency to reduce 
the operating expenses by using the latter in its raw state, without 
first converting it into coke. A non-coking bituminous coal must be 
selected for this purpose. In such cases the gases emanating from 
the blast-furnace carry a certain amount of tar, derived from the 
volatile constituents of the coal, which must be removed before they 
can be used for heating or power purposes. The gases also carry a 
comparatively large amount of dust derived from the ores in the 
blast furnace, of which a good portion is removed by passing the 
hot gases through a device known as a u dry dust-catcher/ 1 

Methods of Recovery. After being dry-cleaned, the gases are 
subjected to a wet-cleaning and cooling process by passing them 
through coolers, scrubbers, or washers. The centrifugal washer is 
usually preferred as it operates rapidly and economically. A part 
o/ the tar condenses in the coolers, and the balance in the scrub- 
bers and washers. , It carries a large quantity of the wash water, 
which may be separated. 

Approximately 7 gal. of blast-furnace tar and 29 Ib. of ammo- 
nium sulfate are obtained from each ton of bituminous coal fed into 
the blast-furnace. It appears that the iron ore and other minerals 
introduced with the coal, influence the yield of tar. Thus the same 
bituminous coal gave the following weights of tar per ton under 
varying conditions: 

Distilled alone in gas works 114 Ib. of tar 

Distilled with English iron ore 66 Ib. of tar 

Distilled with sand 170 Ib. of tar 

The tar derived from blast-furnaces always carries a substantial 
proportion of mineral matter, which the dust-catchers fail to re- 



348 COAL fAR AND COAL-TAR flTCH XVII 

move, and which serves to distinguish it from the other varieties of 
coal tar. 

Blast-furnace coal tar on distillation yields a greenish-brown 
creosote of low viscosity, with 30-35 per cent phenolic content, also 
a pitch of rather paraffinoid character. A typical tar tests as fol- 
lows: specific gravity at 60/60 F., 1.151; water by volume, 0*2 
per cent; phenols in tar, 14.6 per cent; bases in tar, 2.5 per cent; 
pitch at 315 C., 56.6 per cent of medium hardness and paraffinoid 
character; and distillate to 315 C., 43,4 per cent, having a specific 
gravity at 60/60 F. of 0.980; naphthalene little to none; and min- 
eral matter 13.0 per cent 

Production of Producer-gas Coal Tar. 6 Unless the producer- 
gas plants are of a large capacity (above 4000 horse-power) it does 
riot pay to recover the by-products. The smaller producers are 
designed to decompose the tar vapors and convert them into per- 
manent gases, to avoid the expense of operating a tar-separating 
plant on one hand, or the trouble occasioned by the tar clogging the 
pipes and valves on the other. In plants where the producer gas is 
used without separating the tar, it is necessary to shut down about 
one day a week to clean out the gas lines. In spite of this, it is 
only in tin-plate plants, where particularly clean gas is required, that 
the practice is followed of scrubbing the producer gas to remove the 
tar. Of the larger installations, the Mond by-product gas producer 
is virtually the only one which is designed to recover the tar and 
ammonium sulfate. Upon operating this type of producer at low 
temperatures, as high as 150 Ib. of water-free tar is recovered per 
ton of coal, consisting of paraffins, olefines and naphthalenes, with 
smaller quantities of aromatic hydrocarbons and phenols. 

Production of Low-temperature Tars. 7 Low-temperature car- 
bonization processes are carried on at 400 to 700 C., or an average 
of 600 C, in layers about 4 in. thick. The industry dates from 
1906, when Thomas Parker (who originated the term "coalite") 
patented a plant for carbonizing coal at low temperatures. The 
yields are roughly as follows per ton of coal carbonized: 

(1) Gas, 3000 to 3500 cu. ft. from externally heated retorts, 
or 20,000 to 25,000 cu, ft from internally heated retorts. 

(2) Tar, 20 to 25 gal 



XVII 



PRODUCTION OF LOW -TEMPERATURE COAL TARS 



349 



(3) Ammonium sulfate, 10 to 25 Ib. 

(4) Coke, 15 cwt. 

Low-temperature tars are of a liquid consistency and contain a 
comparatively small quantity of free carbon. They consist of 50 
to 80 per cent of hydrocarbons and 20 to 50 per cent of tar acids. 
The hydrocarbons are mainly paraffins and saturated cyclic hydro- 
carbons, with varying amounts of naphthenes and unsaturated hy- 
drocarbons. Benzol, toluol, and other aromatic hydrocarbons are 
entirely absent, or present only in traces. The tar acids consist 
mostly of the higher phenols of viscous to resinous character, with 
very little true phenol, and comparatively little cresol or xylenol. 
They also contain but small quantities of nitrogen and sulfur de- 
rivatives. 

The type of coal used exerts a greater influence upon the char- 
acter of the tar than does the particular mode of treatment, and in 
general, much variation occurs in the composition and character of 
the tars produced commercially. The creosote oils derived from 
low-temperature tars are too low in specific gravity to meet the 
current specifications in the United States. Less pitch is obtained 
than with high-temperature tars, and its character is quite different, 
and generally poorer in quality. 

The following yields are obtained from an average British me- 
dium-coking coal, subjected to various carbonizing temperatures, 
expressed in percentage by weight of the moisture-free coal : 





400C. 


45o e C. 


joo'C. 


55oC. 


6ooC. 


65oC. 


7ooC. 


Tar (per cent) 


l.o 


5.62 


7.06 


8.00 


7.60 


6.00 


6.24 


Tar (gal* per ton) 


9. i 


12.8 


16.0 


17.6? 


l6.4 


14.15 


12. O 


Tar (specific gravity at 60 F.) 
Aqueous distillate (per cent) * . 


0.958 

5.6 


0,980 

7.OI 


0.986 

7.02 


1.015 

7.70 


1.039 

8.12 


1.078 
8. 20 


1. 080 
7.18 


Gas (per cent) 


2.2 


3. 12 


4. O< 


7. 14 


Q.IO 


IO.54 


14. $8 


Coke (per cent) . 


88 2 


8l.7< 


80. <o 


77.OO 


75.00 


71.00 


7I.OO 


Loss (per cent) 


O.I 


O.1O 


O.47 


0.16 


0.18 


0.16 


I.OO 


Pitch (per cent in tar) ,..,.,., 


22.2 


28.8 


27. 


11.4 


14.6 


41.0 


52. I 


Pitch (fusing-point degrees C.) 


41.2 


17. 


52.2 


64.5 


go.5 


01. C 


95.8 


Pitch (specific gravity at 60 F.) ....... 


1. 11 


1. 12 


1. 14 


1. 17 


1.21 


1,25 


1. 20 


Pitch (free carbon per cent) . 


14.. 2 


<, 1 


4.6 


11. 


28.1 


26.8 


25.1 



















In Germany, low-temperature tar is termed "Urteer," and in 
Great Britain it is known under various names, such as "coalite 



350 COAL TAR AND COAL-TAR PITCH XVII 

tar," "carbocoal tar," "Mond tar," "Delmonte tar," etc., depend- 
ing upon the particular type of apparatus in which it is produced. 

The reader is referred to other sources for a complete descrip- 
tion of the numerous types of retorts which have been devised for 
the low-temperature process of carbonizing coal. 

Properties of Coal Tars. As stated previously, the expression 
"coal tar" is properly applied to tars derived directly from coal 
without admixture of petroleum. Coal tars differ in their physical 
properties, depending upon their method of production. The fol- 
lowing types are distinguished: 

( i ) Gas-works coal tar 

(a) Horizontal retorts 

(b) Inclined retorts 

(c) Vertical retorts 
Coke-oven coal tar 
Blast-furnace coal tar 
Gas-producer coal tar 

(5) Low-temperature coal tar. 

The figures in Table XXIII will give a general idea of the 
physical properties of the main types of coal tar in their dehydrated 
state : 

The following colorimetric test may be used to detect low-tem- 
perature tars: on shaking 1-2 ml. of the oily distillate with 5 ml. 
aqueous ferric oxalate or ferric citrate, the aqueous layer will as- 
sume a dark blue coloration, which will turn a lemon-yellow upon 
acidifying with N/io sulfuric acid and then regain its blue tint on 
neutralization, but turns purple and then bright red upon adding an 
excess of alkali. High-temperature tar oils will not give this 
reaction. 3 

Methods of Dehydrating Coal Tar. It is customary to dehy- 
drate coal tars at their point of production, to avoid paying freight 
charges on the water content. Provision is usually made for the 
gravity -separation in storage tanks of as much water as possible, 
but the amount that may be removed in this manner varies in the 
case of different tars, their mode of production, and other factors. 
With high-temperature coal tars the settled product is In the nature 
of an emulsion, with the water as the disperse phase. The amount 
of water held in stable suspension is greater in the ca& of horizontal 



XVII 



PROPERTIES OF COAL TAR 



351 



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O O O O OOHe* 



55 ^ 






rr 
feig feiifefc 



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I fr'f* 
5 lifts 



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till 






.4MilIillii MlPl! 

G&ff&K&gS3&&*ff&& ' s 



ft tn to "tt ' 

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II iiijilsiii Hi 

bfc bbbfcbbfcfcbb bbb 



352 



COAL TAR AND COAL-TAR PITCH 



XVII 



gas-retort tar than in coke-oven and vertical gas-retort tar, and still 
less with water-gas tar, ranging from 3 to 10 per cent in the case of 
the first named, down to i to 2 per cent in the last Sometimes, the 
emulsion is of a different nature, in which the tar forms the disperse 
phase and the water content ranges from 15 to 70 per cent. Such 
emulsions are most difficult to break up by the usual means of set- 
tling, even at high temperatures. They may, however, be treated 
by a partial distillation, as will be described later. 

Dehydration may simply imply the removal of the bulk of the 
water from a tar, so as to render it suitable for distillation, or as is 
the case in Great Britain, it may include the removal of the light 
oils as well, resulting in the production of a refined tar suitable for 
road purposes or other uses. 

The following methods have been used for dehydrating tars: 

(i) Settling. When the tar is allowed to settle in storage 
tanks, the water rises to the surface, where it is drawn off through a 
series of outlet pipes in the side. This process may be facilitated,' 

? articularly in the case of viscous tars, by heating to about 200 F. 
y means of steam coils in the bottom of the tank, supplied with 
exhaust steam from other plant operations. Many variations of 
simple settling have been suggested, but at best they remove but a 
portion of the water, and are generally supplanted by one of the 
methods which follow* 

(2)' Use of Centrifuges. This method has been used with 
more or less success abroad, and only in the case of tars with tars of 
low free-carbon content, so as to avoid the necessity of frequent 
cleaning. The tar is first heated to a temperature of 40 to 50 C. 

and run into the rapidly revolving 
drum of a centrifugal separator, 
illustrated in Fig. 106. The tar 
being heavier than the water is 
forced to the periphery, the water 
forming a cylindrical layer inside. 
An annular diaphragm A attached 
to the upper part of the centrifugal 
has a ring or perforations where it 
comes in contact with the drum at 
B. The crude tar is introduced 
through thepipe C below the dia- 

FIG. 106. Centrifugal Tar Dehydrator* phragm. The speed with which 

the drum revolves causes the tar 
to flow through the perforations into the upper portion of the cen- 




XVII METHODS OF DEHYDRATING COAL TAR 353 

trifugal, where it is removed through the pipe D. The water is 
drawn off through E below the diaphragm, which bars its passage 
into the upper section. This method is particularly suited for treat- 
ing tars having approximately the same specific gravity as water, as 
for example water-gas tar. The centrifugal is revolved at a speed 
between 2000 and 3000 r.p.m. Tars containing between 30 and 
90 per cent of water will have the percentage reduced to less than 
i per cent in one treatment. A large portion of the free carbon 
contained in the tars is also removed, and affixes itself to the inner 
walls of the drum from which it must be scraped occasionally. 

( 3 ) Horizontal Stills. These are used to a considerable extent 
in Great Britain according to the continuous dehydrating methods 
proposed by Hird, Chambers and Hammond. 9 They depend upon 
the use of a horizontal still heated by tubes at the bottom, through 
which the furnace gases are passed. The tar to be dehydrated is 
caused to flow through the still to a depth of about 6 in. over the 
tops of the heating tubes, and a heat-exchanger is used on the incont* 
ing wet tar and the outgoing^ hot dry tar, so as to preheat the for- 
mer. Two or several stills in series may be employed, depending 
upon the amount of water carried by the tar and the tonnage to be 
treated per day. 

(4) Tube Heaters. This process has been devised by T. O. 
Wilton, 10 and has met with favor in Great Britain. The tar is 
treated continuously upon being heated to 170 to 190 C. under a 
pressure of 30 to 50 Ib. per sq. in., by pumping through a coil of 
pipes in a furnace heated with coke. It is then released into a vapor 
chamber at atmospheric pressure, whereupon the water and light 
oils evaporate, since they are maintained at a temperature consider- 
ably higher than their boiling points. This is accompanied by 
copious frothing, due to the fact that each volume of water is 
converted into 1640 volumes of steam. As this method involves the 
charging of hot tar to the tube heater, no heat exchanger is used. 

(5) Cascade System. In Great Britain, this system has been 
patented by William Blakeley, 11 who allows the heated tar to flow 
over a series of trays arranged in a casing, the trays being intercon- 
nected by pipes which also serve to support them. The tar is intro- 
duced in the top tray and is allowed to flow from tray to tray, while 
the steam or other heating medium is introduced in the pipes at the 
bottom tray, and is conducted from tray to tray upwards. A devel- 
opment of this process has been used successfully in the United 
States in a cascade dehydrator, consisting of a rectangular steel 
chamber enclosing a series of steel pans fitted with steam coils. 12 
The pans are set at an incline w r ith alternate pans sloping in oppo- 
site directions, so as to form a cascade. Pumps are provided for 
handling the crude and dehydrated tar, also the distillate. The tar 



354 COAL TAR AND COAL-TAR PITCH XVII 

is introduced through a manifold at the top of the casing wKich 
delivers it to a distributing box over the top pan, whence it over- 
flows from pan to pan and leaves the bottom of the casing free from 
water* The vapors are conducted to a combination vapor-condenser 
and tar-preheater whence they are condensed by the raw tar on its 
way to the distributing box. A second water-cooled condenser is 
provided as a safeguard. The distillate is withdrawn from the 
second condenser by a vacuum pump, which serves to maintain a 
vacuum of 3 to 4 in. of mercury on the casing. The dehydrator is 
operated so that the exit tar attains a temperature of 275 to 
285 F., which assures its complete dehydration. A sufficient pres- 
sure is applied to the tar before entering the casing to prevent the 
evolution/ of vapors, this particular feature being similar to the 
Wilton system. A dehydrating unit of this type handles 37,000 gal. 
of gas-works coal tar in twenty-four hours, reducing the water con- 
tent from 7.7 per cent to o.i per cent; likewise 60,000 gal. of tar 
containing 4 per cent water, and 100,000 gal. containing 1.8 per 
cent water; in both of the latter instances reducing the water con- 
tent to o.i per cent 

Methods of Distilling Coal Tar. 18 Coal tar is transported from 
the gas-works or coke-ovens in cylindrical steel tank-cars 7 to 8 ft. 
in diameter and 28 to 30 ft. long holding about 10,000 gal., pro- 
vided with a dome on top and heating coils inside for the introduc- 
tion of steam in cold weather to reduce the fluidity. It is transported 
by water in tank-vessels constructed similarly to those used for pe- 
troleum, holding up to 300,000 gal. At the distilling plant, the tar 
is generally stored in covered vertical cylindrical steel tanks larger 
in diameter than height, having a capacity up to 2 million gallons. 
A certain amount of water separates during storage which is tapped 
.through pet-cocks in the side. Less often the tar is stored in rectan- 
gular reinforced concrete tanks built underground. 

Tar when heated to a temperature, usually in the neighborhood 
of 700 F., will crack and decompose, giving off permanent gas with 
the formation of insoluble matter, known as "free carbon." This 
reaction increases in velocity as the temperature increases, and 
varies of course with different tars. The effect of this reaction is a 
smaller yield of distillate to a given consistency of pitch residue, or 
in other words, it means that the pitch is produced at the expense 
o the yield of oils. Since the oil is the more valuable product, the 
cracking is regarded as undesirable. The amount of cracking is a 



XVII METHODS OF DISTILLING 'COAL TAR 355 

function of both temperature and time, increasing directly with 
either of these factors. The ideal system of tar distillation may be 
regarded as one which exposes the tar to the lowest temperature for 
the shortest possible time necessary to obtain the desired product. 
The practical effect of these factors may be exemplified by some 
results on a coke-oven tar run to a pitch of 300 fusing-point A 
reduction in the time of heating from twelve to one and one-half 
hours resulted in an increase of 16 per cent in the yield of oils and 
a corresponding decrease in the amount of pitch. Similarly, where 
the time was kept constant, a lowering of the final still temperature 
by 200 F. accomplished approximately the same result. Greater 
yields of oil may be obtained by decreasing both the time and tem- 
perature, although the effects are not necessarily additive. 

One method consists in increasing the still heating surface, so as 
to increase the heat input in a given time, and this leads to the 
continuous tube-still of one type or another, where the time factor 
is reduced materially over the batch stills. Another method is to 
reduce the still temperature by lowering the vapor pressure of the 
oils through the use of steam, vacuum, or inert gases, as will be 
described presently. 

The following methods have been used for distilling coal tars : 

( i ) Simple Batch Stills. The first stills used in the tar industry 
in Europe^were constructed in the form of a "pot" or verticaf still 
having a concave bottom, as illustrated in Fig. 107, where i repre- 
sents the manhole; 2, safety-valve connection; 3, swan neck; 4, swan 
neck stool; 5, dipping tap; 6, steam inlet; 7, steam pipe; 8, tar inlet; 
n, tar outlet. The concave bottom is claimed to have the advan* 
tages of providing a larger heating surface, also to assist in draining 
off the pitch and to accommodate the expansion and contraction of 
the metal plates without setting up dangerous strains. Steam is 
introduced during the process of distillation through a perforated 
pipe (910) at the bottom and serves to carry off the vapors more 
rapidly, also reduce the time of distillation. English stills hold 20 
to 40 tons (4000 to 6000 gal.) of tar, and are mounted on suitable 
brick settings adapted for direct heating with coal or producer gas. 

The vapors leave the still through a large pipe connected with 
the condenser coils immersed in water in a rectangular tank. These 
coils are constructed of pipes ranging from 6 in. down to 3 in^in 
diameter. The distillate is run into small measuring tanks which 
in turn empty into large storage tanks. Each fraction is caught 



356 



COAL, TAR AND COAL-TAR PITCH 



XVII 




6. 



separately, four fractions all told being recovered, viz.: light oil or 
crude naphtha, middle or carbolic oil, heavy or creosote oil and 
anthracene oil. 

In the United States the customary form of batch still consists 
of a horizontal cylinder with convex ends, heated directly with oil, 
coal or gas, constructed to hold in the neighborhood of 50 tons 

(10,000 gal.) tar. Such stills 
are about 9 ft in diameter by 20 
ft. long, and about half the 
diameter, or 500 sq. ft, is avail- 
able as heating surface. They 
take ten to twenty hours to com- 
plete distilling a charge to a 
pitch, where 40 to 45 per cent of 
oil is removed from the tar. A 
typical still is illustrated in Fig. 
1 08. The tar enters through a 
pipe into the top of the still, and 
the vapors are drawn off through 
another pipe of large diameter 
attached directly to the top of 
the still, at the center. The stills 
are not usually provided with 
domes, as is the case with petrol- 
eum stills. The outlet pipe for 
the pitch is located at the bot- 




From "Coal Tar Distillation," 
by A, R. Warnes. 



FlC. 



107. Vertical Still 
Coal Tar. 



for Refining 



torn, together with inlet pipes for 
steam or air agitation. The stills 
are mounted on a brick setting provided with a fire arch to in- 
sure uniform heating, and prolong the life of the bottom. The 
process is an intermittent one. After the tar has been distilled to 
the desired fusing-point or consistency, the residue of pitch is dis- 
charged by gravity, pumping or blowing out with air, 

In recent years the batch stills have been somewhat improved by 
the use of internal flues to increase the heating area and serve to 
reduce the time of distillation, also to minimize the carbon deposi- 
tion. A modern installation is illustrated in Figs. 109 to 113, con- 
sisting of two primary stills of 9000 gal. each and three secondary 
stills of 8000 gal each. The primary stills are of the vertical type 
and serve as preheaters, since they are equipped with spiral steel 
flues through which the gases from the secondary stills are passed, 
as illustrated in Fig. in. From the primary 'stills the heated tar is 
run into the secondary stills, where direct heat is applied, and the 
bulk of the distillation takes place; these are shown in Fig* 112. 



XVII 



METHODS OF DISTILLING COAL TAR 



357 



The pitch is run from the secondary stills to the pitch copiers of 
about 5000-gaL capacity each, which are illustrated in Fig. 113* 
The vapors are condensed in a vertical shell-and-coil type of con- 
denser filled with water, which is located directly below the primary 
stills, from which the distillate is run into the storage tanks. 

Another arrangement consists in operating the batch still in 
connection with a dehydrator of the continuous type, which has the 




of The 'Barrett Company. 
FlG. 108. Horizontal Still for Refining Coal Tar. 

advantage of conserving heat and also obviates the danger of foam- 
ing during the distillation process. 

(2) Vacuum Distillation. Vacuum of 26 to 28 in. mercury 
may be used to advantage in connection with batch stills when run- 
ning to a hard pitch of 280-300 F. fusing-point Much better 
yields of oil are obtained (e.g., about 10 per cent at a 300 F. 
fusing-point pitch) than by distillation under atmospheric pressure, 
and the reduction in cracking also has the effect of lowering the per- 
centage of free carbon in the pitch. In general, the use of vacuum 
does not materially influence the products until a pitch of 140 F. 
fusing-point is reached, but from there on the vacuum has Decided 
advantages as compared with ordinary operations, although when 



358 



COAL TAR AND COAL-TAR PITCH 



XVII 



the fusing-point of the pitch reaches a fusing-point of 300 F. or 
thereabouts, a certain amount of cracking begins, accompanied by 
the evolution of gas, which makes it impractical to maintain the 



HO-J30. t l 

- 




;|| t 

J!^ Ammonia 5,000 Gaf. U J > ~Vg^ 

<? \4^~~T) -J $< 

^ ^Pumped to Ammonia & 

5tomqeby*IOPump 

wi Oil Heavy Ot /s ^ C///5 

25,OOQ6a/ t 25flOQQaL 25 t OOOGai 2$0006al, 

O" O 1 O"" 0"' 

IW2W 230-270* 270-300' 300'+ 

Pumped from Pumped f/vm Pympedf/vm Pumped from 

AccJankfhru Rec Jan k thru RecJanksihru Rcclanksthru 

*IQPump *lOPump *IIPump *HPump 



Tar 



SYMBOLS 

------ Oil-230-270 

-------- 0,1-270'- 300* 

------- OiL300'+ 



FIG. 109, Flow Diagram of Dry Tar to Light and Heavy Oils. 




FIG. no. Cross-section of Tar Distillation Plant 

necessary degree of vacuum. In distilling to a pitch of 220 F. 
fusing-point, the final still temperature is 750 F. at atmospheric 
pressure, in comparison to 570 F. when distilled under a vacuum 



XVII 



METHODS OF DISTILLING COAL TAR 



359 



of 28 in. mercury. In a vacuum distillation plant, the oil receivers 
must be in parallel, connected with suitable piping, so that one may 
be released to empty it, without disturbing the vacuum on the rest 
of the system. 




. 

K- - ~ 3-(f J 



FIG. in. Primary Tar Still. 



An alternate procedure consists in agitating the tar with steam, 
using a vacuum of about 15 in. of mercury. The following figures 
were obtained on coke-oven tars of 9 per cent free carbon : 



360 



COAL TAR AND COAL-TAR PITCH 



XVII 





Final Still 
Temp. C. 


Per Cent by Weight 


Pitch Tests 


Pitch 


Oil 


Air M. Pt. 


Free Carbon 


Atmospheric 


400 
300 


64-3 
55-9 


34-9 
43' I 


220 F, 

216 F. 


35 -3 per cent 
26.1 per cent 


Vacuum of 28-in. . . , 




FIG. 112. Direct-fire Secondary Tar Still. 

' In general, the softer the pitch produced, the less will be the 
advantage of vacuum distillation. 

Heating in a bath of molten metal under vacuum has also been 
suggested. 14 

(3) Steam Distillation. The passage of superheated steam 
through the contents of the batch still also serves to reduce the dis- 




FIG. 113. Pitch Cooler. 

tillation temperature and to minimize the cracking, 15 but the amount 
of steam required is so great, that its use has not proven practicable 
from the standpoint of cost and on account of the greatly increased 
condenser surface required. This, however, does not apply to the 
use of a small amount of steam to agitate the contents of the still, 
where th$ distillation takes place at atmospheric pressure. 

The effect of large volumes of steam is indicated by the follow- 



XVII 



METHODS OF DISTILLING COAL TAR 



361 



ing figures/ 8 where steam was passed at a rate of o.i i cu. ft. (cor- 
rected at 77 F. to 760 mmj per gallon of tar per minute, ap- 
plicable to a coke-oven tar of 8.5 per cent free carbon content: 





Final Still 


Per Cent by Weight 


Pitch Tests 




Temp. C. 














Pitch 


Oil 


Air M. Pt. 


Free Carbon 


Ordinary distillation. 


413 


57.8 


40.1 


280 F. 


40. 7 per cent 


Steam distillation. . . 


340 


47.0 


50.6 


*79 F. 


28,8 percent 



It may be noted that the steam consumption was such that the 
condensed water approximately equaled the volume of the "oil" 
recovered on distillation. 

(4) Gas Re circulation. By circulating an inert gas such as 
nitrogen or carbon dioxide through the contents of the regular batch 
stills at the rate of i to 20 cu. ft. per 100 gal. tar, per minute, the 
vapor pressure of the oil vapors is lowered, coupled with a reduc- 
tion of the still temperatures and an increase in the yield of distil- 
late. 17 This procedure merely involves the addition of a gas recir- 
culation pump and closed distillate receivers to the batch-still equip- 
ment. In practice, no provision is made for the inert gas, as the 
system may be filled with air at the start, since in a short time the 
oxygen is used up and the recirculation gas becomes nitrogen. The 
formation of free carbon is minimized, and the distillation may be 
carried to a much further point without danger of coking of the 
still contents. Whereas pitches of about 300 F. fusing-point rep- 
resent the hardest that may be produced commercially by the fore- 
going distillation methods, with the recirculation method, pitches of 
400 to 450 F. fusing-point may readily be obtained, and with a 
correspondingly greater yield of distillate. Thus, with a coke-oven 
tar of 8.5 per -cent free carbon content, 65 per cent by weight of 
distillate was obtained upon running to a pitch of 400 F. with a 
carbon deposit in the still no greater than was the case upon run- 
ning to a 250 F. fusing-point pitch by the ordinary method, with 
only 40 per cent distillate. 

A comparison of the oil yield by the gas-recirculation method 
on the same type of coke-pven tars referred to under the captions 
"Vacuum Distillation" and u Steam Distillation," is given below* 
The gases were recirculated at a rate of 0.33 cu. ft \ corrected to 
77 F. and 760 mm.) per gallon of tar per minute, in the case of 
CO 2 , and at the rate of 0.40 cu. ft. (corrected to 77 F* and 760 
mm.) per gallon of tar per minute, in the case of N 2 : r 



.16 



362 



COAL TAR AND COAL-TAR PITCH 



XVU 





Final Still 
Temp. C 


Per Cent by Weight 


Pitch Tests * 


Pitch 


Oil 


Air M. Pt. 


Free Carbon 


Atmospheric. 


4i3 
358 
33i 


57.8 
46.9 
46.4 


40.1 
52.6 
52.0 


280 F. 
277 F. 
*77 F. 


40 . 7 per cent 
29.0 per cent 
27 . 2 per cent 


Recirculated COz 
Recirculated N2 





(c) Continuous Stills. Various expedients have been pro- 
posed 18 to transform the batch distillation process into a continuous 
operation, as for example placing several stills in series and flowing 
the tar through them consecutively and taking different fractions 
from each still^ allowing the pitch to flow from the last in the series. 
In Great Britain two continuous systems of tar distillation are in 
use, as devised by H. P. Hird and E. V. Chambers Respectively. 
The Hird process 19 involves the use of four stills, three of which 
are connected in series, the first two being heated by internal flues 
and the third being arranged for the introduction of steam. The 
fourth still is used for the production of pitch. Separate condensers 
for each still and suitable heat exchangers are provided. The first 
still is maintained at 190 C, the second at 240 C., the third at 
325 C, (producing creosote oil), and the fourth at 275 C. The 
stills are provided with a series of vertical baffles and the tar flows 
through the system in a comparatively thin layer. The Hird system 
is only adapted to producing pitches ranging in fusing-point up to 
200 R 

The Chambers process is a modification of the cascade system 
used for dehydrating tars. It involves the use of two stills provided 
with cascades, three condensers and one heat interchanger. The 
crude tar is preheated by flowing through the heat interchanger, 
and then caused to flow down the cascade in still No. i, followed 
by a return through the bottom of the still which is kept about one- 
third full of tar. The tar then passes through the 'still No. 2 in a 
similar manner, and finally into Still No. 3 which is not equipped 
with a cascade, where the residue is distilled to pitch with the intro- 
duction of steam. Still No. i is maintained at 210 C. and pro- 
duces light oil, still No. 2 is kept at 260 C. and produces light oil 
and creosote, still'No. 3 is kept at 320 C. and produces anthracene 
oil and a residue of pitch. It is claimed that a plant of this type 
will successfyilly handle a Mond or water-gas tar containing as 
much as 30 per cent of water. 

(6) Tube Stills. These operate on the principle of heating the 
tar by passing it through a coil of pipe surrounded by the heating 
medium, and then allowing the vaporization of the oils to take 



XVII METHODS OF DISTILLING COAL TAR 363 

place in a vapor chamber at the exit of the coil, thus handling the 
tar continuously. 

In Great Britain the Wilton process 20 has met with much favor, 
and consists of a modification of the method described previously 
for dehydrating tar. The Wilton tube-still for the continuous dis- 
tillation process consists of two successive heating coils in series, 
.followed by a cylindrical still in which superheated steam is intro- 
duced, with expansion chambers in between each unit. The first 
coil heats the tar to 200 C. under a pressure of 30 to 50 Ib. per 
sq. in. and removes the light oils and water. The second coil heats 
the tar to 230300 C. and removes the creosote oil. The last 
still removes the anthracene oil by means of the superheated steam 
at 360 C M and separates the pitch. 

Other types used in Europe include the so-called "Sadenwas- 
ser" 21 and "Leinweber" 22 stills, named after the makers. 

Similar stills are in use in the United States with very satisfac- 
tory results. 23 They utilize a single heating coil when running to 
pitches of about 200 F. fusing-point, and two heating coils when 
running to a 300 F. pitch, which is about as hard as can be pro- 
duced in this type of apparatus. The crude tar is first introduced 
as cooling means in the various oil condensers, whereby it is heated 
sufficiently, so that when released into an expansion chamber, the 
water and light oils are vaporized and condensed, whereupon the 
dehydrated tar is pumped through the first heating coil. After 
passing through the first coil, the tar is sprayed into a second ex- 
pansion chamber where the creosote oil is taken off to fractional 
condensing means, and the residual intermediate pitch pumped 
through a second coil in the same furnace as the first coil, but in a 
hotter zone, and the same process repeated. For the softer grades 
of pitch the second stage may be omitted. The use of vacuum in 
the second stage will serve to still further reduce the operating 
temperatures. 24 The smallest still of this type handles from 30,000 
to 50,000 gal of tar per day, depending upon the character of the 
tar and the grade of pitch desired, whereas the largest unit in op- 
eration in the United States has a capacity of 90,000 to 140,000 
gal. tar per day. The yield of oils in such stills will run 10 to 15 
per cent better than the ordinary batch still in producing pitch of 
300 F. softening-point, due entirely to a reduction in the time of 
heating to less than one-fifteenth that required in the latter. The 
general flow relationship of a well-developed tube-still installation in 
the United States is shown in Fig. 114. * 

^ Continuous fractional condensing columns have been developed 
which separate the vapors into sharper fractions than were previ- 
ously obtainable^ in the batch stills. Furthermore, a number of 
closely cut fractions may be obtained simultaneously and continu- 



364 



COAL TAR AND COAL-TAR PITCH 



XVII 



ously from the mixed tar vapors, in a properly designed and con- 
structed condensing column, including* the separation of creosote oil, 
naphthalene oil, heavy oil and anthracene oil. 

(7) Collector-main Condensers. A process has been devel- 
oped 25 in the United States, in which tars of the desired consistency 
may be separated directly in the collector-main of the coke-oven, by 
scrubbing the hot vapors with the preheated tar, or else with some, 
of the recovered oils, yyhich are introduced in the form of a spray. 
These serve to remove the tarry matter from the vapors, which are 




H..C.~ HEAT EXCHANGE COMtH$tR3. 

FIG. 114. Flow Diagram of Continuous Tube-still for Coal Tar. 

thereby cooled and at the same time the gases are enriched. The 
equipment is illustrated diagrammatically in Fig. 115. 

The process operates as follows : the hot gases from the ovens 
pass up the ascension pipes, i, into the collector main, 2, which is 
connected at one end with the 'foul gas or air-cooled main 3. The 
two mains have a continuous fall in the direction of gas flow, and 
tar is circulated through them by the pump, 4, and gravitates back 
to the tank, 5, accompanied by the heavier tar fractions which have 
condensed from the gas. 

The essentially valuable feature of the process is that road tar 
of any required standard can be withdrawn from the air-cooled or 
foul gas mam at point 6, at which the temperature of the gas is 
stiirabove the dew point of the lighter tar constituents, which are 
carried forward with the gas. By a simple manipulation of this 
fundamental ohvsical condition or the foul eas stream, road tar 



XVII RECOVERY, TREATMENT OF COAL-TAR DISTILLATES 



365 



may be produced, continuously or intermittently, the tar so ob- 
tained being superior in essential respects to that produced by de* 
hydration or distillation in stills. Perfectly dry road tar may be 
run while hot from the seal pot, 12, to the receiver, 11, where the 
viscosity is checked and adjusted, if necessary, by mixing with oil 
or road tar of suitable consistency. 

With a pitch run to 300 F. fusing-point, a 70 per cent oil yield 
is claimed, as compared with 44 per cent in a batch still. Creosote 
oil as well as hard pitch may be collected in a similar manner. Hard 
pitch may be burnt as fuel, or returned to the coke-ovens with the 
charge of coal. 

This process represents quite a forward step, and is rapidly 
being adopted in by-product coke-ovens, both in the United States 




FIG. 115. Collector-main Condenser for Coal-tar Distillation, 

and abroad, since it is both more efficient and economical than the 
use of condensers and scrubbers. 

Recovery and Treatment of Coal-tar Distillates. On refining 
coal tar by any of the distillation processes previously outlined, one 
or more of the following distillates are obtained: 

(1 ) Light Oil. At the commencement of the distillation proc- 
ess, the light oil or u crude naphtha" distils over, and comprises the 
entire distillate lighter than water, being obtained below a vapor 
temperature of 200 C, This fraction is first washed with alkali 
to remove the tar acids, and then redistilled and fractioned into 
crude benzol, toluol, solvent naphtha (xylol) and heavy naphtha. 

(2) Middle Oil This is generally considered to include the 
fraction boiling between 200 and 250* C In some cases it is mi^ed 



366 COAL TAR AND COAL-TAR PITCH XVII 

with the ensuing fraction the heavy oil provided the mixture will 
meet existing specifications for creosote oil. In other cases the 
middle oil is first extracted with caustic soda to remove the tar acids 
before it is mixed with the heavy oil, for use as creosote. Still 
another alternative consists in redistilling the middle, oil in fire- 
heated stills to separate it into the following fractions : crude naph- 
tha up to 210 C, acid-naphthalene oil from 210 to 250 C, and 
creosote oil above 250 C. The crude naphtha is treated with 
caustic soda to remove the tar acids and then worked up with the 
light oil fractions. The acid-naphthalene oil is first cooled in pans 
to crystallize out the naphthalene, whereupon it may either be mar- 
keted as such under the designation "tar-acid oil," according to the 
percentage of tar acid content (e.g., 15 per cent, 25 per cent, 50 
per cent, etc., as the case may be), or it may have the tar acids 
removed and marketed as naphthalene oil. 

In Germany, the practice consists in distilling the middle oil in 
a fire-heated vacuum column still, which gives much closer boiling 
fractions, as follows: crude heavy naphtha up to 200 C., a second 
fraction from 200 to 220 C. containing the bulk of the cresylic 
acid and comparatively little naphthalene, next a closely cut naph- 
thalene oil fraction carrying a high percentage of crude naphtha- 
lene, leaving a residue of so-called creosote oil. 

The tar acids extracted from the various fractions ^ obtained 
principally from the middle oils are obtained as their sodium salts, 
which in turn are treated with carbon dioxide to liberate the tar 
acids, phenols, etc. These acid products are separated and mar- 
keted under the following designations: phenol, cresols, 97-^99 per 
cent straw-colored cresylic acid, 95 per cent dark cresylic acid, 
ortho-cresol, meta-cresol, para-cresol, etc. They are variously used 
for the production of emulsifiable disinfectants, cattle sprays, and 
as flotation oils for the concentration of certain grades of mineral 
oils. 

(3) Heavy Oil. This is variously known under the terms 
heavy oil, creosote oil and dead oil, and may either represent the 
fraction between 250 C. to the end of the distillation, or the frac- 
tion between 250 C. and the anthracene oil fraction. United 
States practice consists primarily in adjusting the heavy oil fraction 
to meet the various specifications established for creosote oil for 
use in wood preservation. 26 This may be accomplished by con- 
trolling the distillation range of the fraction, or by mixing together 
various fractions obtained from the middle and heavy oil respec- 
tively. In either case, it is advisable to remove any naphthalene by 
cooling and filtering. 

(4) Anthracene Oil Unless it is intended to extract anthra- 
certfe, the anthracene oil fraction is not made, and the entire cut is 



XVII RECOVERY AND TREATMENT OF COAL-TAR RESIDUALS 367 

worked up for creosote oil. Where it is intended to produce an- 
thracene, the anthracene oil fraction is cooled in pans or tanks until 
the anthracene crystallizes out, whereupon it is filter-pressed to 
obtain a cake containing 2030 per cent anthracene, or else sub- 
jected to a hot hydraulic pressing to remove more oil and produce 
a cake containing 30-40 per cent anthracene. The anthracene is 
used principally to produce alizarin and other coal-tar dyes. 

Recovery and Treatment of Coal-tar Residuals. At the close 
of the distillation process the residual product consists either of 
coal-tar pitch, or else refined coal tar, depending upon its physical 
characteristics. There is no sharp line of demarcation between the 
two, although, in general, residuals having a fusing-point above 
80 F. (cube method Test 15^) are known as pitches, whereas 
those fusing below are considered refined coal tar. The charac- 
teristics of a given residual will vary with the nature of the tar, 
the particular method of distillation, and the quantity of distillate 
removed. When the distillation has been completed, the hot pitch 
is run into coolers illustrated in Fig. 113, and when the temperature 
falls to 250 to 300 F. the product is either run into barrels or into 
a large rectangular concrete enclosure known as a "pitch bay," 
where it is allowed to solidify. Various methods have been sug- 
gested to facilitate the handling of hard pitches, 27 consisting in 
molding it, 28 rapidly cooling the pitch and breaking it into frag- 
ments, 29 comminuting the product, 30 dropping the melted pitch from 
an elevation into a body of water, 81 forming an aqueous suspension 
with a peptizing agent, 82 etc. 

If the distillation is continued to the desired point, then the 
residue is known as "straight-run coal-tar pitch." On the other 
hand, if the distillation is carried to a point where the residue is 
harder and more infusible than desired, and is thereupon fluxed to 
the desired consistency and fusing-point, either with certain frac- 
tions of the distillate 3S or a flux of different origin usually of little 
value commercially or with other tars, 84 then the pitch is known 
as "cut-back coal-tar pitch." S5 

It has been claimed that coal-tar pitch treated with petroleum 
distillate (e.g., naphtha) and steam in a heated vessel with agita- 
tion, and then being allowed to settle, will separate into (a) a 
clear supernatant liquid suitable for use as a paint vehicle, and (b) 



368 COAL TAR AND COAL-TAR PITCH XVII 

a pitch-like mass suitable for the manufacture of roofing com- 
pounds. 86 Processes have been described in which low-temperature 
coal tar is distilled to a pitch in the presence of NaOH ; * r likewise 
the steam-distillation of coal-tar pitch with Fe 2 3 and FeCl 3 in com- 
bination with montan wax, whereupon distillates are said to be ob- 
tained composed of waxy and resinous products. 88 

The crystallization* of naphthalene, anthracene, phenanthrene, 
etc., from coal tars and their distillates may be inhibited by adding 
a small percentage of stearyl chloride. 89 

Coal-tar residuals have found many uses in the arts, among 
which may be cited the following: very soft pitches and refined 
coal tars are used for saturating felts ; for dust-laying purposes on 
roads and pavements; as the base of various kinds of paints and 
protective coatings for metals, masonry, and other structural ma- 
terials. Moderately soft pitches having a fusing-point between 80 
and 120 F. are used principally for road binders and sometimes 
for waterproofing work. Medium hard pitches having a fusing- 
point between 120 and 160 F. are used for constructing "pitch- 
and-felt roofs"; for laminated membranes used in waterproofing 
foundations of buildings, tunnels, subways and bridges; as pipe- 
dips ; as a binder in constructing bituminous concrete and macadam 
pavements; for filling the joints in block pavements; and for manu- 
facturing the better grades of bituminous paints. Hard pitches 
having a fusing-point between 160 and 212 F. are used principally 
as a binder for fuel briquettes. Very hard pitches having a fusing- 
point above 212 F. are employed as a binder for sand-cores in 
forming castings of iron and steel; for manufacturing electric-light 
carbons, battery carbons, carbon brushes for motors and dynamos, 
black "day pigeons" for target shooting, and sundry plastic com- 
positions for insulating purposes, as a filler for rubber goods, 40 etc* 
It has been pointed out 41 that very hard coal-tar pitches (fusing- 
point between 300 and 400 F.) may be cut-back upon melting with 
pitches of a lower fusing-point. 

Coal-tar pitches are remarkably resistant to the disintegrative 
action of water, and are therefore well adapted for sub-soil water- 
proofing. They are more weather resistant than wood-tar pitch, 
rosin pitch, lignite-tar pitch; shale-tar pitch and bone-tar pitch, but 



XVII RXCOrERY AND TREATMENT OF COAL-TAR RESIDUALS 369 

are Inferior to carefully prepared residual asphalts obtained from 
jaetroleum, blown petroleum asphalts, wurtzilite asphalt, fatty-acid 
pitches and pure native asphalts containing approximately the same 
percentage of volatile matter. 

J The manufacture of pitch-coke has assumed considerable irnpor- 
ance in recent years, for use in the metallurgical industries, espe- 
cially in the production of certain high-grade castings, on account of 
,fts extreme purity and freedom of deleterious mineral constituents 
Whkh are present in coke produced directly from coal, also^ for 
manufacturing electrodes. Pitch-coke results when coal-tar pitch 
fc distilled in a retort until ail the volatile ingredients have been 
Driven off. As the distillation proceeds beyond the anthracene oil, 
the character of the distillate assumes a grease-like consistency, 
\vhich thickens as the distillation proceeds. At the same- time a 
strong evolution of gas (mainly hydrogen) takes place, accom- 
panied with a certain amount of ammoniacal liquor. The residue 
at this stage is very pasty and of a high fusing-point and there is 
Considerable danger of the still foaming over. As the heating is 
continued, the mass cokes and the distillate appears as a transpar- 
ent ruby-red resinous substance, having a specific gravity above 1.22, 
known as "pitch resin," which melts between 40 and 100 C. 4 * The 
temperature at the close of the distillation ranges between 800 and 
1000 F. . The yield of resin may be increased by distilling the 
pitch with steam in the presence of Fe 2 O 8 and FeCX 48 Another 
type of pitch resin (fusing-point 105-110 C) may be obtained 
fft>m the sludge produced in refining the light oils with sulfuric 
a$id, which is neutralized with caustic soda and distilled to 225- 
300 C, under a vacuum of 28 in. 44 The character of the pitch- 
coke varies, depending upon the type of apparatus in which the 
pitch is coked, the time of heating, and the final temperature at- 
t^ined. It consists of practically pure carbon, except for 0.2 to 
0.5 per cent ash. In Europe the distillation is performed in 
special cast-iron pot stills with large doors or man-holes to facili- 
t$te cleaning, holding i to 2J4 tons of pitch, which are run on a 
thirty-six hour cycle. The resulting coke is quenched with water 
and then chopped out of the still by hand. The pitch charged 
ifsually has a fusing-point of 60 to 75 C., and the products ob- 



37$ COAL TAR AND COA&TAR WZTJEf ^ . 

, . * * ' ' ' ' $ * 

tamed include 30 to 40 per cent of aa 0range<plored waxy grft*s? 
(specific gravity 1.14 to 1.22); 4 to 6 per cent of pitch-resin^ 
traces of aimmonia; and 56 to 60 percent of pitch-coke. :' '* 

In the United States a large quantity of pitch-coke has^b^eh 
produced by first preparing d pitch having a fusing-point of 400 t 
450 F. by the recirculation method of distillation, 45 which is therj 
coked in a bee-hive type'of coking oven, 46 no attempt*being rrfadfe 
to. recover the by-products which are employed to furnish the hea^ 
required for the coking operation. The pitch used has a fusing? 
point (cube method Test i$c) of 440 F. and fixed carbon (Teit 
19) 63 per cent. A charge of 6.5 tons may be coked in sixty-foil^ 
hours at a maximum temperattire of 1100 F. The coke is the^ 
quenched with water and removed, whereupon it contains i pe 
cent of volatile constituents, 0.48 per cent ash and 0.38 per cent 
sulfur, being, approximately 98 per cent pure carbon. The usual 
unit is a 5000 gal. still with a 4000 to 4500 gal. charge, operating 
on a 48 hour cycle, yielding 60 to 75 per cent oil from coke-oven 
tars, A modified type of pot-still is also used, consisting of a cyliri* 
drical still set horizontally in brickwork, so that its entire circum* 
ference is surrounded by the hot gases, thereby preventing con- 
densation and speeding the distillation process. 47 Alternate pro- 
cedures consist in distilling in vacuo; mixing the pitch with coke 
breeze and charging same into'the coke ovens; 45 spraying the melted 
pitch with steam into the coke-oven chamber ; 40 etc. A cellular pitch 
coke suitable for use as a decolorizing agent may be obtained by 
distilling coal-tar pitch with NaOH, KOH, MgO, or CaO. 50 * 

The successful coking of pitch has provided the necessary oi#- 
let for the surplus production, which cannot be disposed of through 
the regular channels. 

Table XXIV gives a schematic outline of the various products 
derived from coal upon distilling it destructively, including the 
commercial substances produced from coal tar, as practiced in the 
United States. 

Properties of Coal-tar Pitches. The figures in Table XXV will 
serve to give a general* idea of the limiting physical characteristics 
oi the pnhcipal types of coal-tar pitdht ' in 

: Chttrch and Wfeiss examined representative Specimens of coal- 
tar pitches,** with the following results, in which A represents gas- 



TABLE XXIV 

PRODUCTS DERIVED FROM COAL, 



COAL 







. I , . 


1 


| .A. | 


GAS LIQUOR * 1 COKE | 


1 


1 


1 1 I I I 1 1 1 


II III II 1 1 


1 D?. A o" 1 1 BEN20L 1 1 TOLUOL 1 1 XYLOLS 1 1 SULF UR ||CVANOGE^|"- 1 - UM 3 ,NAT.N!JJ ryEL M | 


|T;;T,A S I 1 s& \ \*T\ K^\\^^^nfo^i\ \'SKS&M \ f ETAL co u K\ CICAt l 1 ** \ \ TO TIC 1 tem^l 


II | 


i . 


1 | _ 


iii 


[xANIHATCEjI^^^IJJ [sULPOCYANIDEJ (FenROCYANIDtj | 1 


1 1 |LUBRICANT| [CRUCIBLE) [iLECTHooEs| 


j ;'.._.._ -L -. T/> 


kR 






r"x||*j]o N J f CYANIDE | |FERRICYANIDE| f~ l '''S!e* N ~l 








1 , 1 


1 




I ... I 







|,M^1| . ||P*,HT| |. OOF,NG||T MM K W ,H.| 








[ HARD 


PITCH [ 







XVIl 



PROPERTIES OF COAL-TAR PITCHES 



371 



I 



I 



ill 



i iJ 



a 

a 



a 



S; 



;1 



!U* 







j! 3S, 

B j ' H'~ I 't!'^'~ l S $J StS^-^S 4> fc*^^ 

1 Hli 



'^^KSS^Iig f-a-s 'aff^ifta^ll Si? 
UBIXIIIIIIiSlI III IIIII'I2|J ||8 



eeeeebbebbbb 



372 



COAL TAR AND COAL-TAR PITCH 



XVII 



works coal-tar pitch obtained from horizontal retorts, B gas-works 
coal-tar pitch from inclined retorts, C gas-works coal-tar pitch from 
vertical retorts, D Otto-Hoffman coke-oven coal-tar pitch, E Semet- 
Solvay coke-oven coal-tar pitch, and F Scotch blast-furnace coal- 
tar pitch. 

TABLE XXVI 





A 


B 


C 


D 


E 


F 


(Test 7) Sp.gr. a t6o/6oF... 
(Test 9*) Hardness at u 5 F . . , . 
Hardness at 77 F 


1.30 

Too soft 

19 


1.28 

Too soft 

4 


1.19 

Too soft 
44 


1.25 

Too soft 
4* 


1.25 

Too soft 
39 


1.23 

3*4 
4 1 


Hardness at 32 F 
(Test i$c) Fusing-point (cube 
method) F 


2 

I2< 


2 
123 


2 
125 


3 
126 


2 
126 


8 
135 


(Test 19) Fixed carbon (per cent) 
(Test 21) Sol. in carbon disul- 
fide (per cent) 


41-5 
64,9 


37-0 
67.8 


I6. 3 
89.5 


28.5 
79*9 


28.2 
82.5 


14.4 
58.2 


Non-mineral matter 
insoluble (per cent). 
Mineral matter (per 
cent) 


34-9 

0.2 


32.0 

0.2 


10,3 
0.2 


19.7 
0.4 


17.4 
O.I 


30.0 
11. 8 


(Test 22) Carbenes (per cent) 
(Test 31) Free carbon (per cent) 


3-5 

34-9 


2.8 
30.8 


" 5-3 
8.0 


7-4 
21. 1 


5-9 
18.3 


2.6 

28.4 



"A sample representing a well-advertised brand of straight-run 
gas-works coal-tar pitch marketed for built-up roofs was tested by 
the author with the following results : 

(Test 7) Specific gravity at 77 F i.*S 

(Test 9*) Hardness at 1 1 5 F 95 

Hardness at 77 F ao 

Hardness at 32 F o 

(Test 9*) Consistency at 115 F 5- 

Consistency at 77 F 

.Consistency at 32 F 

(Test 9<f) Susceptibility index 

(Test 10*) Ductility at 115 F 

Ductility at 77 F 

(Test 9^) Ductility at 32 F 

(Test 1 1) Tensile strength at 1 1 5 F 

Tensile strength at 77 F 4-05 

Tensile strength at 3* F 8.5 

(Test 15*) Fusing-point (cube method) "* F, 

(Test 16) Volatile matter, 500 F. in 5 hrs 8.2 per cent 

(Test 17*) Flash-point * 3$o F, 

The consistency, tensile strength (multiplied by id) and duc- 
tility curves of this specimen are shown in Fig* 116. * 



24.7 
> 150 

> IOO 

35 
75-5 
o 

0.15 



XVII 



PROPERTIES OF COA^TAR PITCHES 



373 



Coal-tar pitches are characterized as follows: 52 

1 ) Jet-black streak on porcelain, 

2) Carbonaceous matter clearly visible under microscope. 
3 ) Comparatively high specific gravity. 

4) High susceptibility index. This means that they are 
largely influenced by changes in temperature, becoming brittle in 
winter, and softening under extreme summer heat. 



77' 



115 



140 
ISO 
120 
110 
100 
90 
60 
70 
60 
50 
40 
30 
20 
10 

A 








ll /" 


N, 
















LEGEND 
Hardness 

_. , jffgjyfafajQ) 

. Ductility 

O Fusing fVnt 








\i 


\ 
\ 

\ 














































i 






\ 




















i 


\ 




\ 




















r 
i 


\ 




\ 






























55 


^ 




{ . 




/^ 


*^V 




















^ 


S 






\ 






15.5 




\ 


























\ 




v 






\ 

\ 


























\ 




1. 






\ 




























\ 


Jl 


46.5 






\ 


























\ 


4 


\ 

\ AOL 








( 3 


s 
























V 

?< 


^. \ 








V 


\ 






















/ 






s, 








\ 


^ 














ft, 


hJHB 


^ 






' 




^l. 


F* 1 ! 


t 


rjri-rr 


=233 


BBtaM 


its 


t i 



10 20 30 40 SO 60 70 80 90 100 110 

Temperature, Degrees Fahrenheit 

FlG. 1 1 6. Chart ot Physical Characteristics of Coal-tar Pitch* 

(5) High ductility when tested at temperatures ranging be- 
tween the solid and fluid states. 

'6) Characteristic odor on heating. 

^7) Pass rapidly from the solid to the fluid state. 

[8) Comparatively high percentage of volatile constituents 

i heated at ?oo r . for five hours. 



when 



(9) Comparatively high percentage of fixed carbon. , 

(10) Comparatively high percentage of non-mineral matter in- 
soluble in carbon disulfide ("free carbon"). 

N ( 1 1 ) Comparative insolubility in petroleum naphtha, 
(12) Comparatively small percentage of sulfur. 



374 COAL TAR AND COAL-TAR PITCH XVII 

( 13 ) Naphthalene present in most instances. 

(14) Solid paraffins are either absent or present in small 
amounts. 

15) The sulfonated constituents are soluble in water. 

(16) The distillate to coke contains a comparatively large 
tmount of tar acids. 

(17) Give the diazo reaction. 

( 1 8 ) Very slightly soluble in ethyl alcohol, forming a yellowish- 
brown solution, with an intense greenish-blue fluorescence. 

Low-temperature coal-tar pitches may be differentiated from 
high-temperature pitches, since the former: 

contain more phenolic bodies. 

contain solid paraffins. 

contain traces to no naphthalene and anthracene. 

Attempts have been made to oxidize coal-tar pitches in the fol- 
lowing ways : heating in air with MnO 2 or HNO 3 ; 53 heating in air 
with MnO 2 and NH 4 C1; 54 blowing at an elevated temperature (e. g. 
370 C.) by the same process used for treating petroleum as- 
phalts ; 55 blowing with air under pressure ; 56 blowing with air in the 
presence of sulfur; 57 blowing with air in the presence of sulfur, 
CaO and KC1O 8 ; 58 blowing with air in the presence of MeCHO 
and NH a ; 59 blowing with air in the presence of H 2 SO 4 ; 60 blowing 
with air in the presence of H 2 SO 4 and a persulf ate or perborate ; 61 
blowing with air in the presence of Fe 2 O 3 ; 62 blowing with air in 
the presence of FeCl s or Fe 2 O 3 containing sulfur; 68 treating with 
oxygen at an elevated temperature in the presence of boric, phos- 
phoric or hydro-iodic acid; 64 blowing with oxygen in the presence 
of nitrous oxides; 65 first emulsifying a mixture of coal-tar pitch and 
heavy tar oils with an aqueous solution of Na 2 CO 3 and Na 2 SiO 3 and 
then adding BaO 2 . 66 Processes have also been described for blowing 
a mixture of coal-tar pitch with saponified vegetable oil, 67 or with 
asphalt or lignite-tar pitch. 68 

The presence of comparatively large amounts of volatile con- 
stituents results in disproportionately high losses in the blowing 
operation. Samples tested by the author showed a slight lowering 
of specific gravity, a decrease in the hardness for a given fusing- 
point, a decrease in the susceptibility factor (L e*, the material was 
less affected by changes in temperature) and no appreciable change 



XVII PROPERTIES OF COAL-TAR PITCHES 375 

in the ductility. Blown coal-tar pitches have not been marketed, 
nevertheless they warrant further development. 

Coal-tar pitches may be vulcanized by heating with sulfur; 69 
or a mixture of sulfur and alum; 70 or a mixture of sulfur and 
CaOCl 2 ; 71 or with an alkaline polysulfide or antimony sulfide ; 72 or 
with spent Fe 2 O 3 (obtained in the purification of coal gas) in the 
presence of FeCl 3 or MnSO 4 ; 73 or with S 2 C1 2 (with or without sul- 
fur) 7 * or by heating with H 2 SO 4 ; 75 or by heating with H 2 SO 4 and 
subsequently heating to a higher temperature until the acid is de- 
composed; 76 or with organic nitro- or sulfochloride derivatives; 77 
or with SaCla or thionylchloride and then combined with phenol- 
formaldehyde resin; 78 or by treating a mixture of coal-tar pitch 
and vegetable oil with nitric acid and vulcanizing with sulfur; 79 
or by heating a mixture of coal tar and vegetable oils or fats with 
H 2 SO 4 . 80 These processes serve to raise the fusing point of the 
pitch and make the product more resistant to temperature changes. 
In Germany, sulfurized coal-tar pitch has been marketed under the 
name "Holzzement" for cementing together layers of coal-tar satu- 
rated felt in constructing built-up roofs. 81 

A type of coal-tar pitch suitable for use in constructing steep 
built-up roofs and which will not run or flow at high sun tempera- 
tures when exposed at angles in excess of 30 may be prepared as 
follows: distilled coal-tar pitch or coke-oven-tar pitch is heated 
to 550 F. and 2 to 3 per cent of ammonium sulfate or zinc sulfate 
is incorporated, the heating being continued until dissolved. During 
this treatment the pitch is hardened and its fusing-point (Test i$c: 
cube-in-air method) raised to about 400 F. It is thereupon cut 
back with 30 to 40 per cent anthracene oil. The final product, 
known as "rubber pitch" has a low susceptibility, and tests as fol- 
lows: 

(Test 7) Specific gravity at 77 F i . 240 

(Test 9^) Penetration at 115 F 55 to 65 

Penetration at 77 F 20 to 22 

Penetration at 32 F 5 to 9 * 

(Test ij<r) Fusing-point (cube method) 180 to 190 F. 

(Test 31) Free carbon 33 to 36 per cent 

Coal tars and coal-tar pitches may be deodorized by treating 
with formaldehyde or paraformaldehyde in the presence of acids or 
alkalies followed by blowing steam through the heated mass. 82 Coal 



376 COAL TAR AND COAL-TAR PITCH XVII 

tars may be hardened and toughened, and thereby rendered less sus- 
ceptible to temperature changes, by converting the phenols, cresols, 
etc., in situ, into formaldehyde condensation products (i.e., phenolic 
resins) as follows: coal tar (1000 parts) is mixed with formal- 
dehyde (10 parts) and ammonia of sp, gr. 0.880 (5 parts), then 
digested 8 hours at 70 C. in a closed vessel, whereupon a catalyst 
(e.g., CuSO 4 or FeSCX) is added and the mass blown with air for 
I o to 30 hours, during which process the temperature is gradually 
increased to 193 C. The resultant product has been marketed 
under the name "Bitural". 88 Similarly, synthetic resins may be pro- 
duced from the fraction of low-temperature coal tar, distilling be- 
tween 170 and 230 C. (containing phenols), by heating to 100 C. 
with aqueous 40 per cent formaldehyde and a basic catalyst, such as 
caustic soda, pyridine, trimethylamine, or tri-ethylamine, until three 
layers are formed. The upper layer consists of neutral oils and 
unaltered phenols, the middle layer is aqueous, whereas the lower 
layer consists of phenolic resins. 84 

Coal-tar pitch may be treated with chlorine in the presence of 
a chlorine carrier, which serves to increase its lustre, hardness and 
fusing-poirit, resulting in a product which resembles asphalt. 85 An 
asphalt-like product may also be obtained by mixing coal-tar pitch 
either with the insoluble constituents precipitated from coal tar by 
treatment with benzol, or with cumarone resin which has been 
heated to 270 C .*' 

A process of cracking at 510-750 C. in a tube-still serves to 
convert coal tars into a product which sulfonates completely upon 
digesting with H 2 SO 4 . 87 

The percentage of free carbon in coal tars and coal-tar pitches 
may be increased by heating under pressure between 700 and 
820 R* 8 

The following pitches are produced in small amounts, princi- 
pally in Germany, as by-products in the refining of coal-tar deriva- 
tive^: 

Anthracene Pitch. (Anthracene-oll-tar Pitch}. This is ob- 
tained as^a residue upon the purification of anthracene by distilla- 
tion^ and is characterized by being hard, black and glossy. Anthra- 
cene pitch may be hardened by heating with sulfur, or with spent 
irbn oxide obtained in the purification of coal gas. 90 Anthracene 



XVII NAPHTHOL AND CRESOL PITCHES 377 

pitch may be used for various purposes, including briquette 
binders. 91 

Naphthol Pitch. This is obtained in the refining of betanaph- 
thol or naphthylamine. 92 It is a glossy black solid, fusing at about 
120 C, and is almost completely soluble in solvent naphtha (xylol) 
chloroform and pyridine. Upon boiling with aqueous caustic soda 
it yields naphthol, which may be identified qualitatively. Its f using- 
point may be increased by heating with formaldehyde in the pres- 
ence of a mineral acid, 93 and a rubber-like product is obtained upon 
fluxing with a vegetable oil and adding fillers. 94 Naphthol pitch 
may be used in the manufacture of lacquers and for molding com- 
positions. 95 Naphthylamine pitch is obtained as a by-product in the 
refining of naphthylamine. 

Cresol Pitch. This is obtained as a residue in the distillation of 
crude cresol, and is known in Germany under the names "Karbol- 
pech," "Kresolharz" and "Phenolpech." It has a fusing-point of 
60 to 80 C., a decided cresol odor on heating and a brownish-black 
color. It is more or less soluble in aqueous caustic potash and al- 
most completely soluble in alcohol and mixtures of alcohol and 
benzol. 98 It is similarly used in the manufacture of lacquers. 



CHAPTER XVIII 
WATER-GAS AND OIL-GAS TARS AND PITCHES 

Water-gas tar, oil-gas tar and their corresponding pitches are 
not classified with "coal tar" and "coal-tar pitch/' as they are inter- 
mediate in their properties between the latter and petroleum 
asphalts, on account of the petroleum products used in their manu- 
facture. They are accordingly included in a separate chapter. 

Carburetted Water-gas Tar. The mechanism of this process 
has already been briefly described. A modern water-gas plant hav- 






Generator Carbureter , Superheater 



Scrubber Condenser 



FIG. 117, Lowe Water-gas Plant. 

ing a capacity of 1 1 / 2 to 3 million cubic feet of gas per day is illus- 
trated diagrammatically in Fig. 117. This is known as the Lowe 
type of apparatus. Either anthracite coal or coke may be used as 
fuel. The fuel is charged into the generator and allowed to under- 

378 



XVIII CAREURETTED WATER-GAS TAR 379 

go partial combustion by admitting a limited amount of primary air 
through the pipe A below the bed of fuel. The gases then pass 
downward through the carbureter and the combustion almost com- 
pleted by means of a carefully regulated supply of secondary air 
introduced through the valve B. From the carbureter the products 
pass upward through the superheater, where the temperature may 
be controlled by admitting a tertiary supply of air through the valve 
C ) and the products of combustion finally passed into the atmos- 
phere through the stack D. 

When the fuel in the gas-generator has been properly ignited, 
and the carbureter and superheater brought to the required tem- 
peratures, the air blasts are cut off in the sequence : C, B, and A 9 and 
the stack valve D closed. Steam is introduced into the generator 
through the valve E below the bed of incandescent fuel and results 
in the production of "blue-gas," according to the following reaction: 
C + H 2 O = CO + H 2 . This is passed into the carbureter where 
it mingles with a spray of carbureting oil consisting of "gas oil" or 
"fuel oil" introduced through F. The mixture is passed downward 
through the carbureter whereby the oil becomes vaporized. Frorri 
the carbureter, the gases are passed up through the superheater, the 
temperature of which is very carefully regulated at 1200-1300 F. 
to crack the oil vapors into permanent gases, and this incidentally 
results in the formation of tarry matters. 

The formation of carbon monoxide and hydrogen by the action 
of steam on incandescent fuel results in a lowering of the tempera- 
ture, on account of the absorption or storing up of thermal energy, 
so that it becomes necessary to turn off the steam and reintroduce 
the air. The "blowing up" process is then repeated. At the same 
time the oil spray is turned off the carbureter, as its temperature has 
fallen to a point below which the oil would not be superheated suffi- 
ciently to convert it into a permanent gas. The "blowing" or "up 
run" lasts three to five minutes, and the "gas making" or "down 
run" lasts two to four minutes. 

The water-gas and accompanying tarry vapors derived from 
the gas oil are passed from the superheater through the pipe G into 
a wash-box which corresponds to the hydraulic main in a coal-gas 
plant The vaporization of water in the wash-box reduces the 
temperature of the gases from 1200 to 190 F. The gases next 



380 WATER-GAS AND OIL-GAS TARS AND PITCHES XVIII 

pass upward through a scrubber and are then passed downward 
through a water-cooled condenser which reduces their temperature 
to 140-150 F., and thence into a relief gas-holder. Most of the 
tar is condensed in the wash-box and smaller quantities in the scrub- 
ber and condenser. An exhauster draws the gases through the fore- 
going train of apparatus and then forces them through a tar extrac- 
tor, to remove the last traces of tar* The temperature of the gases 
as they pass through the tar extractor is in the neighborhood of 
110-115 F. They are finally passed through the purifier filled 
with trays of ferric oxide to remove the sulfur compounds, and 
thence into the main gas holder. 

The carbureting oil, known also as "gas oil" or "enriching oil" 
varies in composition, depending upon the character of the petro- 
leum from which it is derived. Experience demonstrates that oils ob- 
tained from a paraffin-base petroleum generate the greatest propor- 
tion of gas and the smallest quantity of tar. Oils containing unsatu- 
rated straight-chain hydrocarbons are less efficient, and those con- 
taining unsaturated ring hydrocarbons are almost valueless. The 
yield of tar expressed in percentage by volume, based on the various 
types of petroleum used, is as follows: 

Paraffin-base naphtha 2- 4 per cent 

Paraffin-base gas oil 6-10 per cent 

Paraffin-base crude oil 8-12 per cent 

Asphaltic-base gas oil 10-15 P er cent 

Asphaltic-base crude oil 12-18 per cent 

The quantity of carbureting oil ordinarily used varies from 2.5 
to 4.5 gal. per 1000 cu. ft. of gas manufactured, depending upon the 
statutory requirements in the territory where the gas is distributed, 
as to its illuminating and heating values. 

Properties of Water-Gas Tar. On account of the low specific 
gravity of water-gas tar, it readily forms an emulsion with the as- 
sociated water and separates with great difficulty. The water thus 
retained may run as high as 85 per cent and the greater the per- 
centage of water present, the more viscous will be the emulsion. 1 
The water is practically free from ammonia compounds, thus differ- 
ing from coal tar, and the tar is very much thinner in consistency, 
containing but a small amount of free carbon. The methods for 
dehydrating crude water-gas tar are similar to those used for coal 



XVIII , PROPERTIES OF WATER-GAS TAR 381 

tars. The dehydrated water-gas tar complies with the following 
tests : 

(Test i) Color in mass Black 

(Test la) Homogeneity to the eye Uniform 

(Test 2^) Homogeneity under microscope Absence of carbonaceous 

matter 

(Test 7) Specific gravity at 77 F x.oo~i.x8 

(Test 8) Viscosity at 212 F. (100 cc.) 25-50 

(Test i5<r) Fusmg-point (cube method) Less than o to 10 F. 

(Test 1 6) Volatile matter at 50x3 F., 5 hrs 60-85 per cent 

(Test 1 6) Distillation: 

By weight 

Up to 1 10 C. (Naphtha) o - 5 per cent (Sp. gr. o. 85-0. 90) 

iio-i7oC (Light oils) 0.5- 5.0 per cent (Sp. gr. 0.88-0.90) 

170-235 C. (Middle oils) 5 ~35 per cent (Sp. gr. o. 98-1 .00) 

235-270 C. (Heavy oils) 7-30 per cent (Sp. gr. i .00-1 .07) 

270-350 C. (Anthracene oil) . . 10 -25 per cent (Sp, gr. 1 . 07-1 . 10) 
Residue (Water-gas-tar 

pitch) ... 20 -70 per cent 

(Test 17*) Flash-point Low 

(Test 19) Fixed carbon 10-20 per cent 

(Test 21) Solubility in carbon disulfide 95 -100 per cent 

Non-mineral matter insoluble 0.2- 5 per cent 

Mineral matter o - \ per cent 

(Test 22) Carbenes o - 2 per cent 

(Test 23) Solubility in 88 petroleum naphtha 20 - 75 per cent 

(Test 26) Carbon 90 - 95 P^r cent 

(Test 27) Hydrogen 3 - 6 per cent 

(Test 28) Sulfur o. 5-2.0 per cent 

(Test 29) Nitrogen o. 5-1 .o per cent 

(Test 30) Oxygen i - 2 per cent 

(Test 32) Naphthalene Less than 10 per cent 

(Test 33) Solid paraffins o - 5 per cent 

(Test 34^) Sulfonation residue i - 25 per cent 

(Test 37*) Saponifiable constituents Tr. - 2 per cent 

(Test 39) Diazo reaction Yes 

(Test 40) Anthraquinone reaction Yes 

Water-gas tars consist principally of aromatic hydrocarbons and 
contain less naphthalene than coke-oven tars, negligible phenols and 
bases, also small amounts of solid paraffins and considerable naph- 
thalenes. According to Downs and Dean, 2 water-gas tar contains 
substantial amounts of benzene, toluene, xyienes, naphthalene and 
anthracene. The nitrogenous bases and phenols are absent or 
nearly so. Weiss reports further that the percentage of free carbon 
varies from 1.04 to 1.087 per cent, with water-gas tars ranging in 
specific gravity from i. 078-1. 090.* Water-gas tar may be vulcan- 
ized by heating with 5 to 8 per cent of sulfur. 4 



382 



WATER-GAS AND OIL-GAS TARS AND PITCHES 



XVII] 



Oil-gas Tars. These are manufactured from petroleum alon< 
without the use of coal or coke. Several methods have been used 
all embodying the same principle but differing in detail, the mosl 
important of which are as follows: 

Pintsch Gas. This is manufactured by spraying gas-oil derived 
from petroleum in a closed retort constructed of iron or fire clay and 
heated to a temperature of 900 to 1000 C. by combustion of oil, 
gas or tar underneath. The shape of the retort is shown in Fig. 
1 1 8. The vapors pass to the rear and thence downward and through 
a lower chamber into the hydraulic main in front The gases are 
passed successively through a scrubber, condenser and purifier. 




O/J and Sfectm 




Oilond 
Steam 




FIG. 1 1 8. Pintsch Gas Retort 



fffiffi^"$^^ 
FIG. 119. -Oil-water Gas Plant. 



Pintsch gas is used extensively for railroad and buoy lighting. It 
may be stored in holders under a pressure of 5 to 25 atmospheres, 
without suffering in illuminating power, as would prove to be the 
case with most other gases adapted for lighting purposes. 

About 10 per cent tar is recovered in the rintsch process, the 
characteristics of which will be described under the heading "oil-gas 
tar" below. 

Oil-water Gas. This process is used almost exclusively on the 
Pacific coast for manufacturing illuminating gas, owing to the ab- 
sence of coal deposits. The installation is shown diagrammatically 
in Fig. 119, and operates similar to a water-gas plant, except that 
petroleum is used instead of coal or coke. 

It requires about 8 to 8j^ gal of fuel oil per 1000 cu. ft of gas 



XVIII REFINING OF WATER-GAS AND OIL-GAS TARS 383 

(550625 B.t.u.) of which about one-fifth is required for heating 
and four-fifths for gas-making. Higher temperatures are used for 
cracking than is the case in the manufacture of Pintsch gas or Blau 
gas, in consequence of which heavier tars are obtained, higher in 
free carbon and aromatics. 

Oil-water-gas tar has also been termed "fuel-oil gas tar" and 
"reformed-gas tar." 5 At room temperatures it has a soft, semi- 
solid to almost solid consistency. Those produced at medium tem- 
peratures have a specific gravity at 60 F. of 1.15 to 1.20; insoluble 
in benzol 12 to 15 per cent; sulfonation residue 2 to 5 per cent. 
Those produced at high temperatures have a specific gravity at 
60 F. of 1.30 to 1.35; insoluble in benzol 25 to 40 per cent; sul- 
fonation residue less than 0.5 per cent. 

Blau Gas. This is a further development of Pintsch gas, and is 
made by cracking oil vapors at a temperature lower than in the 
Pintsch process (i.e., 550 to 600 C.), but in a similar form of re- 
tort. The resulting gases are first purified by passing in the usual 
manner through hydraulic mains, coolers, cleaners and scrubbers to 
remove the tar, which amounts to 4-6 per cent of the oil used, and 
then compressed in a three- or four-stage compressor to 100 atmos- 
pheres, which causes the high boiling-point constituents to liquefy 
and absorb a large proportion of the non-liquefiable gases. The 
excess of the latter is used for running the compressor and heating 
the retorts. 

The compressed Blau gas is so constituted that upon releasing 
the pressure, the dissolved and liquefied constituents are evolved in 
such proportions that the composition of the gaseous mixture re- 
mains constant. Blau gas is used principally for marine lighting 
purposes and is transported in cylinders of about I cu. ft capacity, 
carrying 20 Ib. of the compressed gas, which will expand to about 
250 cu. ft at atmospheric pressure. Its illuminating value is 
greater than that of Pintsch gas. 

The tar recovered from the Blau gas process (about 1520 
per cent), is similar in its physical and chemical properties to the 
oil-gas tars described previously. 6 

Properties of Oil-gas Tars. Dehydrated oil-gas tars produced 
by the Pintsch process, the Blau gas process, and the oil-water gas 
process comply with the characteristics given on the following page* 

Oil-gas tar may be vulcanized by heating with sulfur, 7 or by 
treating with sulfur dichloride. 8 

Refining of Water-gas and Oil-gas Tars. Oil-gas and water- 
gas tars when suitably dehydrated may be distilled in accordance 
with the methods used for "coal tar." Sometimes, either water-gas- 



384 



WATER-GAS AND OIL-GAS TARS AND PITCHES 



XVIII 





Oil-gas Tars 


Low Temperature 
(Pintsch- and Blau- 
gas Tars) 


I 
High Temperature 
(Oil-water-gas Tars) 


(Test i) Color in mass. * 


Black 

Uniform 
Comparatively free 
from carbonaceous 
matter. 
0,95-1,10 
25-50 
o 


Black 
Gritty 
Contains consider- 
able carbonaceous 
matter. 

i.iS-i-35 
Over 50 
o to 5 

30-100 F. 


(Test id) Homogeneity to the eye 


(Test 2^) Homogeneity under microscope. 


(Test 7) Specific gravity at 77 F 


(Test 8*) Viscosity at 212 F. (100 ml.) 


(Test 9*:) Consistency at 77 F 


(Test 15^) Fusing-point (R. & B, method) 


(Test 15^) Fusing-point (Cube method) . . .* 


<0-20F. 

35-70 per cent 
30-75 per cent 


(Test 1 6) Volatile at 500 F. in 5 hrs. . . 


25-50 per cent 

20-50 per cent 
1.05-1.12 
50-80 per cent 
ioo-i5oC. 
Low 
15-35 percent 
70-90 per cent 
10-30 per cent 
0-0.5 per cent 
0-2 per cent 
25-70 per cent 
< i per cent 
1-2 per cent 
0-5 per cent 
Trace 
Trace to 10 per cent 
Trace 
Yes (marked) 
Yes 


(Test 1 6b) Distillation Test: 
Distillate to 315 C. (vol.) 


Sp. gr. ditto at 6o/6o C 


Residue at 31 5 C. (wt.) 


25-70 per cent 


Fusing-point ditto (R. & B. method) . 
(Test 170) Flash-point . , 


Low 

10-25 per cent 
99-100 per cent 
0-0.2 per cent 
0-0.5 per cent 
0-2 per cent 
50-85 per cent 
< i per cent 
1-2 per cent 
Trace 
0-5 per cent 
20-40 per cent 
Trace 
Yes (slight) 
Yes 


(Test 19) Fixed carbon 


(Test 2i) Soluble in carbon disulfide 


Non-mineral matter insoluble ........ 


Mineral matter 


(Test 22) Carbenes 


(Test 23) Soluble in 88 petroleum naphtha 
(Test 28) Sulfur 


(Test 30) Oxygen . . . * 


(Test 32) Naphthalene 


(Test 33) Solid paraffins 


(Test 34^) Sulfonation residue 


(Test 37*) Saponifiable constituents 


(Test 39) Diazo reaction 


(Test 40) Anthraouinone reaction 





tar pitch or oil-gas-tar pitch is mixed with coal-tar pitch in suitable 
proportions. 

Properties of Water-gas-tar Pitch and Qil-gas-tar Pitch. Water- 
gar-tar and oil-gas-tar pitches may be distinguished from coal-tar 
pitches by: 

(1) The small percentage of "free carbon" (non-mineral mat- 
ter insoluble in carbon disulfide). 

(2) The possible presence of paraffin wax (when non-asphaltic 
or semi-a&phaltic petroleums are used). 

On the other hand, water-gas-tar pitch may be distinguished 
from oil-gas-tar pitch by the following: 



XVIII WATER-GAS-TAR PITCH AND OIL-GAS-TAR PITCH 



385 



1 I ) Lower specific gravity of water-gas-tar pitch. 

(2) Larger percentage of sulfonation residue from oil-gas-tar 
pitch. The sulfonated constituents are soluble in water, which 
serves to differentiate them from lignite- and shale-tars and pitches. 

Water-gas-tar and oil-gas-tar pitches comply with the following 
tests : 





Water-gas-tar 
Pitch 


Oil-gas-tar 
Pitch 


(Test |} Color in mass . 


Black 
Uniform 
Small amount o 
Variable 
Conchoidal 
Bright 
Black 
1.10-1.25 

O-IOO 
>IQO 

Variable 
Variable 
80-275 F. 
100-300 F. 
110-320 F. 

5-i5 
300-400 F. 

25-45 
75-98 
2-25 
o-* 

5-10 

50-70 

<4 
0-2 

0-5 
0-15 

O-I 

Yes (*) 
Yes 


Black 
Uniform 
f carbon visible 
Variable 
Conchoidal 
Bright 
Black 
I.I5-I-35 

O-IOO 
>IOO 

Variable 
Variable 
80-275 F. 
100-300 F. 
i 10-320 F, 
5-15 
300-400 F. 
20-35 
70-98 
2-30 
o~i 
5-10 

60-80 
<4 

O-2 

0-5 
20-40 

O-I 

Yes (*) 
Yes 


(Test 20) Homogeneity to the eye 


(Test 2^) Homogeneity under the microscope 




(Test 4) Fracture 


(Test 5) Lustre 


(Test 6) Streak 


nVt V\ Snecific crravitv at *77 F 


(Test 9^) Penetration at 77 F i . . 


(Test (\\ Susceptibility index 


(Test 10) Ductility 


(Test n) Tensile strength at 77 F 


(Test 1 50) Fusing-point (K. and S. method) 


(Test i$b) Fusing-point (R. and B. method) 


(Test i 5^) Fusing-point (cube method) 


(Test 1 6) Volatile matter 500 F., 5 hrs. (per cent) . . 
(Test 170) Flash-point 


(Test 19) Fixed carbon (per cent) 


(Test 21) Solubility in carbon disulfide (per cent) 
Non-mineral matter insoluble (per cent) 
Mineral matter (per cent) ...,.,,,,,, 


(Test 22) Carbencs (per cont) . 


(Test 23) Solubility in 88 petroleum naphtha (per 
cent) 


(Test 28) Sulfur (per cent) 


rryjt -30^ Oxvcren (oer cent} 


(Test 33) Solid paraffins (per cent) 


(Test 34^) Sulfonation residue (per cent) ............ 


(Test 37^) Saponifiable matter (per cent) 


(Test **(\\ Diazo reaction ......... , , 


(Test 40) Anthratjuinone reaction ............ r , n r - 





Slight contain but a trace of phenols. 



Both of these pitches are largely susceptible to changes in tem- 
perature, they are highly resistant to the prolonged action of mois- 
ture, and they are adapted for manufacturing low-priced solvent 
paints because of their ready solubility in "coal-tar naphtha/' 



CHAPTER XIX 
FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH 

These are classified together because all are derived from sub- 
stances containing animal or vegetable fats or oils, although in 
manufacturing bone tar and bone-tar pitch the crude materials carry 
but a small proportion. 

FATTY-ACID PITCH 

Various generic terms have been used to designate this prod- 
uct, including candle tar, "Kerzenteer" (German) "goudron" 
(French), candle pitch, fat pitch and "Fettpech" (German). Spe- 
cific names have also been applied, descriptive of the raw materials 
used in producing the pitch, such as stearin pitch, palm-oil pitch, 
bone-fat pitch, cotton-seed-oil pitch, cotton pitch, cotton-stearin 
pitch, cotton-seed-foots pitch, corn-oil pitch, corn-oil-foots pitch, 
packing-house pitch, garbage pitch, sewage pitch, fullerVgrease 
pitch, wool pitch, wool-grease pitch, wool-fat pitch, cholesterol 
pitch, cotton-oil pitch, cotton-seed-oil-foots pitch and stearin-wool 
pitch. 

The fatty-acid pitches are obtained as by-products in the follow- 
ing manufacturing processes : 

( i ) Production of candle and soap stocks. 

(2) Refining vegetable oils by means of alkalies. 

(3) Refining refuse greases. 

(4) Treatment of wool grease. 

The raw materials used include the vegetable oils and fats, ani- 
mal oils, fats and waxes (wool grease), also the waste greases de- 
rived from the foregoing. Vegetable and animal fats and oils are 
combinations of the fatty acids with glycerin, known as "triglycer- 
ides," and illustrated by the following generic formula, in which "R" 
represents any fatty acid radicle: 



C 3 H 5 eOR 
N OR 



XIX FATTY-ACID PITCH 387 

Fats and oils may be purified or refined in two ways : 

(1) By treating vegetable oils with a small amount of caustic 
soda to remove the coloring matter, free fatty acids and other im- 
purities, without, however, breaking up the triglycerides. This 
process is used for refining vegetable oils when they are to be used 
for edible purposes. The residue is treated with mineral acid to 
break up the soaps, and then distilled with steam to recover the 
fatty acids, whereupon a residue of fatty-acid pitch is obtained. 

(2) By decomposing or "hydrolyzing" the triglycerides into 
glycerin and free) fatty acids, and then distilling the latter with 
steam, whereby fatty-acid pitch is obtained as a residue. The object 
of distilling the fatty acids is to improve their color or odor and 
thereby adapt same (a} for the manufacture of candles (which are 
commonly light-colored or white), or (b] for manufacturing soaps 
(such as toilet soaps, etc.) which must be odorless and preferably 
light-colored. 

Production of Candle and Soap Stocks. These are obtained 
from various animal and vegetable oils and fats, also from waste 
greases. It is always necessary to subject the fatty acids to a proc- 
ess of hydrolysis and steam distillation for producing candles, but 
not for manufacturing soaps, unless the fatty acids are too dark in 
color for the character of soap required or possess a disagreeable 
odor, in which event they are purified by distillation. Various 
methods of hydrolysis may be used, but they all depend upon the 
same reaction, in which the triglyceride combines with water and 
decomposes into glycerin and fatty acids, as illustrated in the fol- 
lowing equation: 

OR OH 

-OH 



C 3 H 5 A)R + 3H-OH - CaHsf-OH + jR-OH 
fc>OR X OH 

Triglyceride Water Glycerin Free Fatty Acid 

(fat or oil) 

It is necessary to hydrolyze the fats or oils before distilling the 
fatty acids, since the triglycerides themselves are not capable of be- 
ing distilled without decomposition. The following methods of 
hydrolysis have been used: 

(a) Hydrolysis by Means of Water. Formerly, water alone 
was used for the purpose, the fat or oil being heated in an autoclave 
with 30 per cent of its weight of water at 220 Ib. pressure (corre- 
sponding to a temperature of 200 C.) for eight to twelve hours. 



388 FATTY-ACW PITCH, BONE TAR AND BONE-TAR PITCH XIX 

This decomposes the triglyceride into fatty acids and glycerin, but 
with water alone it is difficult to break down the fat completely. 
It has been found that the addition of 3 per cent of lime or mag- 
nesium oxide, and preferably the latter, assists the reaction and 
produces a larger yield of a better product, and at a much lower 
temperature. Accordingly, the fat or oil is heated at 120 Ib. pres- 
sure in a horizontal or vertical cylindrical vessel provided with 
a stirring device, with 20 to 25 per cent by weight of water and 
3 per cent of lime or magnesium oxide. The breaking down of 
the fat is practically complete at the end of eight to ten hours, and 
in addition the color is very much better, as there is less decom- 
position, due to the lower temperature employed. The fats or oils 
used for this purpose may consist of animal or vegetable tallow, 
palm oil, bone fat, lard- or cotton-seed stearin (crystallized at low 
temperatures from lard or cotton-seed oil respectively), shea butter, 
etc. 

At the end of the process, the free fatty acids rise to the sur- 
face and are skimmed off, leaving the aqueous liquor containing the 
glycerin (together with the hydrated lime or magnesia, when the 
Fatter are used). The glycerin is recovered by a special process 
which, however, does not fall within the scope or this treatise. The 
fatty acids are subjected to steam distillation to deodorize and 
whiten them, also to purify them by separating any non-hydrolyzed 
fat The fatty acids are run into lead-lined tanks w r here they are 
first treated with dilute sulfuric acid to remove any traces of mag- 
nesium oxide, etc., then washed with water, heated to expel the 
moisture, after which they are fed into a retort and distilled with 
superheated steam with or without the use of vacuum. The fatty 
acids suitable for distillation should not contain more than 5 per 
cent of non-hydrolyzed fat (neutral fat) nor more than 0.2 per cent 
of mineral matter. To obtain a distillate of good quality, care 
should be taken not to distil the fatty acids at too high a tempera- 
ture, as they are extremely susceptible to overheating and decom- 
position into dark-colored hydrocarbons (unsaponifiable), which 
would, of course, depreciate the value of the product. 1 The still 
should be constructed so that the flames will not come into direct 
contact with the bottom and cause local overheating. The tem- 
perature of the material in the still should preferably be maintained 
between 230 and 250 C, and although in certain instances it is 
permissible to reach a temperature of 270 C., under no circum- 
stances should this be exceeded. 

Two methods are used for conducting the distillation. The 
first consists in continuously replacing the tatty acids as they distil, 
with an equivalent quantity of undistilled material, as long as the 
distillate snows a satisfactory color and is free from unsaponifiable 



XIX 



FATTY-ACW PITCH 



389 



hydrocarbons. The effect of the distillation is to concentrate the 
impurities and unsaponified (neutral) fats or oils in the still. A 
typical installation is illustrated in Fig. I20. 2 

The heating element in the still, a, consists of two copper coils 
of approximately 270 square feet (25 square meters) mean sur- 
face. Steam at about 450 pounds per square inch (32 kg. per 
sq. cm. ) gage pressure is supplied by a motor-driven compressor, b. 
Vacuum is maintained at 7 to 10 mm, of mercury by use of steam 
ejectors, c. Approximately 10,000 pounds (4536 kg.) of crude 
fatty acid are charged to the still at the start of a run, and there- 



To Primary 

Evacuating 

System 




FIG. 120. Distillation of Fatty Acids. 

after for about 20 hours the feed is continuous to maintain an even 
level. The crude stock going to the still is preheated by passing 
through a heat exchanger, d, which also serves as a partial con- 
denser for the fatty acid vapors. Most of the distillate is con- 
densed in the jacketed coolers, e. A small amount of stock is con- 
densed and baffled out in separator / and measured in receiver g. 
The bulk of the distillate is received in h and pumped out, under 
vacuum, to storage. The residue in the still a consists of soft fatty- 
aqid pitch. 

The second method consists in replacing the distilled fatty acids 
for but sixteen to twenty-four hours, then discontinuing the addi- 



390 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

tion, and distilling the contents of the retort until the distillate 
ceases to be of suitable quality, as is evidenced by a change in its 
color. The residue consisting of soft fatty-acid pitch is then drawn 
off into a separate still known as the 4< pitch still," the first still 
recharged, and the process repeated, until after a sufficient number 
of distillations, a sufficient quantity of soft fatty-acid pitch accu- 
mulates for further treatment. It is claimed that the second 
method gives better results and yields a distillate lighter in color, 
containing a smaller percentage of hydrocarbons. 

In either case the soft residue is distilled separately with super- 
heated steam and vacuum. When the neutral fats increase in con- 
centration to 12 to 15 per cent they commence to decompose into 
hydrocarbons, some of which distil with the fatty acids and some re- 
maining with the residue. On distillation, the saturated fatty-acids 
pass over first and the residue contains an increasing proportion of 
unsaturated and hydroxy-acids, such as hydroxy-stearic acid, which 
at higher temperatures is converted into iso-oleic acid. At still 
higher temperatures the fatty acids are converted into hydro-car- 
bons, which are principally unsaturated. The final residue consti- 
tutes the so-called "fatty-acid pitch" which amounts to between 2.5 
and 5 per cent of the fatty-acids distilled. 

(b) Hydrolysis by Means of Concentrated Sulfuric Acid? The 
fats or oils are first freed from moisture by heating to a tempera- 
ture of 120 C. It is essential that all the moisture be removed to 
prevent excessive decomposition. The mass is then rapidly mixed 
with 4 to 6 per cent of concentrated sulfuric acid (66 to 67 Be.) 
and heated in a cylindrical vessel provided with a mechanical agi- 
tator. The heating is continued just long enough to break up the 
triglycerides and no longer. The sulfonated mass is then imme- 
diately run into boiling water and agitated by a steam jet until the 
sulfonated acids hydrolyze. The mass is then allowed to stand 
quietly until the free fatty acids rise to the surface, leaving the 
glycerol and sulfuric acid in the lower layer. 

The fatty acids produced in this manner are dark colored and 
must be distilled. They are first washed with water until neutral, 
then heated to expel the moisture and finally distilled with super- 
heated steam, with or without a vacuum as previously described, 
whereupon a residue of soft fatty-acid pitch is obtained. According 
to modern practice, this residue is again treated with concentrated 
sulfuric acid to hydrolyze any neutral fats remaining, and inci- 
dentally remove the accumulated mineral matter (including any 
copper or iron derived from the stills). It is then washed free from 
the acid and redistilled, leaving a residue of medium to hard fatty- 
add pitch. The dark-colored distillate, known as "still returns," 



XVIII FATTY-ACID PITCH 391 

is worked up in small quantities with the crude fatty acids under 
going their first distillation. 

The yield of stearin known in this case as "distillation stearin" 
is greater than that obtained in the aqueous process of hydrolysis, 
due to the fact that some of the olein (in this case known as "dis- 
tillation olein" or "distilled olein") is converted into a solid prod- 
uct (consisting of stearolactone, isomeric oleic acid, etc.). The 
olein and stearin are separated by cooling, exactly as in the fore- 
going process, A smaller yield of glycerin is obtained due to its 
partial decomposition by the acid, and that of fatty-acid pitch is 
also less and of a darker color. 

To avoid losing the glycerin, which constitutes one of the most 
important and highest priced products, a "mixed process" is now 
used consisting of a combination of the foregoing. ^ 

(c) Hydrolysis by the "Mixed Process" This is a combina- 
tion of the two foregoing processes, and consists in first hydrolyz- 
ing the fats or oils in an autoclave with water and an alkaline accel- 
erating agent (such as lime or magnesium oxide), and in this way 
recovering the full amount of glycerin. The resulting fatty ^ acids 
are dehydrated and treated with concentrated sulfuric acid in ac- 
cordance with process (b) to increase the yield of stearin and com- 
plete the hydrolysis of any neutral fat which may have escaped the 
first treatment, and thus minimize the formation of hydrocarbons 
in the distillate, 

(d) Hydrolysis by Means of Sulfo-compounds. This process, 
known as the E. Twitchell method, is rapidly replacing the others, 
and is now employed in soap factories for treating the fats or oils 
before soap-making, as it separates a purer glycerin and at the same 
time results in a greater yield (88 to 90 per cent of the theoretical 
quantity contained in the fat or oil w. 80 to 84. per cent obtained 
in the direct caustic soda saponification method for soaps). More- 
over, the liquor separated in the Twitchell process is not contami- 
nated with the sodium chloride used for "salting out" the soap in 
the ordinary method, and it contains 15 per cent by weight of gly- 
cerin against 3 to 4 per cent in the liquor obtained on direct saponi- 
fication of the fats or oils with sodium hydroxide. The former 
therefore effects a saving in evaporation. 

The fat or oil is first purified by steaming with I per cent of 
60 Be, sulfuric acid for about two hours. It is then transferred 
to a wooden vessel equipped with perforated steam pipes, also a 
well-fitting cover to exclude air which would cause the fatty acids 
to darken, and mixed with 50 per cent water and 1.5 per cent of the 
Twitchell reagent The latter is prepared by allowing an excess of 
sulfuric acid to act on a solution of naphthalene (or other aro- 



392 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

matic hydrocarbon) in oleic acid, which results in the production 
of a body having the general composition: 



/SOaH 
6 < 
X 



CioHe 

Naphthalene-sulf o-stearic acid. 

It is advisable to introduce a small percentage of free fatty acids 
to start the hydrolysis which otherwise takes a little time to begin. 
The material is steamed for twenty-four hours, whereupon a small 
quantity (o.i to 0.2 per cent) of 60 Be. sulfuric acid is added to 
break up the emulsion and permit the fatty acids to rise to the sur- 
face and the glycerol to pass into the aqueous liquor below. About 
0.05 per cent of barium carbonate is finally added to neutralize the 
mineral acid. 

The resulting fatty acids are dark in color and must be distilled. 
This is usually affected after a preliminary treatment with concen- 
trated sulfuric acid as in method (b) to increase the yield of stearin, 
which is of special importance when the product is to be used for 
manufacturing candles. The yield is the same as obtained from 
the saponification or mixed process respectively, depending upon 
the exact method of treatment. 

(e] Hydrolysis by Means of Ferments. This method is also 
meeting with some favor, as it produces a large yield of glycerin 
uncontaminated with salt or other solids difficult of separation. 
Many soap manufacturers accordingly hydrolyze their stock by 
means of ferments to separate the glycerin, and then saponify the 
resulting fatty acids with sodium carbonate, either directly, or after 
first purifying them by steam distillation. 

The ferment is derived from the castor plant by grinding the 
decorticated castor beans with water and filtering through cloth, 
whereupon a white creamy filtrate is obtained which is set to one 
side and allowed to ferment spontaneously. The ferment which 
rises to the surface is skimmed off and used while fresh. It is com- 
posed of a thick creamy substance containing approximately 38 per 
cent of fatty acids derived from castor oil, $8 per cent of water and 
4 per cent of an albuminoid substance containing the active material. 

The fat or oil to be treated is mixed with 40 per cent water, 5 
to 8 per cent of the ferment and 0.2 per cent of manganese sulfate 
in a lead-lined vessel equipped with a steam coil and a perforated 
compressed-air pipe. Heat is then turned on, and the temperature 
maintained 2 to 3 C. above the melting-point of the fat or oil. 
The mass is agitated by air introduced through the perforated pipe 
and the treatment continued one to three days until the hydrolysis 



XIX FATTY-ACID PITCH 393 



is complete. Sufficient steam is then turned on to bring the mass 
to a temperature of 80 to 85 C, whereupon 0.30 to 0.45 per cent 
of 50 per cent of sulfuric acid is stirred in by air. This breaks up 
the emulsion, the clear fatty acids rising to the top and the aqueous 
liquor containing the glycerin settling to the bottom. 

When the separated fatty acids are pale in color they may be 
saponified directly for manufacturing soaps. Where dark-colored 
fats, oils or greases have been employed, which result in the produc- 
tion of dark-colored fatty acids, the mass is distilled with steam, 
whereupon the fatty-acid pitch is obtained as residue. Candle stock 
may also be produced by subjecting the purified fatty acids to a low 
temperature and filtering, as described previously. 

It is, of course, understood that when the crude oils or fats (tri- 
glycerides) or the free fatty acids derived from them (by any of 
the foregoing processes of hydrolysis) are saponified directly with 
sodium carbonate (soda ash), no fatty-acid pitch is produced. 

Refining Vegetable Oils by Means of Alkali. Most vegetable 
oils intended for edible purposes, whether they are to be used for 
salad oils, lard substitutes, margarine manufacture, or directly for 
cooking oils and shortening, are first treated with caustic soda for 
the purpose of removing free acids, coloring matter, albuminous 
material, resins, etc. The oils chiefly treated are cotton-seed, corn, 
soya bean, cocoanut and peanut oils. 

(a) Refining Cotton-seed Oil. Crude cotton-seed oil when 
obtained fresh from the seed varies in color from reddish brown to 
almost black. This is due in part to the coloring matter, which is 
a dark resinous substance capable of combining with caustic soda, 
forming a water-soluble salt, also albumin and pectin bodies. The 
method of refining the oil consists in agitating it with varying quan- 
tities of caustic soda solution, the strength of which will range from 
i.io to i. 20 specific gravity, according to the percentage of free 
fatty acids present and the practice of the individual refiner. The 
agitation is effected by mechanical stirrers in large tanks provided 
with heating coils. The quantity of alkaline liquor added is deter- 
mined by careful laboratory tests and run in through perforated 
pipes. The effect of the alkali is first to darken the oil and appar- 
ently thicken it. After a short time small flakes begin to separate 
and heat is then applied. As the temperature increases, the flakes 
become larger, owing to the soap softening and running together. 
When the right point is reached, at temperatures varying from 100 
to 130 R, steam and agitation are shut off and the soap drops to 
the bottom of the kettle, forming a mucilaginous mass, varying in 



394 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

* 

color from yellow to brown, through all shades of green and red. 
This material is known as the "foots." The clear light yellow oil 
which is pumped off the foots is then refined further for edible pur- 
poses. Cotton-seed oil purified in this manner is known to the 
trade as "summer yellow oil/* When used in making lard substi- 
tutes it is bleached with fuller's earth and then deodorized, gen- 
erally by the use of steam. Salad oil is obtained by chilling the 
summer yellow oil s& as to crystallize out the palmitin which is 
separated by pressing or filtering. 

In the United States alone the annual production of cotton-seed 
foots amounts to approximately half a million barrels. The foots 
vary in gravity from 0.97 to 1.04, averaging about i.oo. They con- 
tain the soda salts of the coloring matter, the soda soaps of any free 
fatty acids present in the cotton-seed oil (30 to 45 per cent), the 
coagulated albumin (8 to 12 per cent), phytosteryl, and varying 
quantities of mechanically entrained cotton-seed oil (triglycerides). 

Cotton-seed foots are sold on the basis of "50 per cent fatty 
acid." As a matter of fact they contain between 35 and 65 per 
cent, averaging about 45 per cent. A representative sample con- 
tained : * 

Fatty anhydrides (corresponding to a "5o-per cent soap stock") 48. 50 per cent 

Glycerin 3-98 per cent 

Caustic soda (NaaO). 3- 20 per cent 

Foreign organic matter 5- 9 per cent 

Coloring matter 2.41 per cent 

Water 36.00 per cent 

Total * 100. oo per cent 

The cotton-seed foots may be converted directly into soap by 
boiling up with a small excess of caustic soda and "salting" it put 
in the usual manner, when no pitch will be obtained. The resulting 
soap is known as "killed foots" and the dark lye containing the 
coloring matter and impurities are run to waste. A process has also 
been described for recovering a shellac-like substance from cotton- 
seed foots by oxidizing with hydrogen peroxide in an alkaline solu- 
tion and acidifying to separate the fatty matter. 5 

Usually, however, the cotton-seed foots are subjected to distilla- 
tion. They are first boiled with sufficient alkali to complete the 
saponification and then treated with mineral acid to liberate the 
fatty acids. Or the foots may be acidified while hot with dilute 
sulfuric acid, whereupon a "black grease" containing about 90 per 
cent of the total fatty acids (calculated as oleic) rises to the sur- 
face. This is separated and subjected to the Twitchell or other 
hydrolyzing processes to break up any neutral fat and recover all 



XIX FATTY-ACID PITCH 395 

the glycerin. The fatty acids obtained in this manner are equiva- 
lent to 7,5 to 8.5 per cent of the original weight of the cotton-seed 

011 used. They are subjected to vacuum distillation with super- 
heated steam to separate the pure fatty acids from the residue of 
fatty-acid pitch, variously called "cotton pitch," "cotton-oil pitch/' 
" cotton-seed-oil pitch," "cotton-stearin pitch," "cotton-seed-oil-foots 
pitch," etc. The quantity of pitch produced will range between 10 
and 20 per cent of the weight of the crude fatty acids (black 
grease) distilled, which is equivalent to i to 2 per cent by weight 
of the original cotton-seed oil. The yield will depend upon the 
degree the oil is saponified, the amount of impurities present, the 
efficiency of the distilling apparatus and the extent to which the dis- 
tillation is carried. The still generally used holds 3 to 5 tons and 
the distillation is conducted intermittently. Two types of conden- 
sers are used, viz.: (i) water-cooled and (2) air-cooled. From 
these the vapors are passed through another condenser in which a 
water spray removes the lower fatty acids. Any volatile fatty acids 
distil over first, followed by the free fatty acids of higher boiling- 
points. The decomposition of any neutral fat present into unsat- 
urated hydrocarbons and unsaturated fatty acids does not com- 
mence until the concentration of the neutral fat in the still reaches 

12 to 15 per cent 

The purified fatty acids recovered by distillation are used for 
manufacturing soaps. The fatty-acid pitch is usually soft in con- 
sistency, moderately stringy and of a pale brown color when exam- 
ined by transmitted light in thin layers. 

(b) Refining Corn Oil. Corn oil is sometimes refined by treat- 
ing with a small proportion of caustic soda in a manner similar to 
the method described for cotton-seed oil. Upon deodorizing the re- 
fined product with superheated steam under reduced pressure, while 
heated to a temperature of 400 F,, an edible product is obtained, 
used as a salad oil, also for cake and biscuit making. It may also 
be converted into a lard compound by a hydrogenation process. 
The corn-oil foots are treated by a method similar to the one used 
for refining cotton-seed foots. A pitch is obtained known as "corn- 
oil pitch," possessing a comparatively high fusing-point, character- 
ized by its rubber-like properties and lack of ductility. If the dis- 
tillation is carried too far, the pitch will actually solidify in the still 
and can only be removed with great difficulty. 

Refining Refuse Greases, (a) Refining Packing-house and 
Carcass-rendering Greases. "Tallow" is the name applied to the 
purified solid fat or "suet" obtained from cattle. It is used ex- 
tensively for producing soap and candle stock. The crude fat is 
first "rendered" by boiling with water in an open vessel to separate 



396 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

it from any albuminous matter or other impurities present, and then 
clarified by washing with weak brine. "Lard" is obtained by ren- 
dering the soft fats which surround the kidneys, intestines and backs 
of pigs. Tallow and lard may be used as such for manufacturing 
soaps, but for producing candles they must first be hydrolyzed and 
purified by steam-distillation. 

The waste meat scraps obtained from packing houses, also the 
carcasses of animals freed from the bones, are treated with steam in 
large digestors at a high pressure to separate the fat. When the 
cooking is complete, the batch is allowed to stand quietly to permit 
the grease to rise to the surface and the disintegrated meat-fibers 
to settle. The grease is skimmed off and mixed with any additional 
grease recovered from the settlings by filter-pressing. The residue 
is then converted into fertilizer, and the aqueous liquid used for 
making glue. The grease recovered from this process has a dis- 
agreeable odor and a dark color, and must be hydrolyzed and steam- 
distilled before it can be used for manufacturing either candles or 
soap. The residue from the steam distillation process, amounting 
to between 5 and 6 per cent of the grease, constitutes a variety of 
fatty-acid pitch having a light brown color when viewed in a thin 
layer and great ductility (unless the pitch is distilled too far). A 
packing-house grease has been extensively marketed in this country 
under the name of "yellow grease." 

(b) Refining Bone Grease. The bones recovered from pack- 
ing houses or carcass-rendering works are used for manufacturing 
glue, bone-black (used for decolorizing petroleum distillates), and 
fertilizer. Bones from the head, ribs and shoulder-blades contain 
12 to 13 per cent of fat, whereas the large thigh bones ("mar- 
rows") contain 20 per cent. The fat is extracted by breaking up 
the bones into small fragments and then either: 

1 i ) Treating with steam in an autoclave under a pressure of 
2 to 3 atmospheres, whereupon a portion of the fat separates and 
floats to the surface, the gelatin or glue goes into solution, and the 
mineral ingredients (calcium phosphate, etc.) remain as residue. 
From 8 to 9 per cent of fat (based on the dry weight of the bones) 
is recovered in this manner. 

(2) Extracting the dried bones with a volatile solvent such as 
naphtha, carbon tetrachloride, or benzol in a suitable apparatus. . A 
much higher percentage of fat is extracted in this manner, but the 
cost of operation is higher, due to unavoidable losses of solvent, and 
the odor of the product is very strong. 

In either event the extracted bone fat is first hydrolyzed by any 
of the foregoing methods and then steam-distilled, whereupon a 
variety of fatty-acid pitch, known as "bone-fat pitch," is recovered 
as residue, amounting to 5 to 6 per cent by weight of the bone-fat. 



XIX FATTY-ACID PITCH 397 

The product may be used for manufacturing soap, or after cooling 
and filtering, the "stearin" may be converted into candles, and the 
"olein" either used for manufacturing soap or else marketed as 
such for "wool oils." 

(c) Refining Garbage and Sewage Greases. The average city 
garbage as collected contains : 

Water 70-80 per cent 

Grease 3- 4 per cent 

Tankage 10-20 per cent 

Tailings (rubbish) , 3- 6 per cent 

. It is treated in a manner similar to that used for working up the 
refuse from packing houses and carcass-rendering establishments, 
namely by boiling in large digesters holding 8 tons for six hours 
under a pressure of 70 to 80 Ib. (Arnold-Egerton System), 6 This 
reduces the material to a pulpy mass, which is filter-pressed to re- 
move the water and grease. The residue, known as "tankage," is 
dried and ground for use as fertilizer. The filtrate is allowed to 
stand, whereupon the grease rises to the surface and is skimmed off. 
The grease, when dehydrated, has a dark brown color. It is hydro- 
lyzed to separate the glycerin, and the resulting fatty acids purified 
by steam-distillation to render them suitable for manufacturing soaps 
and candles. The residue, known as "garbage pitch," amounting 
to 5 to 7 per cent by weight of the garbage, has a dark color when 
viewed in a thin layer, and is quite susceptible to temperature 
changes. 

Sewage also carries a proportion of grease which is now often 
being recovered, especially in large cities. The sewage is first run 
into large tanks, where the solid matter known as "sludge" settles 
to the bottom. The precipitation may be accelerated by adding a 
small percentage of slaked lime. After drawing off the liquor, the 
sludge is treated with a small quantity of sulruric acid to break 
up any insoluble soaps, and then boiled in large digestors under 
pressure to hydrolyze the fats, and enable the grease to separate. 
The residue is dried and used as fertilizer. The grease is dehy- 
drated, then hydrolyzed and finally distilled with superheated steam, 
yielding about 25 per cent of a fatty-acid pitch known as "sewage 
pitch." The characteristics of this are similar to those of garbage 
pitch. The distillate contains about 50 per cent of liquid olein and 
50 per cent of solid stearin melting at about 113 F. 7 

(d) Refining Woolen-mill Waste. Olive oil, lard oil, neat's- 
foot oil, saponification olein (or saponified olein) and distillation 
olein (or distilled olein) are sold under the names "wool oils" or 
"cloth oils," and used in woolen mills for lubricating the wool be- 
fore spinning into yarn, or for oiling old woolen rags before grind- 



398 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

ing and "pulling** in the manufacture of "shoddy/' One of the 
perquisites of the wool oils is that they shall have no tendency to 
dry or oxidize, and they must also be easily removable on boiling 
the finished woolen goods or shoddy with a solution of soap or so- 
dium carbonate. The presence of hydrocarbons, even in small quan- 
tities, is objectionable, as they tend to prevent the removal of the 
wool oils during the scouring process. 

After the goods are scoured, the liquid is mixed with freshly 
slaked lime which serves to precipitate the soaps. The curds are 
settled out and separated, then acidified with dilute sulfuric acid 
to separate the free fatty acids, which are skimmed off and filtered 
to remove any dirt. The product known as "fuller's grease," "seek 
oil," or "magma oil/* is distilled with steam, whereby the wool oils 
are recovered, and a residue of fatty-acid pitch obtained, amounting 
to to per cent by weight of the grease; known as "fuller's-grease 
pitch," or "seek-oil pitch." This will vary in its properties depend- 
ing upon the raw materials entering into the composition of the 
original wool oils. 

Treatment of Wool Grease. Wool grease, known also as 
"wool wax," or "wool degras," represents the oily material natur- 
ally present in sheep's wool, and differs entirely from the so-called 
"wool oil" discussed previously. Wool grease is in reality an ani- 
mal wax, as it contains no glycerin or glycerides whatsoever. It is 
extracted by boiling the cut wool with an alkaline soap solution or 
sodium carbonate. Formerly, volatile solvents were used for this 
purpose, but the method is no longer practiced. After boiling with 
soap or sodium carbonate, the liquor is acidified with sulfuric acid, 
whereupon grease rises to the surface and is skimmed off. Dehy- 
drated wool grease melts between 86 and 104 F. and contains ap- 
proximately 55-60 per cent fatty acids, also 40-45 per cent higher 
alcohols ( unsaponifiable ) . 

Wool grease is treated in various ways, and among others by a 
direct process of distillation with superheated steam without pre- 
vious hydrolysis (as the waxes present are not amenable to such 
treatment) whereby the following reactions take place: 8 (i) dis- 
tillation of the free fatty acids, which continues up to one-third of 
the distillate; (2) decomposition of free hydroxy acids principally 
into lactones, some of which distil over and some decomposing into 
carbon dioxide and solid unsaturated acids; (3) decomposition of 
neutral esters into unsaturated acids and unsaturated hydrocarbons. 



XIX FATTY-ACID PITCH 398 

Since wool grease contains an average of 65 per cent esters, this 
will account for the high percentage of unsaponifiable matter in 
wool grease products ; (4) distillation of hydrocarbons. About 39 
per cent of the total fatty acids in wool grease is oxidized acids, and 
of these about 25 per cent work their way into the distillate and the 
remainder are found in the residual pitch. The pitch consists of 
about 85 per cent polymerized hydrocarbons and 12 to 15 per cent 
fatty acids (of which 40 to 65 per cent are oxidized acids). The 
course of the treatment is shown in Table XXVII. The residue of 
fatty-acid pitch is known as "wool-grease pitch," "wool-fat pitch," 
"wool pitch," or "cholesterol pitch." The olein (known as "dis- 
tilled-grease olein" or "degras oil"), is used as a leather or wool 
oil, and the stearin (known as "degras stearin"), is used in the 
soap industry or as a leather "stuffing grease." 

TABLE XXVII 

Wool Grease 
(distilled) 



Gas oil 
(distilled or 
marketed) 


Pale distillate 
(cold pressed) 


4 4 
Back ends Pitch 
(distilled 01 (left in the 
marketed) still) 


1 
Olein 
(redistilled) 

1 - 
(cold pressed) 


(he 


4 
Stearin 
t pressed) or (redistilled) 

(cold pressed, then 
hot pressed) 


4 
Pale olein 
(marketed) 


4 i 
Stearin Stearin 1 
(marketed) (marketed) 


i i 


Hot-pressed 4 4 
Olein Hot-pressed Stearin 
(marketed Olein (marketed) 
or redis- (marketed 
tilled) or redis* 
tilled) 



Physical and Chemical Properties of Fatty-acid Pitches. 
Fatty-acid pitches vary considerably in their physical and chemical 
properties, depending upon the following circumstances : 9 

1 i ) The nature of the fat or oil from which the fatty acids are 
derived. If these contain low melting-point fatty acids, the fatty- 
acid pitch will be soft in consistency, provided the distillation has 
not been carried too far. On the other hand, if high melting-point 
fatty acids predominate, the fatty-acid pitch will be semi-solid to 
solid in consistency. 

(2) The proportion of neutral fats or oils present in the fatty- 



400 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

acid mixture, which will prove substantial if the process of hy- 
drolysis is not carried to theoretical completion. Since the neutral 
fats or oils (triglycerides) do not distil with superheated steam, 
they concentrate in the fatty-acid pitch, and are very apt to decom- 
pose into hydrocarbons (unsaponifiable) if the distillation is carried 
too far. If the distillation is stopped at a point without decom- 
posing the neutral fats or oils, the value of the fatty-acid pitch is 
enhanced by their presence, as they are more stable and weather- 
resistant than the fatty acids themselves. 

(3) The extent to which the distillation is carried and the 
temperature at which it is performed. If distilled too far or at too 
high a temperature, the fatty acids decompose in the presence of 
steam, first into hydroxy acids, which in turn break down into lac- 
tides, unsaturated products and lactones in the following manner: 

(a) -hydroxy acids are converted into lactides. 

(b) jS-hydroxy acids become converted into unsaturated 
products. 

(c) y and 8 hydroxy acids are transposed into cyclic esters of 
the nature of y and 8 lactones respectively. 

It follows, therefore, that the fatty-acid pitches contain free 
fatty acids (mostly polymerized), their lactones (anhydrides), un- 
decomposed glycerides (neutral fats or oils), condensation products 
of unknown composition, hydrocarbon decomposition products, and 
in the case of fatty-acid pitches derived from wool grease, we find 
cholesterol and higher alcohols. 10 Their cryoscopic molecular 
weights vary from 370 to 680, and the so-called "rubber pitches" 
show the highest molecular weights and contain up to 80 per cent 
saponifiable matter. 

The presence of hydrocarbon decomposition products is evi- 
denced largely by the color of the pitch when examined in a thin 
layer. If these are present, the pitch will be a black, otherwise it 
will have a rich brown color. The percentage of saponifiable con- 
stituents present in the fatty-acid pitch is a criterion of its quality. 
The larger the percentage, the better will be the quality from the 
standpoint of weather-resistance. Fatty-acid pitches of the opti- 
mum quality contain not less than 90 per cent of saponifiable con- 
stituents. They are as weather resistant as any bituminous sub- 
3tance. The smaller the percentage of saponifiable constituents in 
the pitch, the less weather-resistant it will prove to be. 

In recent years there has been a tendency to remove more and 



XIX FATTY-ACID PITCH 401 

more of the saponifiable ingredients from the fatty-acid pitches, in 
view of the high price commanded by the fatty acids, and also be- 
cause of improvements effected in the distillation process. The 
author has examined fatty-acid pitches containing as high as 98 
per cent unsaponifiable constituents. These appear glossy black in 
color and almost opaque in a thin layer, and therefore find a ready 
use in the manufacture of cheap lacquers and japans, not intended 
for exposure out of doors. 

All fatty-acid pitches are converted in a more or less infusible 
and insoluble mass upon exposure to the weather for a long period, 
or upon heating a short time to a temperature of 250 to 350 C. in 
contact with air. 11 This is equally true whether or not unsaponifi- 
able constituents are present, and makes this class of pitches espe- 
cially valuable for manufacturing, baking japans and varnishes. 12 
They may also be hardened, or converted into insoluble and infusible 
substances by heating with sulfur, 13 or with sulfur and an alkaline 
"accelerator" (e. g., thiocarbanilide or diphenylguanidine ) , 14 or by 
heating a mixture of fatty-acid pitch and phenol or cresol with 
sulfur dichloride or selenium monochloride, 15 or by heating a mix- 
ture of fatty-acid pitch and phenol or cresol with formaldehyde or 
hexamethylenetetramine which results in the formation of a hard 
resinous condensation product. 16 

Various methods have been proposed for blowing fatty-acid 
pitches, including: blowing wool-fat pitch with air at an elevated 
temperature; 17 blowing a mixture of fatty-acid pitch and montan 
wax, with or without the addition of colored mineral pigments; 18 
etc. Blowing with air at elevated temperatures rapidly increases 
their fusing-point and at the same time tends to convert them into 
the insoluble modification. 10 

The insoluble (polymerized) form of fatty-acid pitch may again 
be rendered soluble in organic solvents by a process of mechanical 
mixing (i. e., "hot-rolling") with natural resins, resin esters, or syn- 
thetic resins. 20 

A highly elastic form, termed "rubber pitch/' is obtained by 
heating soft fatty-acid pitch to 240-250 C., with 10 per cent of 
either sulfuric or nitric acid, 21 and the resultant product is charac- 
terized by being extremely resistant to temperature changes, ap- 
proaching vulcanized rubber in its physical properties. Soft pitches 



402 FATTY- ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

may also be hardened by heating with oxides of magnesium, man- 
ganese or lead ; lime, 22 picric acid, 28 etc. 

Fatty-acid pitches containing a large proportion of saponifiable 
constituents show an extremely low susceptibility index, in fact lower 
than any other class of bituminous materials. Conversely fatty- 
acid pitches in which the unsaponifiable constituents predominate 
are apt to have quite a high susceptibility index. 

In general, the various classes of fatty-acid pitch are character- 
ized by the following predominating physical properties, assuming 
that they have been carefully prepared and neither overheated nor 
distilled too far, viz. : 

Fatty-acid pitches made from lard are usually very ductile with a 

low susceptibility index. 
Fatty-acid pitches made from tallow are generally hard, lacking in 

auctility with a low susceptibility index. 
Palm oil pitches are hard, lacking in ductility with a moderately 

high susceptibility index. 
Cotton-seed-foots pitch is usually soft, of moderate ductility having 

a low susceptibility index. 
Corn-oil-foots pitch is extremely rubbery, shows little ductility and 

has an extremely low susceptibility index. 

Packing-house pitch is ductile and has a low susceptibility index. 
Bone-fat pitch lacks ductility and has a moderately high suscepti- 
bility index. Its color in a thin layer and streak are black. 
Garbage and sewage pitches are ductile with a high susceptibility 

index. Their color in a thin layer and streak are usually black. 
Wool-grease pitch is ductile and has an extremely high susceptibility 

index. Its color in a thin layer and streak are usually black. 

Fatty-acid pitches (referring to all types) comply with the fol- 
lowing characteristics : 

(Test i) Color in mass Dark brown to black 

(Test la) Homogeneity to the eye at 77 F. , Uniform to gritty 

(Test a) Homogeneity under miscroscope Uniform to lumpy 

(Test 3) Appearance surface aged indoors one week. Bright 

(Test 4) Fracture None to conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak on porcelain Light yellow, brown to black 

(Test 7) Specific gravity at 77 F 0.90-1 . 10 

(Test 9*) Penetration at 77 F , 8 to above 360 

(Test 9*) Consistency at 77 F 0-40 

(Test 9</) Susceptibility index, f 8-40 

(Test 10) Ductility Variable 



XIX FATTT-ACID PITCH 403 

(Test 154) Fusing-pojnt (K* and S. method) 35-225 F. 

(Test 15^) Fusing-point (R. and B. method) 50-245 F. 

(Test 16) Volatile matter 500 F., 5 hours o. 5-7. 5 per cent (Set Note) 

(Test 17*) Flash-point 450-650 F. 

(Test 19) Fixed carbon 5- 35 per cent 

(Test 21) Solubility in carbon disulfide 95-100 per cent 

Non-mineral matter insoluble o- 5 per cent 

Mineral matter o- 5 per cent 

(Test 22) Carbenes o- 5 per cent 

(Test 23) Solubility in 88 petroleum naphtha 80-100 per cent 

(Test 28) Sulfur o per cent 

(Test 30) Oxygen 2- 10 per cent 

(Test 33) Solid paraffins Trace 

(Test 340) Saturated hydrocarbons o- 5 per cent 

(Test 34^) Sulfonation residue o- 5 per cent 

(Test 370) Acid value (including lactone value) 2-100 

(Test 37<r) Ester value , , 40-125 

(Test 37 d) Saponification value 60-200 

(Test 37?) Saponifiable constituents 5~ 98 per cent 

Unsaponifiable constituents 2-95 per cent 

(Test 37/) Hydrocarbons in unsapomfiable matter. . . 90-100 per cent 

Higher alcohols (cholesterol) in unsaponi- 

fiable matter o-io per cent 

(Test 37^) Glycerol Tr.-2. 5 per cent 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction No 

(Test 41) Liebermann-Storch reaction Yes in the case of the wool 

grease pitches only 

NOTB. In nearly all cases, a skin will form over the surface of the pitch during the determination of the volatile 
matter. This is characteristic. Certain fatty-acid pitches, especially those containing a large percentage of 
saponifiable constituents, often toughen up and solidify to a rubber-like mass during this test, 

Table XXVIII contains the results of the examination of repre- 
sentative samples of fatty-acid pitch by the author. 

According to Julius Marcusson 24 the saponification value of 
fatty-acid pitches ranges from 24 to 106, whereas the saponification 
value of petroleum asphalts does not exceed 21. Lukens 2C reports 
that the saponification value of fatty-acid pitches ranges from 45 to 
100 and of petroleum asphalts from 5 to 18. 

Fatty-acid pitches may be distinguished from asphalts by the 
small percentages of sulfonation residue and sulfur. Marcusson 
contends that fatty-acid pitches contain a trace of sulfur compounds, 
derived from impurities present in the original fats and also from 
the sulfuric acid used for hydrolysis. Such sulfur compounds are 
distinguished from those occurring in asphalts by the fact that they 
-are not precipitated by mercuric bromide (Test 28). It is also 
interesting to note in this connection that no such precipitate is ob- 
tained from fatty-acid pitches that have been vulcanized with sulfur. 



404 



FATTY-ACID PITCH 



XIX 



TABLE XXVIII. CHARACTERISTICS 



No. 


Test 


From Lard 


From 
Tallow 


From 
Packing- 
house 
Refuse 


2fl 

ab 
3 
4 
5 
6 
7 


Physical Characteristics: 
Homogeneity to eye at 77 F. 


Homo. 
Homo. 
Bright 


Homo. 
Homo. 
Bright 


Homo. 
Lumpy 
Bright 


Homo. 
Homo. 
Bright 


Homo. 
Homo. 
Bright 
Conch. 
Bright 
Brown 
i 060 


Homo. 
Homo. 
Bright , 


Homogeneity under microscope. 


Appearance surface aged seven days 
Fracture . 














Streak 


Yellow 
0.972 


Yellow 
0.980 


Yellow 
0.990 


Brown 

1,000 


Brown 
1.003 


Specific gravity at 77 F 




9* 
9<? 

9<* 
xofr 

ii 


Mechanical Tests; 
Penetration at 115 F 


Soft 
Soft 
88 
o.o 
0.7 

8.2 

18.3 



42 

75 

0.0 

o.o 
o 75 


Soft 
Soft 
85 

O 

1.3 

9-8 
16.7 



36 
88 
o.o 
0.05 
o 9S 


Soft 
280 
83 
o.o 
2.4 

10. 

14.3 

IO 

25.5 
27 

0.0 

0.05 
i 75 


22O 

99 

69 

1.5 

5 8 

IS 2 
12. S 

2-5 

28 S 
18 
o 05 

O.2O 

2 35 


36 

21 

16 
ii. 3 

23 2 
52.0 
22 3 

18 5 
4 
o 
1-75 
3 10 
6 2 


Soft 

IOO 

68 
0.6 
6 3 
15-7 
15-6 
23 
81 5 * 
20 
o.o 
o 40 

3.25 


Penetration at 77 F 


Penetration at 32 T 


Consistency at 115 F . 


Consistency at 77 F 


Consistency at 32 F 




Ductility in cms. at 115 F 


Ductility in cms. at 77 F 


Ductility in cms. at 32 F 


Tensile strength in kg. at 115 F 


Tensile strength in kg. at 77 F 


Tensile strength in kg. at 32 F 


150 
IS* 

16 

i?a 
19 


Thermal Tests: 
Fusing-point, deg. F. (K. and S. method) 
Fusing-point, deg.F. (R. and B. method) 
Volatile 500 F. in 5 hours, per cent. . . . 


44- S 
57 

2.6 

Little 
Change 
452 

6.2 


59 
74 
3 o 
Little 
Change 
525 

II. 2 


70 
85 
5-3 

Gelat. 

485.5 
10 4 


110 
130 

5-0 
Little 
Change 
486 

12.0 


182 
202 

1.2 

Little 
Change 
482 

18.4 


97 
115 
1.7 
Little 
Change 
Sio 

12.6 




Flash-point deg. F 


Fixed carbon per cent 




21 
22 

33 


Solubility Tests: 
Soluble in carbon disulfide 


IOO.O 

o.o 

0.4 

0.0 
IOO O 


IOO.O 
0.0 

1-4 

0.0 
IOO.O 


99-7 
0.3 
1.5 
o.o 

IOO.O 


IOO.O 
O.O 

0.5 
0.0 

98.0 


98.5 

2.1 
1.3 
O.I 

86.7 


IOO.O 

o.o 

2.O 

o o 

IOO.O 


Non-mineral matter insoluble. .......... 




Carbenes 


Soluble in 88 petroleum naphtha 




98 

33 
34* 
37* 
37* 
37* 
37<* 
S7 
37/ 
37/ 
37* 


Chemical Tests 
Sulfur 










o.o 




Solid paraffins * ... 


0.0 

o.o 
17.6 

63. 2 \ 

86. 4 / 
167.2 
0.5 


o.o 
0.3 
65.0 

79-8 

144-8 
5-5 
95-0 
5-0 


o.o 

0.0 

63.3 

75.9 
139.2 

1.5 


o.o 


o.o 


o.o 

3.7 
23.5 

74.1 

97-6 
5-0 


Sulf onation residue * 


Acid value . , 


81.95 
97.55 
179.5 

I.O 


44.1 

112. 

I56.I 
15.2 

97.0 
3.0 
o.o 


Lactone value 


Ester value '. * ... 


Saponification value. * 


Unsaponifiable matter ,..,... 


Hydrocarbons In unsaponifiable matter. . 
Higher alcohols in unsaponifiable matter. 

















XIX FATTY-ACID PITCH 

OF TYPICAL FATTY-ACID PITCHES 



405 





f 




















From 






From 
Bone-fat 


From 
Garbage 


From 
Sewage 


From 
Cottonseed-oil 
Foots 


Corn- 
Oil 
Foots 


From 
Palm-oil 


From 
Wool- 
grease 


Homo. 


* 
Homo. 


Gritty 


Homo. 


Homo. 


Gritty 


Homo. 


Homo. 


Gritty 


Gritty 


Gritty 


Lumpy 


Lumpy 


Homo. 


Lumpy 


Homo. 


Gritty 


Lumpy 


Bright 


Bright 


Bright 


Bright 


Bright 


Bright 


Dull 


Bright 


Bright 














Conch. 


Conch, 
















SI. dull 


Bright 




Black 


Black 


Black 


Yellow 


Brown 


Brown 


Brown 


Black 


Black 


1.036 


i 063 


i. or i 


0.992 


0-955 


o 998 


1.042 


1.087 


1.020 


ISO 


145 


130 


Soft 


260 


61 


46 


35 


Soft 


76 


50 


14 


200 


120 


34 


19 


10 


150 


r4 


12 


18 


72 


66 


46 


14 


5 


34 


2.4 


2.6 


2.9 


o.o 


i.i 


7 2 


9 3 


11. 7 


o.o 


7-9 


II.7 


30.0 


2.7 


5-1 


15.8 


24.7 


35-2 


4.2 


55-4 


60. 1 


48.3 


14.1 


I6. 5 


25.1 


56.5 


82 o 


32,8 


41.9 


40 5 


33-9 


19.7 


15-3 


8.5 


29-5 


41.0 


35.8 


18 


72-5 


52 


8.5 


31 


5 


35-5 


25 


15 


s 


60 


15 


19 


26,5 


2 


2 


0.5 


47-5 


o 





o.S 


28.5 


10 


0.5 





o 


31 


0.05 


0.50 


0.25 


o o 


o 05 


0.75 


I.OO 


2.20 


o.o 


o 30 


1.25 


I 10 


O.IO 


o.S 


1-55 


2.2 


5.00 


0.25 


4 ?o 


6 2 


8.0 


a 30 


4.2 


5-4 


9-5 


11.25 


1.05 


126.5 


142 


134 


71.5 


JOI 


210 


161.5 


172 


91.5 


144 


162 


I5I.5 


92 


120 


235 5 


186 


193 


1 08 5 


o 5 


0.6 


0.55 


4.2 


0.38 


0.25 


3-5 


1.2 


7.2 


Little 
Change 


Little 
Change 


Gelat. 


Gelat. 


Gelat. 


Gelat. 


Much 
Change 


Little 
Change 


Little 
Change 


575 


590 


540 


635 


525 


580 


462 


504 


4 6o 


19-4 


33-5 


18.3 


10.8 


9-2 


8.2 


26.2 


34-0 


30.6 


97-7 


98.2 


98.2 


99-8 


97.5 


97.3 


98.2 


96.2 


98.8 


o.o 


0.7 


1.7 


O. 2 


0.4 


2.O 


0.8 


3.8 


0.5 


0.3 


0.35 


0.8 


1.4 


0.3 


0-5 


1.2 


1.3 


i.i 


O.I 


0.4 


i.i 


0.0 


o.o 


O.2 


2.1 


4-3 


o.o 


94-6 


88 3 


95-2 


IOO.O 


92.1 


96.4 


92.O 


82.2 


99-0 




o o 






o.o 




O O 






0.0 

4Q 


0.0 


O.I 

a o 


o.o 
o.o 


o.o 


O.O 
O.S 


0.2 
1.2 


0.3 


0.0 


,o 






60 5 






46.5 


*3-4 


36.5 


39*5 


103.5 




95.4 






92.9 


53.9 


88.7 








59-7 


106.0 


120.4 


155.9 


151.0 


172.0 


139-4 


67.3 


125.2 


98,0 


97.o 


7.0 


2,0 


4.6 


2-7 


6.0 


75-0 


60.6 


O2 fi 


GT *i 


QO < 


Qsj o 






96.0 




90.0 


93 .0 

fi A 


yi . y 
8 * 


9t 


S-o 






4.0 




10,0 


O.4 




0.55 


0,8 


2-35 























406 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

Only cyclic bodies containing sulfur in ring formation give precipi- 
tates with mercury. 

E. Donath and B. M, Margosches 2 * state that wool-grease 
pitch may be identified by boiling 10 g. of the material with 50 cc. 
N 2 alcoholic potash under a reflux condenser for ^ hour, and 
then filtering the hot liquid. A precipitate will form in the filtrate 
on cooling, consisting of the potassium salts of hydroxy fatty acids, 
which upon recrystallizing from boiling 95 per cent alcohol and 
transposing with hydrochloric acid, will form a white crystalline 
mass of the hydroxy fatty acids melting at 80-82 C., which is in- 
soluble in water and soluble in hot naphtha. It is claimed that by 
this method 25 per cent of wool-grease pitch may be detected in 
admixture with other pitches. A further means of identification 
depends upon the fact that wool-fat pitches give the cholesterol 
reaction. 

The author has found the lineal coefficient of expansion of fatty- 
acid pitches for i F. (length = i) to average 0.00023. 

Fatty-acid pitches flux satisfactorily with mineral waxes, native 
and pyrogenous asphalts, tars and pitches. They also flux satisfac- 
torily with gilsonite and glance pitch, but not with grahamite* 

The following figures indicate that the hardening (toughening) 
of fatty-acid pitches on exposure to the weather is due to oxidation. 
A sample of soft fatty-acid pitch (the first in Table XXVIII) was 
melted and poured into a shallow glass dish, forming a layer 
exactly I millimeter thick. This was exposed out of doors for one 
year in a dust-free receptacle, protected from the direct action of 
the weather, and the following increases in weight noted : 

After i month gained 0.62 per cent After 7 months gained 4.20 per cent 

2 months 2 . 52 per cent 8 4 . 27 per cent 

3 3.27 per cent 9 4.30 per cent 

4 3. 50 per cent 10 4.38 per cent 

5 3. 86 per cent n 4.42 per cent 

6 4.12 per cent 12 4.46 per cent 

The original pitch was soft and semi-liquid, but after exposure 
for one year it hardened to a tough, leathery mass. The original 
fusing-point was 44^ F. (K. and S. method), and at the end of 
the year it was 185 F. 



XIX BONE TAR AND BONE-TAR PITCH 407 



BONE TAR AND BONE-TAR PITCH 

In the production of bone tar and bone-tar pitch the crude bones 
are first steeped in a i per cent solution of brine for three to four 
days, to separate the fibrous matter. They are then degreased by 
one of the following methods : 

(1) Boiling the bones with water in open vessels; 

(2) Boiling with water in closed tanks under a pressure of 
10 ib.; 

(3) Extracting the bones with a solvent (usually a petroleum 
distillate boiling at 100 C.) and removing the last traces of solvent 
from the bones by blowing in live steam. The degreased bones are 
then treated to extract the glue by again subjecting the bones to the 
action of live steam for a lengthy period under a pressure of I C to 
20 Ib. in an upright cylindrical boiler with a false bottom. The 
glue gradually leaches from the bones, the quantity extracted de- 
pending upon the duration of the treatment. When it is desired 
to convert the bones into "bone charcoal" (used for the purification 
of petroleum distillates and paraffin wax), only one-half of the 
gelatinous matter is extracted from the degreased bones, whereupon 
the water is drained off and the bones allowed to air-dry. They 
are then distilled destructively in horizontal cast-iron retorts, the 
distillate being condensed, and the permanent gases consumed under 
the retort. The distillate consists of an alkaline aqueous liquor 
containing ammoniacal bodies, and 1.5-2.0 per cent (based on the 
weight of raw material used) of a tarry layer known as "bone tar," 
"bone oil," "Dippel oil," or "Oleum animale foetidum." The resi- 
due remaining in the retort, known as "bone charcoal" or "animal 
charcoal," is removed while still hot, and transferred to an air-tight 
vessel in which it is allowed to cool. It is then passed through 
grinding mills and sieved. The bone charcoal is composed of ap- 
proximately 10 per cent of carbon, 75 per cent of calcium phos- 
phate, the balance consisting of various other mineral ingredients 
and moisture. 

The following yields are obtained : 

Non-condensable gases 10-15 per cent 

Aqueous liquor 10-15 per cent 

Bone tar 25-10 per cent 

Bone charcoal 55~6o per cent 

Total loo-ioo per cent 

The bone tar floating on the surface of the aqueous liquor is 
drawn off. It consists of fatty substances derived from the fat 



408 FATTY-ACID PITCH, BONE TAR AND BONE-TAR PITCH XIX 

which escaped extraction from the bones, also derivatives of pyri- 
dine possessing a most disagreeable and penetrating odor, and inci- 
dentally serving to distinguish it from all other tars. The charac- 
teristics of bone tar are included in Table LXXXIV. 

The aqueous liquor is distilled, and the distillate caught in sul- 
furic acid to recover the ammonium compounds as ammonium sul- 
fate. The residue is used as a fertilizer. 

The bone tar is subjected to fractional distillation to recover the 
bone-tar pitch, the properties of which are also embodied in 
Table LXXXIV. 

Bone-tar pitch is intermediate in its physical properties between 
asphalts and the fatty-acid pitches. On destructive distillation, it 
yields an aqueous distillate which reacts distinctly alkaline. It is 
moderately susceptible to temperature changes, and on a par with 
higher grades of residual asphalts and inferior grades of fatty-acid 
pitches in its weather-resisting properties. It is the blackest of all 
pitches and is therefore valued by the varnish maker to deepen the 
color of japans. It is soluble in pyridine bases and only partly 
soluble in benzol and petroleum distillates, but upon fluxing with 
rosin and vegetable oils it becomes soluble. Since it is produced in 
comparatively small quantities, it can scarcely be regarded as a 
commercial product 

GLYCERIN PITCH 

This pitch is obtained upon the purification of glycerin by dis- 
tillation with superheated steam. It is greenish brown to black in 
color and contains a certain amount of water-soluble constituents. 
It is produced in limited quantities and has a restricted use. 27 

Glycerin pitch contains polyglycerins, metallic soaps, metallic 
salts, etc. It is used as a lubricant in boring, for making printing 
inks, as a core binder, 28 etc. Upon heating with phthalic anhydride 
and succinic, malic, fumaric, citric, or malomalic acid, a water- 
resistant synthetic resin is obtained. 29 



PART IF 
PYROGENOUS ASPHALTS AND WAXES 

CHAPTER XX 
PETROLEUM ASPHALTS 

"Petroleum asphalts" are obtained from petroleums by distilla- 
tion, blowing with air at elevated temperatures, and in the refining 
of certain distillates with sulfuric acid. These methods will be 
described in greater detail later. 

Varieties of Petroleum. Petroleum as it occurs in different 
parts of the world, varies widely in composition. Certain varieties 
are composed of open chain hydrocarbons, others are made up 
exclusively of cyclic hydrocarbons, and still others occur showing 
every possible gradation between these two extremes. Numerous 
classifications have been proposed, based on its chemical composi- 
tion in general, or the presence of a substantial proportion of char- 
acteristic bodies, such as the paraffin series of hydrocarbons, the 
naphthene series, sulfur derivatives, nitrogenous bodies, benzols, 
terpenes, etc. 1 

From the standpoint of the asphalt content, petroleums may be 
divided into three groups, viz. : 

(1) Asphaltic petroleums. These carry a substantial amount 
of asphaltic bodies, with solid paraffins either absent or present only 
in traces. 

(2) Semi-asphaltic petroleums. These carry a moderate 
amount of asphaltic bodies, but in any event generate or produce 
asphalt-like bodies during the distillation process. Solid paraffins 
may or may not be present 

(3) Non-asphaltic petroleums. These do not carry asphaltic 
bodies but may generate them during the distillation process. Solid 
paraffins are usually present, but not necessarily so. 

409 



410 



PETROLEUM ASPHALTS 



XX 




XX 



DEHYDRATION OF PETROLEUM 



411 



Table XXIX contains a list of the most important occurrences 
of petroleum throughout the world, classified according to the as- 
phalt content and solid paraffins present. 

Different crudes yield varying amounts of asphalt on steam or 
vacuum distillation, dependent upon the character of the oil and the 
amount of asphalt content The following figures are illustrative, 
and indicate in a general way the yield of asphalt by weight, having 
a fusing-point of 100 F. (R. and B. method) : 



Type of Crude Oil 


A. P. I. Gravity 


Yield of Asphalt 


Mid-continental (Oklahoma) 


42 


2 per cent 


Seminole 


36 


ik oer cent 


Peruvian 


36 


4 per cent 


Mid-continental (Illinois) 


32 


5J per cent 


Light Californian 


26 


12 per cent 


Texan. 


24 


14 per cent 


Heavy Californian. 


12 


65 per cent 


Mexican (Panuco) 


12 


65 per cent 









DEHYDRATION OF PETROLEUM 

Nearly all crude petroleums carry more or less water, some 
being entrained mechanically, and in other cases held in a state of 
emulsion. Ordinarily the oil is permitted to stand long enough by 
itself for the water and sand to separate. Crude oils containing 
less than 2 per cent of water are accepted by the pipe lines and re- 
fineries. If they contain more than 2 per cent, they must first be 
dehydrated. Certain heavy asphaltic and waxy crudes carry as 
much as 70 to 90 per cent of water held in suspension by brine and 
colloidal mineral matter (e. g., hydrated aluminium silicates). The 
following methods may be used to remove the water, where it is 
necessary to deliver the oil to the pipe line or refinery within the 
prescribed limitations : 

1 i ) Settling. Heating and subsidence will break up emulsions 
in many cases. This may be facilitated by adding chemicals, as for 
example i per cent of a mixture of sodium oleate, sodium resinate 
and sodium silicate ; or else sulf onated pleic acid. 2 

(2) Centrifugtng. This consists in centrifuging the oil at a 
temperature of no to 180 F. in a centrifuge operating at 17,000 
r.p.m. by means of a turbine. 3 



412 PETROLEUM ASPHALTS XX 

(3) Tube Stills. The most satisfactory manner to break up 
emulsions consists in running the oil through a tube- or pipe-still 
under pressure and heated to 300 F., whereupon it is released in 
a vaporizer at atmospheric pressure. The water and oil vapors 
are recondensed, but will not again emulsify on account of the ab- 
sence of emulsifying agents and the low viscosity of the oil. 

DISTILLATION OF PETROLEUM 

Petroleum is separated into various commercial products by 
means of distillation, of which the following methods are in vogue : 

(i) Batch Stills. These are still in use in the older refineries, 
but are rapidly being superseded by tube stills. The efficiency in 
transmission of heat to the oil in the batch still is very poor, being 
rarely better than 30 per cent, equivalent to a consumption of 6 
bbl. of fuel oil for each 100 bbl. of distillate. Approximately 0.85 
bbl. distillate is produced per day, per sq. ft. of surface fired, or 
expressed differently, 2.5 gal. distillate will vaporize per hour, per 
sq. ft. vaporizing surface. Fig. 121 illustrates a typical batch-still 
installation. The still proper holds 1000 to 1500 bbl. of 42 gal", 
each. The distillation process may be carried on either with, 4 or 
without the use of steam. Where steam is employed, the process 
is known as "steam distillation," otherwise it is termed "dry dis- 
tillation." 

Steam Distillation. This is also known as the "fractional" dis- 
tillation process and consists in introducing dry steam, termed "bot- 
tom steam" into the still, which assists in the vaporization of the 
volatile constituents and minimizes decomposition of the distillate 
and residue. Its action is based on the physical law that the boiling- 
point of a pair of non-miscible or slightly miscible liquids is lower 
than that of either pure component. The introduction of steam, 
therefore, serves materially to lower the boiling-point of the petro- 
leum, and produces the maximum yield of heavy lubricating oils. 
It also tends to economize in fuel, and to shorten the distillation 
process. The steam upon being dried by passing through a trap is 
introduced through perforated pipes at the bottom of the still when 
the temperature of the contents exceeds the boiling-point of water. 

In treating ^asphaltic petroleums by the steam-distillation proc- 
ess in batch stills, the charge is distilled until the residue attains 
the proper consistency, which is controlled by sampling the residue 
through petcocks set in the still, or by recording the temperature of 
the residue, or by observing the character of the distillate. The 
further the process is continued, the higher will be the fusing-point 
and the harder the consistency of the residue. The temperature of 
the residue at the termination of the process will vary between 600 



XX 



DISTILLATION OF PETROLEUM 



413 



and 750 F., and the time of distillation between twelve and thirty- 
six hours. When the distillation is completed, the residuum is run 
or blown into a closed cylindrical vessel constructed of steel, where 




it is allowed to cool until the temperature is reduced sufficiently to 
permit its being filled into barrels or drums without danger of ig- 
niting on coming in contact with air. 



414 PETROLEUM ASPHALTS XX 

Where the residue is distilled to a definite consistency without 
further treatment, the distillation is known as Straight running, 
and the residue a "straight run asphalt." In certain cases a portion 
or "fraction" of the distillate is mixed with the residue at the close 
of the distillation, which is termed "cutting back," 5 the object of 
which is to modify the properties of the residual product or to 
dispose economically of a fraction which otherwise has little value 
commercially. 

Cut-back residual oil is composed of residual oil, cut back with 
a petroleum distillate, which should be of a character which will 
volatilize within a reasonably short time after application to a sur- 
face. Relatively volatile distillates are generally used in the manu- 
facture of cut-back asphalts. The larger the quantity of distillate 
added, the more fluid will be the cut-back product. 6 

In treating semi-asphaltic and non-asphaltic petroleums by the 
steam-distillation process in batch stills, steam is introduced when 
all the naphtha has distilled off, and the distillation continued until 
the lubricating oils have distilled over, whereupon the temperature 
reaches 620 F. At this point the distillation is stopped. In the 
case of non-asphaltic crude oil, the so-called "cylinder stock" re- 
mains in the still, and with semi-asphaltic crude, an asphaltic residue 
remains behind, which may either be marketed as such, or treated 
with air to produce a "blown asphalt." 

Table XXX gives an outline of the steam-distillation process as 
applied to asphaltic petroleum, and Table XXXI as applied to 
semi-asphaltic and non-asphaltic petroleums. ^ 

Dry Distillation. This is sometimes termed the straight or 
"destructive" or "cracking" distillation, by means of which a certain 
proportion of the higher boiling-point constituents decompose or 
break down, forming correspondingly larger yields of the low boil- 
ing-point constituents. The dry distillation process is accordingly 
used when the distiller wishes to produce a maximum amount of 
gasoline and illuminating oil, or in cases where the crude is unfit 
for manufacturing lubricating oil. 

Upon treating semi-asphaltic and non-asphaltic petroleums by 
the dry-distillation process in batch stills, a large amount of crack- 
ing taices place when the crude kerosene fraction distils over and 
the temperature of the still reaches 625 F. The fires are accord- 
ingly moderated to slow down the distillation and accelerate the 
decomposition as much as possible. The "cracked" distillate is 
fractioned until the temperature in the still reaches 675 to 700 F., 
whereupon the distillation is brought to a close. There remains a 
viscous dark-colored "residuum" varying in gravity from 20 to 25 
Baume which may either be marketed under the name of "residual 
oil" or "flux oil" or else distilled separately in another still, known 



XX 



DISTILLATION OF PETROLEUM 



415 




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416 



PETROLEUM ASPHALTS 



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XX DISTILLATION OF PETROLEUM 417 

as a "tar still," to obtain the wax or paraffin distillate, wax-tailings 
and coke bottoms. The operation is carried on as rapidly as pos- 
sible to avoid unnecessary cracking, and render the paraffin crystal- 
line* The paraffin distillate comes over first, followed by the wax- 
tailings, until nothing but the coke remains in the still, which after 
cooling is removed with a pick and shovel. The method of pro- 
cedure is illustrated in Table XXXII. 

(2) Continuous Stills. Stills of this type are now encountered 
infrequently. They are constructed similar to batch stills, the oil 
flowing from one still to another, and each producing a predeter- 
mined grade of distillate. The whole circumference of a continuous 
still may be fired and approximately 1.42 bbl. of distillate will be 
obtained per day, per square foot of firing surface, similarly 2.5 gal. 
of distillate will evaporate per square foot of vaporizing surface. 
The efficiency of continuous stills is approximately 40 per cent, 
equivalent to a consumption of 5 bbl. of fuel oil per 100 bbl. dis- 
tillate produced. 

(3) Tube or Pipe Stills. Tube or pipe stills, aiso termed 'Vac- 
uum flash coils" when connected with vacuum fractioning (or 
"flash") chambers 7 are rapidly replacing the other types of stills 
on account of their lower initial cost, greater through-put, and econ- 
omy in operation. The oil is pumped under pressure through a 
series of interconnecting tubes heated in a furnace. Such stills are 
built in units capable of handling up to 15,000 bbl. of crude oil per 
day. It is possible to heat the oil as high as 900 to 950 F. because 
of the high rate of heat transfer through the tubes and the4iigh 
velocity of the oil. This heat transfer may run as high as 200 
B.t.u. per sq. ft., per hour, per degree F. difference in temperature. 
Their efficiency will range from 65 to 80 per cent, equivalent to a 
consumption of less than 3 bbl. fuel oil per 100 bbl. distillate 
produced. 

By means of a tube still, as much as 90 per cent of the crude 
may be recovered as distillate and it is not infrequent that 10 per 
cent more gasoline will be obtained than is present in the crude oil 
under treatment, due to the cracking which takes place. Where 
more than 80 per cent of the crude is converted into distillate, there 
results a small amount of gas, which tends to lower the distillation 
temperature. The tube still has the advantage over the batch still 
in that the temperature may be controlled more accurately, due to 
the smaller volume of oil in the still, localized overheating is pre- 
vented, and the fractioning takes place within much sharper limits. 
Moreover, the cost of operation is from Vio to %5 that of batch 
stills, and in addition remove the possibility of recondensation and 
run back of the distillate. Whereas the asphaltic residue may re- 
main at extreme temperatures for 12 to 24 hours in a cylindrical 



418 PETROLEUM ASPHALTS XX 

batch still, the residue is subjected to the maximum temperature for 
only a fraction of a minute in a tube still, thereby minimizing any 
tendency towards carbonization. 

Tube stills are now used successfully for all types of distillation, 
including the topping or skimming of crudes, the manufacture of 
lubricating stock, the cracking of gas oils and other distillates, and 
even for running the oil to coke, provided a speed of flow is attained 
in the tubes that the coke will not separate except in the vaporizer. 
They are accordingly designed to accomplish the following : dehy- 
drate the oil and remove one or more fractions in the following 
order, viz.: gasoline, kerosene, gas oil and/or wax-distillate (in the 
case of semi-asphaltic and non-asphaltic petroleums). The residue 
consists either of fuel oil or residual oil, depending upon the extent 
to which the distillation has been carried. 

The construction details of a tube-heater is shown in Fig. 122. 

The successful operation of the tube still is closely connected 
with the improved fractioning equipment developed during the past 
five to ten years. It is now possible to produce fractions of the 
proper distillation range in one operation. The so-called bubble- 
cap tray-tower has given phenomenal results. It consists in an ar- 
rangement for the repeated absorption and redistillation of the 
distillate, thus separating the heavier hydrocarbons, which are car- 
ried over by the associated lighter hydrocarbons. Such a tower is 
illustrated in Fig. 123. The tower is insulated to keep it at an 
unvarying temperature and means are provided to keep a definite 
relation between the up-flowing vapors and the down-coming liquid 
which flows from tray to tray in the tower. It has been found that 
very volatile distillates can only be fractioned at high pressures- 
usually 250 Ib. per sq. in.; and moreover difficultly volatile distil- 
lates can be fractioned most closely in towers operating under a 
vacuum of 29, or in some cases above 29^4 i n - 8 

The general arrangement of a two-stage combination atmos- 
pheric and vacuum distillation unit for treating 10,000 barrels of 
crude in 24 hours is illustrated in Fig. 124.* This procedure in- 
volves the recovery of the lighter distillates, including naphtha, 
kerosene and a portion of the gas oil by distillation at atmospheric 
pressure, and thereupon transferring the residue to a vacuum dis- 
tillation unit in which the balance of the gas oil and several lubri- 
cating-stock fractions are recovered as distillates and asphalt as a 
final residuum. 

The general operation of this unit is as follows : crude is taken 
from storage and pumped through the atmospheric vapor heat ex- 



JtX 



DISTILLATION OF PETROLEUM 



419 



changer and thence to a settling tank for removal of solids and 
water. The crude then flows through the vacuum-stage exchangers, 
acquiring a final preheat temperature of approximately 350 F. 






h 



rt 

I 



The preheated crude is transferred to the atmospheric stage tube 
still and heated to a temperature sufficient to effect the desired 
vaporization in the atmospheric f ractioning tower. 



120 



PETROLEUM ASPHALTS 



XX 



'SkctionThno' 

Dephlecmating 

Tower 



Section A. A 



!6"Manhole 

*** 




& Boiler 
Flange" 

I 1 1 ii . - v 

3 "Recharging "Stock 
fo Cond Box 

Courtesy Kansas City Testing Laboratory. 
FIG. 123. Bubble-cap Tray-tower for Fractioning Petroleum. 



XX 



DISTILLATION OF PETROLEUM 



421 








B 


U 



a 



I 

! 

M 

c 



422 PETROLEUM ASPHALTS XX 

In the atmospheric tower four distillate streams are recovered : 
gasoline as the top vapor stream, and naphtha, kerosene, and gas 
oil as liquid side streams. 

The side streams are removed from respective plates in the 
main tower to external stripping sections for steam stripping to 
remove the lighter ends. The stripping steam and vapors are re- 
turned to the main tower at points above the respective stream 
take-offs. 

The atmospheric stage bottoms are subjected to steam stripping 
on plates below the tower inlet The reduced crude is pumped hot 
from the base of the atmospheric tower directly to the vacuum-stage 
tube still for further heating. 

The vacuum tube still discharges into the vacuum fractionating 
tower, which is maintained at a low absolute pressure. Three distil- 
late streams are recovered from the vacuum stage : heavy gas oil as 
the top vapor stream and paraffin distillate and cylinder stock as 
liquid side streams. Asphalt bottoms are recovered as a residue 
from the base of the tower. Steam is introduced into the base of 
the tower for stripping the asphalt and for partial-pressure effect. 

Vacuum is maintained on the system by a barometric condenser 
backed by steam jet ejectors. The overhead vapor stream, consist- 
ing of gas oil and process steam, passes through vapor heat ex- 
changers and water-cooled surface condensers. Because of the 
temperature and pressure conditions maintained at the condenser 
outlet, the process steam remains in the vapor state and flows to 
the barometric condenser, while practically complete condensation 
of the gas oil is obtained. The desirability of obtaining sharp 
phase separation at the vacuum condenser outlet with a low partial 
pressure of gas oil vapor in the uncondensed steam, dictates the 
quantity of gas oil to be removed in the atmospheric stage ; i.e., the 
initial boiling point of the vacuum-stage gas oil must be sufficiently 
high to insure substantially complete condensation. 

Process conditions and sizes of the major items of equipment 
for this installation are shown in Table XXXIII. 

Two-stage crude distillation units with individual unit capacities 
up to 50,000 barrels per day are now under construction. Based on 
330 stream days per year, 50,000 barrels per day correspond to 
16,500,000 barrels of crude oil per year. These figures indicate 



XX DISTILLATION OF PETROLEUM 423 

the enormous capacity which can be built into single process units 
of this type. 

The two-stage units effect a separation between asphalt and 
lubricating stocks by distillation. Because of overlapping in boiling 
point range between the heaviest lubricating fraction and the lower 
boiling asphaltic material, a sharp separation is difficult. Hence it 

TABLE XXXIII 
TWO-STAGE DISTILLATION UNIT 

Crude charge, bbl./24 hr 10,000 

Vacuum-stage charge, bbl./24 hr 5,ooo 

Final asphalt residuum, bbL/24 hr 837 

Temp., F,: 

Atmospheric tower inlet 599 

Atmospheric tower top 224 

Atmospheric naphtha draw-off 328 

Atmospheric kerosene draw-off 420 

Atmospheric gas oil draw-off. 537 

Atmospheric bottoms draw-off 530 

Vacuum tower inlet 772 

Vacuum tower top 364 

Vacuum tower light lube draw-off (wax dist.) 504 

Vacuum tower heavy lube draw-off (cylinder stock) 690 

Vacuum tower bottoms draw-off 709 

Absolute pressure at top of vacuum tower, mm 60 

Atmospheric tower: 

Diam., ft II 

No. plates (30 above inlet, 4 below) 34 

Vacuum tower: 

Diam., ft 17 

No. plates (16 above inlet, 4 below) 20 

Process steam, lb./hr.: 

Atmospheric tower and strippers 3>5oo 

Vacuum tower 45oo 

Vapor velocity: 

Atmospheric tower: 

Ft./sec 2.21 

Lb./sq. ft./hr 1,360 

Vacuum tower: 

Ft./sec 7.05 

Lb./sq. ft./hr 600 

has been found advisable in some instances to remove a clean, 
heavy, lubricating stock several trays above the flash zone and a 
small quantity of material containing the lighter asphaltic materials 
as a total draw-off from the tray immediately above the tower in- 
let. This stream can be treated separately from the clean bulk 
heavy lubricating stock, or if the heavy lubricating available in the 
crude exceeds requirements, it can be routed to cracking. 



424 PETROLEUM ASPHALTS XX 

Several lubricating-stock rerun operations are commonly prac- 
ticed. The modern equipment in general use consists of atmos- 
pheric or vacuum pipe stills similar in design to those used for crude 
units. Major operations are as follows : 

Rerunning of Pressed Wax Distillate. This operation consists 
in the redistillation of stock which has been dewaxed by filter press- 
ing. The rerun operation eliminates non-viscous gas oil, and the 
balance of the dewaxed oil is fractioned into two or more neutral 
oils for use in blending for automotive lubricant or in the manufac- 
ture of light machine oils. Atmospheric distillation is customarily 
employed with tube still outlet temperatures of 700 to 730 F. 

Cylinder Stock Solution Rerunning. The cylinder stock-naphtha 
mixture from centrifuge dewaxing is rerun in atmospheric tube stills 
for removal of the naphtha diluent. Tube-still outlet temperatures 
of 475 to 550 F. are required. 

Rerun of Treated and Dewaxed Long Residuum for Motor 
Oil Grades. A vacuum operation is dictated by the fact that lubri- 
cating fractions of high boiling point are taken overhead. 

CRACKING PROCESSES 

These have been developed for the purpose of increasing the 
yield of gasoline, which is accomplished by heating the crude oil to a 
high temperature under pressure. 

(1) Liquid Phase Cracking. This involves heating and crack- 
ing at high pressures without permitting distillation to take place 
during the reaction stage. The heat is accordingly applied to the 
liquid under a sufficiently high pressure to maintain it as a liquid 
and prevent the distillation and consequent drop in temperature in 
the reaction chamber. These processes usually operate continu- 
ously, with separate heating and reaction chambers. 

(a) Tube-and-Tank Process. This is illustrated diagrammat- 
ically in Fig. 125, and consists of a tube heater A in which the oil 
enters under a pressure of 400 Ib. per sq. in. At the exit the pres- 
sure is 350 Ib. and the temperature 850 F. The oil then enters an 
insulated vertical reaction chamber JS, which is kept filled with liquid 
under 350 Ib. pressure, and at its exit the temperature has fallen 
to 785 F. Before it enters the bubble tower C, the pressure is re- 
duced to 50 Ib. by the release valve D, and its temperature as it 
enters the tower is 700 F. The bubble tower separates the gas oil 
(i.e., cycle stock) and the pressure tar. The cycle stock is run 
through the process again, mixed with a certain proportion of fresh 



XX 



CRACKING PROCESSES 



425 



crude oil. The gasoline is then condensed and separated from the 
fixed gas which is consumed as part fuel in the tube heater. 

(b) Cross Process. This is illustrated in Fig. 126 and consists 
of two tube heaters A and B using common vaporizing and frac- 
tioning towers D and E. The first heater operates on crude oil, or 
fuel oil, or in fact any petroleum product and heats the charging 
stock to 850 F. under 350 Ib. pressure. The second heater B op- 
erates on the recycling stock, which it heats to 900 F. under 600- 
700 Ib. pressure. From here the oil is forced into an insulated reac- 
tion chamber C, where it is maintained in liquid condition for fifteen 
minutes at a temperature of 600-700 F., during which all the 
carbon formed in the cracking operation is deposited as coke, which 
must be cleaned out from time to time. At the exit of C there is 



Crude oil* 




FIG. 125. Tube-and-Tank Cracking Process. 

a reducing-valve which discharges the product into a vaporizer D 
maintained at practically atmospheric pressure.^ As the cracked oil 
enters the vaporizer, it blends continuously with the stream from 
the tube still A. The fractioning tower E separates the recycling 
stock (gas oil), and the gas-separator F separates the gasoline 
from the gas. Tube still A acts as a skimming plant which sepa- 
rates the gasoline normally present in the crude oil, plus gas-oil, 
plus pressure-tar. The final operation results in the production of 
gasoline, recycling stock (gas oil), pressure-tar, gas (which is 
burned underneath the tube stills), and carbon (which must be peri- 
odically removed from the reaction chamber). ^ The pressure-tar 
may be marketed as fuel oil, since it is very fluid, and practically 
free from carbon (less than */ 2 per cent). A plant of this type will 
operate successfully on all types of crude oil, emulsified crudes, as 
well as any fraction distilled therefrom. 



426 



PETROLEUM ASPHALTS 



XX 



(c) Holmes-Manley Process. This is very similar to the Tube- 
and-Tank Process, the only material difference being that four or 
more vertical reaction chambers are mounted side by side in a com- 
mon gas-fired furnace, and in addition each reaction chamber is pro- 
vided with a motor-driven shaft having scrapers to assist in re- 
moving the coke. The oil enters the tube heater under 350 Ib. 
pressure and leaves at 300 Ib* and 800 F. A reducing-valve is 



Crude off* 




" Recycling 
stock 

FIG. 126. Cross Cracking Process. 

located between the condenser and the gas-separator in which a 
pressure of 80 Ib. is maintained. 

(2) Mixed Phase Cracking. This involves pressure distillation 
with simultaneous heating, cracking and distillation. The efficiency 
is stated to be less than in the liquid phase cracking, because of the 
added heat consumed in the repeated vaporization and condensation 
of the uncracked distillates. 

(a) Burton Process. This is a batch operation and takes place 
in stills with refluxing. The modern high-pressure Burton still 10 
consists of a pair of heat-insulated cylinders A (Fig. 127), attached 
to a tube heater 5, mounted in a furnace below. This is connected 
with a bubble-tower C, which separates the gas^ and gasoline from 
the heavier distillate which is allowed to recycle into the still Con- 
denser D separates the gasoline, which in turn is separated from 
the gas in the gas-separator E. The entire system up to the release- 
valve F is maintained under a pressure of 925 Ib. The still AB is 
heated to 750 F. and the bubble tower C to 550 F. The carbon 



XX 



CROCKING PROCESSES 



427 



assumes a granular condition and is cleaned out after each run of 
forty-eight hours, whereupon the still is recharged. Upon running 
gas-oil there are produced 80 per cent gasoline, 6 per cent gas, 0.4 
per cent coke and 13.6 per cent pressure-tar. The pressure-tar 




far -- 



rx, ry O 

'>. ' Coke \^s<?as.*^S 



FIG. 127. Burton Cracking Process. 

carries but a small amount of carbonaceous matter and when sub- 
jected to steam-distillation in a batch still produces a hard asphalt 
of high ductility, almost completely soluble in carbon disulfide, and 




FIG. 128. Dubb's Cracking Process. 

which is quite susceptible to temperature changes* 11 This has been 
marketed in the United States under the name "Stanolite," which, 
according to the experience of the author, is lacking in weather- 
resisting properties. 



428 PETROLEUM ASPHALTS XX 

(b) Dubb's Process. This process operates continuously at a 
high temperature. The lay-out is illustrated in Fig, 128 and con- 
sists of a tube still A heated partly with the fixed gas produced in 
the cracking operation and partly by means of fuel oil, which raises 
it to 850900 F. under a pressure of 250 Ib. The product there- 
upon enters the reaction chamber B in which it is vaporized, accom- 
panied by a drop in temperature and deposition of coke. The va- 
pors next pass into a dephlegmator C where they encounter a stream 
of the raw charging stock and upon mixing pass downward and 
back to the tube still A. The uncondensed vapors pass out at the 
top of the dephlegmator and then into a coil-condenser D. The 
valve E releases the pressure and the separator F removes the gas 
from the gasoline. Where it is desired to produce pressure-tar (in 
this case residual oil), it is drawn off the bottom of the reaction 
chamber JS, otherwise the valve is kept shut and a slightly higher 
temperature is carried on the transfer liquid. The hot residue may 
be quenched by running into water and separating. 12 The foregoing 
process results in the production of cracked vapor and coke, instead 
of cracked vapors, coke and residual oil. The following are re- 
ported to have been obtained on one cycle : 

From Mid-continental gas oil 44.3 per cent gasoline 

From Mid-continental fuel oil 40. 9 per cent gasoline 

From Panuco 10 B6. residuum 21 . i per cent gasoline 

From Venezuela 13 B6. residuum 26. 9 per cent gasoline 

The various cracking processes ranked as follows in the United 
States in relation to the respective through-puts: Burton, Cross, 
Holmes-Manly, Tube-and-Tank and Dubbs. The following types 
of stock may be used in the cracking operations : crude oils of any 
type, emulsified crudes of any type, topped crudes, fuel oil, gas oil, 
and mixtures of the foregoing with recycling stock. The following 
in general represent the products obtained: fixed gases (used as 
fuel), gasoline, pressure-tar and in special cases an intermediate 
cut known as recycling stock (which is retreated and still further 
cracked), also coke. After removal of the soluble oils, the coke 
tests as follows: volatile matter 13 per cent, fixed carbon 80 to 86 
per cent, ash i to 7 per cent, and sulfur i to 2 per cent 

The pressure-tar may be utilized in the following ways, viz.: 
marketed as fuel oil (provided it is sufficiently liquid and free from 
carbonaceous ^matter ); or it may be marketed as soft asphalt flux 
(provided it is more viscous than fuel oil) ; or it may be mixed in 
suitable proportions with residual asphalts derived from the regular 
distillation process ; n or it may be steam-distilled in a batch still 
to produce residual asphalt of various grades; or distilled under 
vacuum to the desired grade ; 14 or it may be blown with air to pro- 



XX 



LIQUID PRODUCTS 



429 



duce blown asphalts of the desired grade, either alone, 15 or in ad- 
mixture with other products, such as an "aromatic extract of a pe- 
troleum oil/' le or an untreated residual oil in combination with an 
asphalt of naphthene base, 17 or the oily layer separated from 
sludge asphalt 18 Pressure-tars may be hydrogenated under pres- 
sure at 345400 C. in the presence of a catalyst. 19 

Various tars from coal (e. g., low-temperature coal tar, water- 
gas tar, coke-oven tar, etc. ) , shale, lignite, peat, or wood, may like- 
wise be treated by the cracking process. 20 The following figures 
will indicate the yields when such tars are submitted to the crack- 
ing process : 





Spec. Grav. 
(A. P. I.) 


Gas 

Cu. ft. 
per bbl. 


Motor 
Fuel 
Per Cent 


Fuel or 
Diesel Oil 
Per Cent 


Coke. 
Lbs. per 
barrel 


Low-temperature coal-tar. 
Intermediate temperature 
coal-tar 


8-9 
6.0 


570 
<oo 


28.8 
14.5 


10.3 

17.7 


241 


High-temperature coal-tar. 
Lignite tar 


7.0 
IT. Q 


706 

767 


12. 1 

38.3 


22.6 


i 5 8 

241 


Brown-coal tar 


Q.2 


835 


28.6 




96 















The following constitute the various products pertaining to, or 
derived from petroleum : 21 

Liquid Products 

Petroleum Naphtha. A generic term applied to refined, partly 
refined or unrefined petroleum products and liquid products of nat- 
ural gas, not less than 10 per cent of which distils below 347 F. 
(175 C.) and not less than 95 per cent of which distils below 
464 F. (240 C.), when subjected to distillation in accordance 
with the standard method of test (A.S.T.M. Designation: D 86). 

NOTE. The "naphthas" used for specific purposes such as cleaning, manufacture of 
rubber, manufacture of paints and varnishes, etc., are made to conform to specifications 
which may require products of considerably greater volatility than that set by the limits 
of this generic definition. 

Gasoline. A refined petroleum naphtha which by its composi- 
tion is suitable for use as a carburant in internal combustion engines. 

Petroleum Spirits (White Spirits). A refined petroleum dis- 
tillate with a minimum flash point of 70 F. (21 C.) determined 
by the Tag Closed Tester (A.S.T.M. Designation: D 56), or by 
the Abel Tester, with the volatility and other properties making 



430 PETROLEUM ASPHALTS XX 

it suitable as a thinner and solvent in paints, varnishes and similar 
products. 

NOTE. The term "turpentine substitute" as applied to petroleum spirits is to be con- 
demned as false and misleading. The term "mineral spirits" which is frequently used 
in the paint and varnish industry is a misnomer as it includes within its scope not only 
petroleum products, but other hydrocarbon mixtures, such as coal-tar distillates. In 
Great Britain the term "petroleum spirits" is applied to a very light hydrocarbon mixture 
having a flash point below 32 F. (o C.). 

Engine Distillate. A refined or unrefined petroleum distillate 
similar to naphtha, but often of higher distillation range. 

Tops. The unrefined distillate obtained in topping a crude pe- 
troleum. 

Kerosene. A refined petroleum distillate having a flash point 
not below 73 F. (23 C.), as determined by the Abel Tester 
(which is approximately equivalent to 73 F. (23 C.) as deter- 
mined by the Tag Closed Tester; A.S.T.M. Designation: D 56), 
and suitable for use as an illuminant when burned in a wick lamp. 



E. In the United States of America local ordinances or insurance regulations re- 
quire flash points higher than 73 F. (23 C), Tag Closed Tester. 

Gas OIL A liquid petroleum distillate having a viscosity inter- 
mediate between that of kerosene and lubricating oil. 

N OTEt it should be understood that oils, other than gas oil as defined above, may be 
and are used in the manufacture of gas. 

Fuel OIL Any liquid or liquefiable petroleum product burned 
for the generation of heat in a furnace or firebox, or for the gen- 
eration of power in an engine, exclusive of oils with a flash point 
below 100 F., Tag Closed Tester, and oils burned in cotton or 
wool-wick burners. Fuel oils in common use fall into one of four 
classes: (i) residual fuel oils, which are topped crude petroleums 
or viscous residuums obtained in refinery operations; (2) distillate 
fuel oils, which are distillates derived directly or indirectly from 
crude petroleum; (3) crude petroleums and weathered crude pe- 
troleums of relatively low commercial value; (4) blended fuels, 
which are mixtures or two or more of the three preceding classes. 

Lubricating Oils. A heavy distillate suitable for use in lubri- 
cation. 

Semi-Solid to Solid Distillates 

(a) Petrolatum. This term is applied to the product obtained 
by diluting either crude paraffinaceous petroleum, or the residue 
known as u cylinder stock" (obtained when paraffinaceous petroleum 
has been steam-distilled to remove the lighter distillates and gas- 
oil) with naphtha. The mixture is then chilled or allowed to "cold 



XX SEMI-SOLID TO SOLID RESIDUES 431 

set" until an amorphous residue settles out, which is separated 
either by sedimentation or by centrifuging. The naphtha carried 
by the petrolatum is recovered by steam distillation. Petrolatum 
is also known under the names vaseline, petroleum grease, petro- 
leum jelly, and liquid paraffin. 

(b) Paraffin Wax. This is derived from paraffin-bearing pe- 
troleums, and is separated from the lubricating oil and paraffin dis- 
tillates by crystallization at low temperatures and filter-pressing. It 
is classified by its color and melting-point. The terms "paraffin 
scale" and "scale wax" are generally applied to the low melting- 
point variety, and "refined paraffin wax" to the harder variety. Its 
melting-point varies from 100-135 F. 

(c) Wax Tailings. This represents the fraction obtained in 
the dry distillation of petroleums, and recovered immediately prior 
to coking. It is peculiar in its properties and generally free from 
paraffin wax. 

Semi-Solid to Solid Residues 

(0) Residual Oil. This term is applied to the liquid to semi- 
solid residues obtained from : ( I ) the destructive distillation of non- 
asphaltic petroleum; (2) the distillation of semi-asphaltic and 
asphaltic petroleums; (3) the distillation of pressure-tar; (4) the 
fluxing of harder residual asphalts with heavy distillates (known as 
"cut-back asphalt"). The following terms are used synonymously 
with residual oil, viz. : asphaltum oil, liquid asphalt, flux, flux oil, 
fluxing oil, roofing flux, road oil, dust-laying oil, black oil and petro- 
leum tailings; and abroad as mazout, mazut and masut (Tartar), 
ostatki or astatki (Russian), also pacura (Rumanian). 

(b) Residual Asphalt. This term is applied to the semi-solid 
to solid residues obtained from the distillation of semi-asphaltic and 
asphaltic petroleums and pressure-tars. The following terms are 
used synonymously with residual asphalt, viz. : petroleum asphalt, 
petroleum pitch, petroleum residue, road binder, carpeting medium, 
and seal-coating material. 

(c) Blown Asphalt. A term used to designate the product ob- 
tained by blowing air through residual oil at elevated temperatures. 
Also known under the names oxidized asphalt, oxygenized asphalt, 
oxygenated asphalt and condensed asphalt. 

(d) Sulfurized Asphalt. This term is applied to the product 
obtained by heating residual oil* or residual asphalt with sulfur at 
high temperatures. Also known under the names Dubbs asphalt, 
Pittsburgh flux and Ventura flux. 

(e) Sludge Asphalt. This term is applied to the asphaltic 
product separated from the acid sludge produced in refining petro- 



432 PETROLEUM ASPHALTS XX 

leum distillates with sulfuric acid. It is also known under the 
names acid-asphalt, acid-sludge asphalt, etc. 

RESIDUAL OILS 

Residual oils are distinguished from fuel oils by having a 
higher specific gravity, a higher fusing-point and generally a smaller 
amount of volatile matter and higher flash-point (except in the case 
of cut-back residual oils). The two classes of products merge to- 
gether, so that there is no sharp line of demarcation between them. 

The characteristics of residual oils depend upon three factors, 
viz. : 

(1) The type and nature of the petroleum from which they 
are produced. 

( 2 ) The particular form of apparatus in which the distillation 
is carried out. 

(3) The extent to which the distillation has been conducted, 
and whether or not the product has been cut back. 

The following will indicate in a general way the effect of these 
factors upon the nature of the residual oil. 

Fusing-point. All types of residual oil fall within the range of 
32 to 1 10 F., R. and B. method (Test 156) ; or 20 to 100 F., K. 
and S. method (Test 150). 

Specific Gravity. The type of petroleum and the nature of the 
distillation process affects the specific gravity at 77 F. (Test 7) as 
follows : 





When Straight- 
distilled 


When Distilled 
from Pressure-tar 




0.95-0.9$ 


1.00-1.03 


From semi-asphaltic petroleum 


o . 90-1 . oo 


1.02-1.05 


From asphaltic petroleum 


0.9<-I.O2 


1.03-1.07 









Solid Paraffins. The percentage of solid paraffin (Test 33) 
is an indication of the types of petroleum from which the residual 
oil has been produced, regardless of the particular form of appa- 
ratus in which the distillation has been carried out. Thus, residual 
oils derived from non-asphaltic petroleums will contain ^from 4.0 
to 15,0 per cent solid paraffin, those derived from semi-asphaltic 
petroleums from a trace to 5.0 per cent, and those derived from 
asphaltic petroleums from 0,0 to 0.25 per cent 



XX 



RESIDUAL OILS 



433 



Fixed Carbon, Sulfur, Saturated Hydrocarbons and Proportion 
Soluble in 88 Petroleum Naphtha. The following means may be 
used to differentiate between residual oils derived from various 

22 



sources : 



Residual Oils from: 


Fixed 
Carbon 
(Test 19) 


Sulfur 
(Test 28) 


Saturated 
Hydrocarbons 
(Test 34*) 


Soluble 88 
Naphtha 
(Test 23) 


U. S. non-asphaltic petroleum 
U. S. semi-asphaltic petroleum 
U. S. asphaltic petroleum 
Trinidad, Venezuela and 
Colombian petroleums 


Per Cent 
<5 
<5 

5-7 

7-10 


Per Cent 
<i.S 
<i.S 

1.5-2.5 

2 . 5-3 . 5 


Per Cent 

>75 
50-75 
30-40 

30-40 


Per Cent 
> 9 o 
> 9 o 
80-95 

80-95 


Mexican petroleum 


>io 


3 5-5 o 


30-40 


80-95 













The foregoing figures apply to the residual oils produced on 
straight distillation as well as from the corresponding pressure-tars. 

Flash-point and Volatile Matter. These two criteria are closely 
related and interdependent. The lower the flash-point, the greater 
will be the percentage of volatile matter, and vice versa. Both 
fluctuate within wide limits in the case of residual oils. Excepting 
for cut-back products, the flash-point of residual oils is generally 
above 300 F. Cut-back products may run as low as 200 F., which 
is likewise the case w r ith fuel-oils and undistilled pressure-tars. 
Similarly the volatile matter at 500 F. in five hours will generally 
run below 15 per cent or at most 20 per cent, except in the case of 
cut-back products, which will run in excess of 20 per cent Where 
residual oils are used to flux harder asphalts and asphaltites, or 
where they are converted into blown asphalts, it is desirable that the 
flash-point shall be as high as possible, (preferably above 450 F.) 
and the volatile matter as low as possible (preferably below 3 or 4 
per cent at 500 F. in five hours). On the other hand, if the re- 
sidual oil is to be used for dust-laying purposes the presence of 
volatile constituents is not detrimental, but on the contrary may be 
desirable, and hence cut-back products will answer satisfactorily. 
Residual oils produced from Colombian petroleum (asphaltic) 
show the highest flash-point and the smallest amount of volatile 
matter. In fact, Colombian petroleum is so difficultly volatile that 
it must be distilled under vacuum after the lower boiling fractions 
have been removed by topping in a shell or pipe still 28 Residual 
oils produced from Venezuela and Trinidad (asphaltic) petro- 
leums, also U. S. Mid-continental (semi-asphaltic) and U. S. Gulf- 



434 PETROLEUM ASPHALTS XX 

coast (asphaltic) show a somewhat lower flash-point and a corre- 
spondingly greater amount of volatile matter. Residual oils ob- 
tained from Mexican (asphaltic) and LJ. S. Californian (asphaltic) 
petroleums show a still lower flash-point and greater quantity of 
volatile matter .than the preceding, basing the comparisons on prod- 
ucts of similar fusing-poihts and hardness (viscosity). 

Residual oils from non-asphaltic petroleums are not produced 
today in appreciable quantities, as this grade of petroleum is usually 
distilled destructively to recover the lubricating oils and paraffin 
wax. Moreover, such residual oils have certain inherent disadvan- 
tages, including the fact that they are poor fluxes, they cannot be 
blown successfully, and they contain a quantity of greasy and waxy 
constituents which contaminate any other substances with which 
they may be combined. Residual oils derived from asphaltic petro- 
leums constitute the best fluxes and produce the most desirable 
grades of blown asphalts. Those produced from pressure-tars will 
show evidence of free carbon under the microscope and sometimes 
also to the naked eye, and it is contended that unless used in ad- 
mixture with other products, they are undesirable for producing 
blown asphalts, since they are likely to result in a non-homogeneous 
product. It is contended, however, that pressure-tars may be blown 
with a mixture of air and steam at temperatures of 45-55 F-i 
above which temperature carbon will be generated. 24 Any free 
carbon may be removed by filtering the tar ; 25 by mixing the pres- 
sure-tar with fuel oil, heating to 340 F. and either filtering or 
centrifuging the mixture; 26 by treatment with sulfuric acid; 27 by 
the addition of CaO during the cracking process, which results in 
an agglomeration of the carbon and facilitates the filtration, 28 

Another residual oil, which may suitably be used to flux harder 
asphalts, consists in the semi-liquid residue produced in the refining 
of lubricating oils with selective solvents. 29 

Residual oils, with the exception of cut-back products, comply 
with the following characteristics: 

(Test i) Color in mass Brownish black to black 

(Test la) Homogeneity to the eye Uniform to gritty 

(Test it) Homogeneity under microscope Uniform to lumpy 

(Test 7) Specific gravity at 77 F o. 85-1 .07 

(Test Sa) Specific Engler viscosity at 140 F 10-50 

(Test 9^) Penetration at 77 F 100-350 

(Test 9*) Consistency at 77 F o- 7 

(Test 15*) Fusing-point K. and S. method 20-100 F. 

(Test 1 5*) Fusing-point R. and B, method 32-1 10 F. 

(Test 16) Volatile at 325 F. in 5 hours fr-ia per cent 

Volatile at 500 F. in 5 hours 1-10 per cent 



XX RESIDUAL OILS 435 

(Test 160) Residue of 100 penetration at 77 F. ob- 
tained on evaporation 40-80 per cent 

Ductility of residue at 77 F. (Test 100) . . 2-100 + cm. 

(Test 170) Flash-point 300-550 F. 

(Test 18) Burning-point 350-650 F. 

(Test 19) Fixed carbon 2-10 per cent 

(Test 21) Solubility in carbon disulfide 98-100 per cent. 

Non-mineral matter insoluble o- i per cent 

Mineral matter o- $ per cent 

(Test 22) Carbenes o- I per cent 

(Test 23) Solubility in 88 petroleum naphtha. . . . 80- 99 per cent 

(Test 28) Sulfur Tr.- 5 per cent 

(Test 30) Oxygen o- 3 per cent 

(Test 33) Solid paraffins o- 15 per cent 

(Test 340) Saturated hydrocarbons 30- 90 per cent 

(Test 34^) Sulfonation residue 90-100 per cent 

(Test 37*) Saponifiable constituents Tr.- 5 per cent 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction No 

Table XXXIV includes a few tests on typical residual oils ex- 
clusive of cut-back products. 

Pressure tars, also known as cracking-still tars have a smaller 
percentage of hydrogen than the original charging stock, or fraction 
thereof. Dehydrogenation is one of the steps by which such prod- 
ucts are formed. The various steps include dehydrogenation, poly- 
merization, condensation, intermolecular rearrangement, and vari- 
ous combinations of these reactions. Polymerization and condensa- 
tion, accompanied by dehydrogenation, account for the formation of 
asphalt in the cracking process. It is of interest to note that asphalt 
is formed in the cracking process from fractions of non-asphaltic 
crude oils (e. g., Pennsylvanian), or semi-asphaltic crudes (e. g., 
Mid-continental) which are more paraffinic than asphaltic, and from 
which asphalts are not otherwise produced in commercial quantities. 
The formation of asphalts from paraffin-base oils (i. e., non-asphal- 
tic) is a most striking example of the synthesis of asphalts from 
paraffin hydrocarbons. 80 

Table XXXV shows the characteristics of residual oils obtained 
from cracking various fuel oils and topped crudes made by a so- 
called flashing operation of the cracking process, in which the prod- 
uct is withdrawn from the cracking still and transferred to a vapor- 
izing chamber or zone of reduced pressure. This reduction in 
pressure causes the vaporization of controlled amounts of the prod- 
uct The residue withdrawn from the vaporizing chamber is termed 



436 



PETROLEUM ASPHALTS 



XX 



II 






M *& 



* 





ffl 



. 



O O 

d 



MOO 

o d d 



S "<S 

On M W "t 



*l 10 to 

tO O> <-O 

00 O to Ti- O 



<*+ 




OV N ^ 



9k H O t* 

d O *i 



gt 



O O 



o? 



00 O 

<y o d 



00 M 00 

M O I 1 * 



00 M 

H d 



M O VJ 

n O oO 00 



a 

I 

a 






to O fr 
O O O 



-i- 10 M* to (O 



MOO 

4 d d 





w *- "* N 



to O to 
00 4 



to O 
*O 00 fO *0 fr 



00 WO *- 

en O O M 

Cft O% 



VO O 

O 



oo w o oo 

j d a 



to O 

? d 



o 

(JO 



MO CT> 

o o o 



VO O> O 




O 1 * 

M d to 



C/3 

P 



8? 



VO O O 
Jf* O <O 



o 

Tt- to t 



o o o 

O O M 



to to 

H 




en MO oo 
gl 6 d ^ 



00 O 

to d 



O MO M 

cr o O * 

9k O^ 



00 M M 

d t^id 



O 

d 



O O O <O 

8 d i 



I 




Thermal Tests: 
Fusing-point (K. and S. m 
deg.F 
Fusing-point (R. and B. m 
deg.F 
Volatile, 500 F., 5 hrs., per 
Flash-point, deg. 
Fixed carbon, per 





to *O S. < 

M H H 



XX 



RESIDUAL OILS 



437 



"flashed residue." The yield of pressure tar based on the weight 
of charging stock depends upon the character of the oil treated. 
The particular examples given range in yield from 10 to 20 
per cent. 

TABLE XXXV 
ASPHALTS PRODUCED FROM FLASHED RESIDUES 



Property 


Kentucky* 


Midcontinent and West 
Texas 


Midconti- 
nent 
Gushing 


Midconti- 
nent II 


Coating 
Asphaltt 


Asphalt 
Cement t 


Specific gravity at 25 C. (77 F.) 


i 075 
231 (448) 
0.58 
48 
S3 (127) 
680 
93-8 
99-1 
5-3 
17.2 

IOO 
>I22 
>I22 


1.065 


1.099 


1.0867 
171 (340) 
0.765 
54 
54 (129) 

I2IO 
91.2 
98.7 

3 6 
17-8 
97 
78 


1.1195 
177 (35o) 
1. 15 
49 
5i (123) 
693 
92.7 
99.8 
2.17 

20.2 

103 

>I22 
>I22 


FlocK P f F ^ 


Loss at 163 C (325 F,), per cent 


Trace 

4-0 
126 (259) 


1-7 


Penetration of residue at 35 C. (77 F.), mm 
Softening-point C ( F.) 


55 d3i) 
829 


Flnnt tf>*t at CO C* ^T22 F 1 SCC 


^nliihflitv in PPL ner cent 


96.9 
98,6 


Solubility in CSg 


97-9 
2.63 

20.0 
IOO 

I2S 
63 






I9.O 
5-5 
o.3 


Penetration at 25 C. (77 F.), mm 
Ductility at 25 C (77 F.) cm 


DnrHlitv at rfi P f6o F } cm < . . . . 









* 100-120 mm, penetration for macadamized roads. 

t Coating asphalt, air-blown for 3 hours at 254 C. (490 F.). 

t Asphalt cement for use in asphalt macadam pavements. 

85-100 mm. penetration for macadamized roads. 

|J 100-120 mm. penetration used in building asphalt concrete roads or macadam roads. 

Table XXXVI gives a comparison of the properties of the as- 
phalt derived from a cracked Gushing topped crude, by steam-dis- 
tillation and air-blowing, respectively. 

TABLE XXXVI 

f 

PROPERTIES OF ASPHALT MADE FROM GUSHING TOPPED CRUDE BY STEAM DISTILLATION AND 

BY AIR-BLOWING 



Property 


Residue 
from Steam 
Distillation 


Air-blown 
at 232 C. 
(450 F.) 


Flashed residuum per cent 


71.5 


70.2 


^Jrvfr^nincr ooint C. ( F.} 


51 (124) 


63 (146) 


Penetration at 25 C. (77 F.), mm. . , 
Ductility at 2< C. (77 F.), cm 


105 

40 


93 
11.3 


^nlnWlifv in CS oer cent 


IOO 


100 


Solubility in CCli. per cent 


99.3 


99-5 









438 



PETROLEUM ASPHALTS 



XX 



Table XXXVII similarly compares the properties of asphalt 
derived from the flashed residuum from a cracked Pennsylvania 
kerosene distillate by steam-distillation and air-blowing, respectively. 

TABLE XXXVII 

PROPERTIES or ASPHALT MAI>E FROM PENNSYLVANIA CRUDE BY AIR-BLOWING AND STEAM- 

% DISTILLATION 



Property 


Cracked Residuum 


Air-blown 


Steam-distilled 


Per cent asphalt recovery 


5.26 
1.099 
103 
5i (1^3) 
38i 
125 
0.67 
60 

202 (395) 

21 8 (425) 

99-59 
97.71 
None 


5-09 
1.116 
105 
44 (112) 
297 
125 
0.7 
70 
i 88 (370) 
207 (405) 
99.86 
98.95 
None 


Specific gravity at 25 C, (77 F.) 


Penetration at 25 C. (77 F.), mm 


Softening point (ring-and-ball), C ( F.) 


Float test) sec 


Ductility at 25 C. (77 F.) cm 


Volatility at 163 C. (325 F.), per cent 


Penetration of residue at 25 C, (77 F.), mm 


Flash point (Cleveland open-cup), C. ( F.) 


Fire point (Cleveland open-cup), C. ( F.) 


Solubility in CS2, per cent 


Solubility in CCU, oer cent 


Water 





Such asphalts may be produced to meet specifications for roofing 
or shingle saturants, coating asphalts for composition roofings, 
floorings, blowing stock, emulsions, etc. For a given stock, the 
pressure tar obtained from a cracking coil operated at 250 Ib. per 
square inch will be less asphaltic than a tar obtained from the same 
unit operated at 750 to 1000 Ib. per square inch. In no case is a 
present-day cracking unit operated under conditions where appre- 
ciable quantities of free carbon is formed. 

The outstanding features of high temperature-pressure conver- 
sion residues are as follows : 

(1) Up to a certain point, the higher the temperature and 
pressure, or the longer the time element, the more asphaltic will be 
the residue obtained. 

(2) Cracking-coal residues of a given fusing-point have a 
higher specific gravity, ductility and susceptibility to temperature 



XX 



RESIDUAL OILS 



439 



changes, likewise lower viscosity than equivalent residues produced 
by direct distillation processes. 

(3) Cracking-coil asphalts are less soluble in petroleum naph- 
thas than straight-distilled residues produced from the same crude. 

Straight-reduced asphalts from cracking processes resemble 
coal-tar pitch in certain physical properties, f^ince they have ex- 
tremely low viscosity when melted and produce cut-backs and 
primers that are if anything superior to coal-tar products. 81 Inci- 
dentally, pressure tars are completely miscible with coal tars and 
coke-oven tars. 32 

The following figures 8a show the characteristics of residual oils 
derived from various sources, as well as sundry mixtures : 



TABLE XXXVIII 














a 






4 


S 






u 


x 




u 


a 


g 





'8 






o 


*i 




Hi a 


U 


M 


8 













C "H 








M 




Nature of OU 




ts 

'3 


u 


S 8 

* w 

2l 


ii 


d 

1 


J 


!I 

3 h 


S i 




3 

*o 


i 


C/5 o 


.S jg 


?| 


.sj 


H ^j 
*J U 


12 S 


^j 




1 


I 




11 


11 


ii 


rt 


si 


|| 




cS 


C/3 


W 


cfl 


A 


E 


3 


(X 


G 


Straight-run residual oil from U. S. non- f 
asphaltic petroleum (paraffin base) . . . j 


Light 
Medium 
Heavy 


0-933 
0.939 

o 939 


13-7 

21 4 

31.5 


99.9 

99 9 
99 6 


1.4 
2.9 
1,4 


190 

210 
238 


0.7 
0.7 
0.45 


56 

66 
68 


ii 

13 
22 


Straight-run residual oil from Arkansas f 


Light 


o 980 


13 8 


99-6 


ii. 9 


130 


7-9 


66 


10 


semi-asphaltic petroleum blended with < 


Medium 


I 002 


23.9 


99-6 


14.0 


I2S 


9-7 


67 


4 


pressure-tar derived from ditto I 


Heavy 


i .013 


30.1 


98.8 


16.4 


134 


4-5 


69 


5 






















Pressure-tar derived from U. S. non- f 


Light 


1.030 


13.6 


99-9 


n. 8 


170 


2.7 


61 


100 4- 


asphaltic and semi-asphaltic petrole-j 


Medium 


1.045 


189 


99 9 


12.4 


l85 


2 


68 


ioo-f 




Heavy 


1.056 


32.3 


99 9 


14.2 


195 


x.6 


72 


100+ 


Pressure-tar derived from U. S. non- ( 


Light 


0.938 


10.3 


99.6 


5-1 


165 


4-1 


65 


2 


asphaltic and semi-asphaltic petroleum { 


Medium 


0.944 


16.1 


99.6 


6.3 


180 


1.9 


74 


a 


Mixture of straight-run residual oils de- f 
rived from Mexican asphaltic petrole-j 
um and U. S. non-asphaltic petroleum I 


Light 
Medium 


0.947 
0.959 


13.2 
23.8 


99 9 
99-6 


5.7 
10. S 


150 

126 


5.2 
6.1 


57 
64 


21 

35 


Straight-run residual oil from Mexican 






















Medium 


0.963 


23.5 


99.9 


15.6 


105 


5-6 


63 


xoo-t- 


Cut-back residual oil from Mexican petro- 






















Light 


0.961 


15.6 


99-8 


14.9 


98 


15.2 


59 


87 























440 PETROLEUM ASPHALTS XX 

BLOWN PETROLEUM ASPHALTS 

These are manufactured from residual oils derived from as- 
phaltic, semi-asphaltic or non-asphaltic petroleums, by blowing with 
air at elevated temperatures. 

It has been recognized for many years that petroleum products 
become changed in their physical properties by treating with oxi- 
dizing agents or air. One of the first to report this was Abraham 
Gesner in i865, 84 who remarked that: 

"Organic substances are oxidized by the atmosphere, and its 
action promoted by a high temperature. Hot air has therefore 
been forced through hydrocarbon oil during the process of purifi- 
cation, and in some instances with advantage.' 1 

In 1876 W. P. Jenney patented the process of treating sludge 
oil obtained in refining petroleum with sulfuric acid, with a current 
of air at a temperature of 250 C. 85 He observed that a resinous 
substance was produced by the absorption of atmospheric oxygen 
by the oil. 

De Smedt patented a process for oxidizing coal tar with potas- 
sium permanganate or permanganic acid at a temperature of 
300 F., 8 * also the method of oxidizing petroleum residues in a 
similar manner, 87 or by distilling petroleum in the presence of an 
oxidizing agent. 3 * 

Next Schall 8 * discovered that paraffin, vaseline and heavy min- 
eral oils oxidize rapidly and almost completely by introducing a 
well-divided stream of oxygen at 140-150 C., especially in the 
presence of insoluble manganese compounds. Dorsett oxidized coal 
tar by heating with manganese dioxide and ammonium chloride. 40 
Baillard oxidized a mixture of petroleum and oleic acid by means 
of air at 160 C. 41 Busse blew air through a heated mixture of 
asphalt and vegetable oils in the presence of nitric acid, sulfur, or 
sulfur dichloride. 4 * Salathe blew heated air through melted native 
asphalt, either alone or in the presence of manganese dioxide or 
litharge. 48 Schreiber proposed blowing melted asphalt, coal-tar 
pitch, fatty-acid pitch, wool-fat pitch, etc., with air in the presence 
of manganese dioxide, with or without the addition of sulfuric acid, 
and finally adding formaldehyde. 44 Incidentally, it is of interest to 
note that vaseline, liquid or solid paraffin wax may be converted into 



XX BLOWN PETROLEUM ASPHALTS 441 

fatty acids by oxidation with potassium permanganate in acid or 
alkaline solution, or with a mixture of potassium permanganate and 
sodium hypochlorite, or a mixture of manganese dioxide with hydro- 
chloric or nitric acid. 45 

The first to manufacture blown asphalt on a commercial scale 
was F. X. Byerley, who obtained a patent in i894 46 for drawing 
air through petroleum residues (and especially those derived from 
Lima, Ohio, crude oil), at temperatures between 400 and 600 F. 
In this way he obtained "pitches" of variable properties depending 
upon the temperature and the duration of the blowing process. For 
the softer grades (fusing under 200 F,), the Lima residuum was 
blown three days at 400 F., during which 2 per cent of distillate 
was produced. For the harder grades (fusing at about 400 F.) 
the residuum was blown four to five days at 500 F., during which 
between 5 and 6 per cent of distillate was recovered. The product 
was claimed to be resistant to changes in atmospheric temperature, 
and to differ from the corresponding steam-distilled asphalt by being 
readily soluble in petroleum benzine or naphtha. Byerley marketed 
the product under the name of "byerlite." Air under suction was 
passed through a 6000 gal. still of the oil, at the rate of 450 cu. ft. 
per minute. Ohio petroleum residue of 21 to 27 Baume, also 
Texas Gulf-coast residue of 12 to 15 Baume were first used for 
this purpose. 

J. W. Hayward 47 and also G. F. and G. C. K. Culmer 4 * ob- 
tained patents for a similar process, according to which a mixture 
of petroleum residue and refined Trinidad asphalt or gilsonite is 
heated to 193 C. and blown for forty hours at the rate of 15 to 
30 cu. ft. air per minute, per ton asphalt. After a time the external 
source of heat was removed, since it was found that the temperature 
of the residue increased spontaneously, due to the chemical changes 
induced by the action of the air. It was also found that the oxida- 
tion progressed very rapidly at first, and then more slowly, as it 
approached the end of the process. 

According to present practice, the residual oil is blown at 525 to 
575 F. at the rate of 30 to 50 cu. ft air per minute, per ton of 
asphalt, for a period of five to twelve hours. It is found unneces- 
sary to use any of the catalyzers referred to in the earlier patents. 
The air may either be blown through the still under pressure, or 



442 PETROLEUM ASPHALTS XX 

else sucked through the still by subjecting the contents of the still 
to a partial vacuum (up to 20 in. mercury). There are proponents 
of both systems. The loss depends largely upon the amount of 
volatile matter contained in the residual oil, and varies from prac- 
tically o up to 10 per cent of the weight of the charge, depending 
of course upon the extent the' product is blown. Water and carbon 
dioxide are also given off. It is contended that the vacuum process 
removes the oily and greasy matters from the residual oil and forms 
a brighter and cleaner looking blown asphalt. The more asphaltic 
the crude from which the residual oil was derived, the better will 
be the quality of the blown product, and the shorter the duration 
of the blowing process. Residual oils derived from semi-asphaltic 
and non-asphaltic petroleums must be blown longer to obtain a prod- 
uct of the same fusing-point, and the blown asphalt is apt to appear 
quite oily and greasy. Non-asphaltic petroleums will yield a good 
grade of blown asphalt if first subjected to a high temperature and 
pressure, which serve to convert saturated hydrocarbons into poly- 
merized unsaturated compounds. 40 Blown asphalts may likewise 
be produced from naphthenic residual oils or naphthenic derivatives 
i.e., non-asphaltic and non-paraffinic in character) obtained by ex- 
tracting petroleum with SO 3 , aniline, phenol, etc. 60 

The best blown asphalts are produced from the following pe- 
troleums, viz. : U. S. Gulf-coast field (Texas) ; Mexican heavy vis- 
cous crudes of 8 to 15 Baume obtained from the Panuco and To- 
pila regions (20 to 30 miles southwest of Tampico), also from 
the Ebano region (40 miles west of Tampico) ; Venezuela crudes 
from the Lagunillas, La Roza and Mene Grande fields; Colombian 
crudes from the Barranca-Bermeja region; likewise from Trinidad 
crudes. 

Mid-continental (U. S.) semi-asphaltic petroleums form re- 
sidual oils which when blown at 450 to 475 F. for nine to ten 
hours produce blown asphalts having a fusing-point of 350 to 
400 F. (R. and B. method) and without the formation of "free 
carbon/' If a small proportion of gilsonite is added to the mix- 
ture, the time of blowing will be increased, but the product will be 
improved materially in the following respects: it will be harder, 
have a higher gloss, greater cohesiveness, greater ductility, lower 
susceptibility to temperature changes, and improved weather-re- 



XX BLOWN PETROLEUM ASPHALTS 443 

sistance. The use of grahamite does not give as satisfactory results, 
since the product will be lacking in ductility, 

California residual oils produced from asphaltic petroleums 
when blown at 425 to 450 F. for twelve to eighteen hours will 
produce blown asphalts having a fusing-point of 175 to 190 F. 
(R. and B. method). If the temperature exceeds 530 F, free car- 
bon will be formed. Blown California asphalts have a good gloss 
and are considerably harder than Mid-continental, Gulf-coast 
(Texas), Mexican, Venezuelan, Colombian and Trinidad products. 
They are also more susceptible to temperature changes. 

Texas residual oils derived from asphaltic petroleum produce 
excellent blown asphalts that are glossy, resistant to temperature 
changes, free from oily or greasy constituents, highly ductile, and 
are excellent weather-resistants, 

Mexican, Venezuelan, Colombian and Trinidad asphaltic petro- 
leums produce residual oils which behave similarly on blowing. Such 
residual oils having a fusing-point of 90 to 100 F. (R. and B. 
method) when blown at 450 to 500 F., for six and one half to ten 
hours, at the rate of 40 cu. ft. air per minute, per ton, will produce 
blown asphalts having a fusing-point of 220 to 235 F. (R. and B. 
method) and a penetration at 77 F. of 15 to 17. The resultant 
asphalts have a good gloss, are free from oily constituents, moder- 
ately ductile and fairly resistant to temperature changes. 

A method has been patented for blowing a mixture of topped 
Mexican residuum (8 to 10 Be.) with topped Mid-continental re- 
siduum (12 to 14 Be.) derived from Illinois semi-asphaltic petro- 
leum, at 450 to 500 F., which is claimed to result in a product of 
greater ductility than when Mid-continental residuum is used alone. 61 

Various catalyzers and oxidizing agents have been proposed for 
augmenting the air-blowing process, including : manganese dioxide ; 52 
manganese dioxide and nitric acid; 53 finely powdered limestone; 54 
caustic soda or sodium carbonate; 56 bentonite or finely powdered 
coke ; 56 sulfur ; 67 sulf uric acid with or without the addition of metal- 
lic persulfates or perborates; 58 boric acid, phosphorus acid or ar- 
senious acid; 69 potassium chlorate; 60 chlorides or sulfates of zinc, 
iron, copper or antimony; 61 basic acetylacetonate of manganese, ce- 
rium, nickel, cobalt or zinc; 62 copper, iron, manganese or cobalt 
soaps; 68 as well as the various agents referred to previously. It 



444 



PETROLEUM ASPHALTS 



XX 



has been proposed that any excess catalyzer be removed after the 
blowing operation by boiling the product with dilute hydrochloric 
acid and washing with hot water. 64 

The use of various gases has been suggested for blowing 
through the melted asphalt, including: air alone; air under super- 
atmospheric pressure ; 65 air followed by a mixture of air and steam 
in varying proportions under atmospheric or reduced pressure; 66 
carbon dioxide with or without air; 6T ozone; 6 * a mixture of air or 
oxygen with NO 2 or SO 2 ; 69 carbon monoxide activated by a cata- 
lyst such as nickel or palladium, or by first heating the asphalt with 
cerium oxide or tin oxide and blowing as aforesaid; 70 air containing 
up to 1 1 y 2 per cent chlorine ; 71 chlorine followed by carbon diox- 
ide ; 72 bromine or boron fluoride ; air and halogens in the presence 
of sulfur; 73 etc. 

It has been shown that the use of air containing up to 1 1 T / 2 
per cent of chlorine for blowing asphalts maintained at 475 F. 
speeds up the process, and that chlorine is both absorbed and com- 
bined chemically with the asphalt. The fusing-point is increased 
more rapidly, and the ductility and penetration are decreased more 
rapidly than when air alone is used. Thus, with a residual oil hav- 
ing a fusing-point of 86 F. (R. and B.) and a penetration of 253 
at 77 F. (50 grams in 5 seconds), the following relative blowing 
times were required: 





To increase the 


To decrease the 


To decrease the 




Fusing-point 


Penetration 


Ductility 




to 200 F. 


(50 g./5 sec./ 


at 77 F. 




(R. & B. method) 


77 F.) to 20 


to 10 cm. 




22 hrs. 


1 8 hrs. 


19 hrs. 


Air with 1 ,3 per cent chlorine 


1 8 hrs. 


15 hrs. 


14 hrs. 


Air with 6 o per cent chlorine 


8 hrs. 


5 hrs. 


5i hrs. 


Air with 1 1 2 per cent chlorine. .... 


5 hrs. 


3 hrs. 


3i hrs. 











The blowing operation may either be intermittent or continu- 
ous/ 4 In the intermittent or batch process the apparatus consists 
essentially of an open, or preferably closed cylindrical still in which 
the air or other gas is introduced through a series of perforated 
pipes at the bottom. Various means have been suggested to sub- 
divide the gas into fine streams or jets, 76 or to accomplish a more 



XX BLOWN PETROLEUM ASPHALTS 445 

intimate mixing of the elements by rapidly agitating the asphalt in 
a closed vessel through which a current of air is passed. 76 Con- 
tinuous processes involve the following expedients: circulating the 
asphalt through a horizontal still divided into compartments into 
which air is blown individually; 77 circulating the asphalt through 
a series of stills into each of which air is blown; 78 passing the as- 
phalt in conjunction with a stream of air through a tube-heater; 79 
flowing or spraying the melted asphalt through a chamber in which 
a counter-current of air is passed. 80 

Various mechanical expedients have been suggested to facili- 
tate the blowing process, including the following. To conserve fuel, 
the freshly distilled residual oil, before it is permitted to cool, is 
blown in a heat-insulated still without the application of external 
heat. 81 Constant temperature is maintained during the blowing 
operation by a thermostatically controlled cooling device. 82 To 
prevent further oxidation of the blown product while still at a high 
temperature, it is maintained in contact with an inert gas. 83 De- 
vices for condensing and returning to the still any vapors that are 
evolved during the blowing process. 84 Recirculating the air as well 
as any evolved vapors through the charge in a closed system. 85 The 
blown product may be "stabilized" by maintaining at a high tem- 
perature for 24 hours. 86 

The use of different mixtures has been suggested for the pur- 
pose of improving the characteristics of the finished product, in the 
way of imparting rubber-like properties, greater toughness, increas- 
ing its resistance to temperature changes, augmenting its weather- 
resistance, etc., including the following: a mixture of semi-asphaltic 
residual oil and fatty-acid pitch, with or without gilsonite; 87 a mix- 
ture of residual oil, pine tar and rubber; 88 a mixture of residual 
oil or residual asphalt with vegetable drying oil; 89 a mixture of 
residual asphalt with cylinder oil stock; 90 a mixture of gilsonite with 
cylinder oil stock; 91 asphalt mixed with the high-boiling point, SO 3 
insoluble residue derived from the Edeleanu extraction process; 92 
a mixture of asphalt with pressure tar (cracking-still residue) ; 98 a 
mixture of sludge asphalt neutralized with magnesium oxide; 94 
blowing an aqueous-clay dispersion of residual oil with metallic 
driers at a comparatively low temperature. 95 

Blown asphalts vary in consistency from semi-liquids to moder- 



446 * PETROLEUM ASPHALTS XX 

ately hard solids at room temperature. They are marketed under 
various proprietary names such as Byerlite, Sarco, Hydrolene, Tex- 
aco, Parolite, Korite, Stanolind, Obispo, Ebano, etc. 

The advantages of "blowing" over the steam-distillation process 
are as follows: 

(1) The yield of asphaltic residue from the blowing process 
is mucn greater than when steam distilled. 

( 2 ) Blown petroleum asphalts are less susceptible to tempera- 
ture changes than steam distilled products, and in addition acquire 
a certain amount of elasticity and resilience, usually termed "rubber- 
like" properties. Upon comparing a residual asphalt with a blown 
product of the same fusing-point, it will be found that the latter is 
considerably softer, as evidenced by its consistency or penetration. 
Conversely, upon comparing a residual asphalt with a blown prod- 
uct of the same hardness or penetration, the fusing-point of the 
latter will be found to be considerably higher. 

(3) In many cases it is possible by blowing to obtain a residue 
of better quality than if the steam-distillation process were used, and- 
in fact the blowing process renders many crude petroleums available 
which could not otherwise be used for preparing high fusing-point 
asphalts. Non-asphaltic petroleum will produce fairly good as- 
phalts when blown, whereas the same crude will produce worthless 
residual asphalts by the steam distillation process. 

(4) It is easier to control the "grade 11 of asphalt by blowing. 
As previously noted, the progress of blowing is more rapid at the 
start of the process than towards its conclusion. In other words, 
the blown asphalt is said to "come to grade" very slowly. With 
steam distillation, the alteration is much more marked at the end 
of the distillation process, so that the steam-distilled asphalts "come 
to grade" very rapidly. In attempting, therefore, to produce a resi- 
dual asphalt of a definite fusing-point or hardness, the blowing proc- 
ess is preferable, since it may be controlled to better advantage. 

Figure 129 shows the effect of prolonging the blowing process 
(at 425 F.) on the fusing-point (Ring and Ball method, Test 15*), 
and penetration (needle penetrometer, test 9^) of a topped mixed- 
base petroleum. 96 The ductility-fusing-point curve is almost a 
straight line for residual asphalts derived from the same crude oil, 
whereas in the case of blown asphalts a decided break or change in 
direction is found to occur. 97 

Figure 130 illustrates the consistency, tensile strength (multi- 
plied by 10) and ductility curves of a typical blown petroleum as- 



XX 



BLOWN PETROLEUM ASPHALTS 



447 



phalt produced from mid-continental petroleum, having a fusing- 
point of 127 F. (K. and S. method). 

The care with which blown asphalts are prepared largely influ- 
ences their physical characteristics. When made from improper 



280 



*l 


I 



60 



320 

300 

260 

260 

240 

C 220 

.2200 

2 100 

160 

5 140 

a 120 

100 

80 

eo 

40 

to, 



12 



16 



18 20 22 24 26 26 30 32 34 36 36 40 42 
Hours Blown 



..-/Va ? Needle, lOOg, 5s, 777T 




10 12 14 ie 



is eo 32 e4 ^& ee 30 32 34 3& 33 40 

Hours Blown 

From "Good Roads" 



FiO. 129, Effect of Blowing on the Fusing-point and Hardness of Petroleum Asphalt. 

crudes or by careless treatment, blown asphalts are apt to have 
certain defects, viz.: 

(i) When made from non-asphaltic or semi-asphaltic petro- 
leums, they are likely to present a "greasy" surface, and especially 
on standing a few days, due to the partial separation of vaseline- or 
paraffin-like bodies. Blown asphalts made from asphaltic crudes 



448 



PETROLEUM ASPHALTS 



XX 



do not behave in this manner. The oily constituents and wax may 
be separated by first treating the crude petroleum with a selective 
solvent, as for example propane, 08 or liquid SO 8 , aniline, phenol, 
etc.," distilling off the solvent and blowing the residue in the usual 
manner. It is also claimed that these objectionable constituents may 
be eliminated if the asphalt is blown with air containing ammonia 



gas 



100 



( 2 ) Blown asphalts, and especially those of high f using-point, 
have the disadvantage of being "short," or in other words, they lack 
ductility. By carefully regulating the process, this defect may be 
minimized, particularly if the asphalt is subjected to a moderate 
amount of blowing. It is a fact, however, that the longer the blow- 
32* 77* N5* 



90 
60 
70 

50 
40 
30. 
3D 
10 

A 


X 


























LE6END 

Hardness 

Tensile 
Stren <gthfric) 

Ductility 
O Fusing font 




\ 


























\ 

V 


























\ 


























V 




























\ 

\ 




































\ 
































^ 


X. 




f 


































23 




v 












, 


^ 


?/ 




















\ 


t^ 


---*. 


JO 


^ 

s 


s 








X 
















/_ 


. 





'>* 




" I 


>~'ll,,^. 




ifnr 


1 ~- 


*- 


^ 





10 eO 30 40 50 60 70 60 90 100 110 120 130 140 150 160 

Temperature , Degrees Fahrenheit 
FIG. 130. Physical Characteristics of Blown Petroleum Asphalt. 

ing is continued, the less ductile will be the asphalt The ductility 
of the product may be decidedly improved by adding to the base 
material a proportion of the product derived from the Edeleanu 
extraction process (L e., hydrocarbons soluble in liquid SO 2 ) and 
blowing the mixture. 101 

(3) Asphalts when over-blown, or blown at too high a tempera- 
ture, show a separation of non-mineral matter insoluble in carbon 
disulfide, and a large percentage of carbenes. The former may 
readily be detected under the microscope (see Test 2&), also in cer- 
tain aggravated cases by the eye, by presenting a dull surface upon 
being disturbed (see Test 2a). 

When the blown asphalts first appeared on the market, they 
unfortunately did not enjoy a good repute, but their quality has 



XX BLOWN PETROLEUM ASPHALTS 449 

improved to such an extent, that blown asphalts may now be pro- 
cured of almost any fusing-point up to 400 F M which are not only 
more resistant to temperature changes, but are at the same time as 
ductile as any unblown product of the same "grade" (L e., fusing- 
point or hardness at 77 F.). 

f ln general, blown asphalts comply with the following charac- 
teristics : 

(Test i) Color in mass Black 

(Test 2#) Homogeneity to the eye at room temperature Uniform to gritty 

(Test 2^) Homogeneity under the microscope . . Uniform to lumpy 

(Test 3) Appearance surface aged indoors one week. . . Bright to dull and greasy 

(Test 4) Fracture Soft grades do not show a 

fracture, hard grades 
present a conchoidal 
fracture 

(Test 5) Lustre Bright to dull 

(Test 6) Streak on porcelain Brownish black to black 

(Test 7) Specific gravity at 77 F o. 90-107 

(Test 9^) Penetration at 77 F ' 25-200 

(Test 9^) Consistency at 77 F 2-30 

(Test gd) Susceptibility index 8-40 

(Test 10) Ductility Variable 

(Test n) Tensile strength Variable 

(Test 15*) Fusing-point (K, and S. method) 80-400 F. 

(Test i$) Fusing-point (R. and B. method) 100-425 F. 

(Test 1 6) Volatile matter, 500 F. in 5 hours 1-12 per cent 

(Test 170) Flash-point 35o~55o F, 

(Test 18) Burning-point 400-650 F, 

(Test 19) Fixed carbon 5- 20 per cent 

(Test 21) Solubility in carbon disulfide 95-100 per cent 

Non-mineral matter insoluble 0-5 per cent 

Mineral matter o-J per cent 

(Test 22) Carbenes o-io per cent 

(Test 23) Solubility in 88 petroleum naphtha 50-90 per cent 

(Test 25) Water Absent 

(Test 28) Sulfur Tr - 7. 5 per cent 

(Test 30) Oxygen 2- 5 per cent 

(Test 33) Solid paraffins o- 10 per cent 

(Test 340) Saturated hydrocarbons 30- 75 per cent 

(Test 34^) Sulfonation residue 90-100 per cent 

(Test 37*) Saponifiable constituents Tr.- 2 per cent 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction No 

Figure 131, plotted by the author from hundreds of determina- 
tions, shows the relation between the specific gravity and fusing- 
point of residual oils, blown asphalts and residual asphalts. 

Residual oils range in specific gravity from 0.85 to 1,07 at 77 
F., and in fusing-point (K. and S. method) from 20 to 100 F.; 



450 



PETROLEUM ASPHALTS 



XX 



blown asphalts range in specific gravity from 0.90 to 1.07, and in 
fusing-point from 80 to 400 F. ; residual asphalts range in specific 
gravity from i.oo to 1.17 and in fusing-point from 80 to 225 F. 
The chart shows that residual oils verge into the residual and blown 
asphalts respectively, and it also graphically illustrates the differ- 
ence between the residual and blown asphalts. It will be observed 
that the effect of blowing is to increase the fusing-point and decrease 
the specific gravity of the product 

Another method for distinguishing between blown and residual 
asphalts, devised by the author, consists in finding their hardness 
by means of the consistometer (Test gc) at a temperature exactly 







20 100 225 300 400 

Fusing Point, Degrees Fah. 

FIG. 131. Relation between the Specific Gravity and Fusing-point of Residual Oils, 
Blown Petroleum Asphalts and Residual Asphalts. 

50 F. lower than their fusing-point by the K. and S, method. Blown 
asphalts show a hardness of less than 15, whereas residual asphalts 
show a hardness greater than 15 under these conditions. This is 
illustrated by the examples given in Table XXXIX. 

It is of interest to note in connection with the foregoing figures, 
that for any particular crude, the hardness at the " fusing-point less 
50 F." decreases with the extent of the blowing, but remains practi- 
cally constant in the case of the residual asphalts, regardless of the 
extent to which the distillation may have been carried. 

Blown asphalts, due to their greater softness, and correspond- 
ingly large proportion of "life-giving" constituents, are better 
weather-resistants than residual asphalts derived from the same 
crude, having the same fusing-point and showing the same propor- 



XX 



BLOWN PETROLEUM ASPHALTS 
TABLE XXXIX 



451 





Fusing-point, 
(Test 15*) 


Hardness (Test 9^) at 
50 F. below the 
Fusing-point 


Blown Petroleum asphalts: 
Lima, grade 120 


QI . r F. 


Hd. at 41.5 F. = n 2 


Lima, grade 1 50 


i 


Hd. at 105 o F. =* 10 i 


Lima, grade 185 


* j j 

214. 


Hd. at 164 o F. ~ 78 


Lima grade 285 ..... 


271 C 


Hd. at 221 5 F = 67 


Mid-continental, grade 115, . 
Mid-continental, grade 180. . 
Mid-continental, grade 215. . 
Residual asphalts: 
California, grade E, 


* 1 * O 
100 
164 
215 

oo 


Hd. at 50.0 F. - ii 9 
Hd. at 114.0 F. 10.3 ' 
Hd. at 165.0 F. = 8.4 

Hd, at 40.0 F. = 21.5 


California, grade DE . . .... 


108 


Hd. at 58 o F. =* 22 2 


California, grade D 


124 


Hd. at 74.0 F. = 22 2 


California grade C 


146 


Hd. at 96 o F = 22 9 


California, grade CB 


168.5 


Hd. at 118.5 F, = 23 5 


California, grade B 


2OQ 


Hd. at 159 o F = 22 9 


Mid-continental, grade 140. . 
Mid-continental, grade 180. . 


119.5 
158 


Hd. at 69,5 F, = 21.5 
Hd. at 108.0 F. 21.5 



tion of volatile matter. They are about equal in weather-resistance 
to residual asphalts of the same hardness prepared from the same 
crude, and far superior to sludge asphalts regardless of their hard- 
ness or fusing-point. It is a mooted question whether the native 
asphalts or the blown asphalts excel in weather-resisting properties, 
and to which in the author's opinion no categorical answer may be 
given. 

It has been observed that blown asphalts have a higher saponifi- 
cation value than residual asphalts, upon comparing grades of the 
same fusing-points. 102 Three samples of the same product tested 
as follows: 





Fusing-point 
(K. and S.) 
(Test 1 50 ) 


Acid Value 
(Test 37*) 


Saponification 
Value 
(Test 37</) 


Sample No. i 


70 C, 


O.OT 


12. O< 


Sample No, 2 


100 C. 


O.O7 


18. 


Sample No. 3 


icoC. 


O.O'l 


42.O 











It is concluded that the saponification value of asphalts is in- 
creased by blowing, in a manner similar to that observed with 



452 PETROLEUM ASPHALTS XX 

paraffin waxes, etc., and that ester-like bodies and anhydrides are 
produced during the blowing process. On the other hand Edmund 
Graefe 108 ascribes the high saponification values (some of which 
he found to be as high as 60) to the presence of sulfuric acid in the 
blown asphalt. He points out that all asphalts normally carry sul- 
fur in combination, and that in some of them, e. g., Mexican as- 
phalts, the sulfur is loosely combined with the associated hydrocar- 
bons, so that during the blowing process this loosely combined sulfur 
unites with the oxygen of the air introduced into the heated asphalt, 
forming sulfuric acid. He predicts that if this sulfuric acid re- 
mains in the asphalt, it is apt to cause its disintegration upon ex- 
posure to the elements. Graefe also reports that the oily distillate 
condensed during the blowing process will combine with strong 
alkalies, which when neutralized with mineral acid forms a light col- 
ored, stringy resinous mass. On the other hand, it has been claimed 
that the weather-resistance of blown asphalts may be improved by 
treating the product with a 10 per cent solution of hydrochloric 
acid. 104 

Table XL includes the results obtained by the author upon 
examining representative blown asphalts derived from different 
crudes and blown to different extents. 

SULFURIZED ASPHALTS 

The process of treating asphalt with sulfur was first disclosed 
by A. G. Day 105 and subsequently by J. A. Dubbs 106 who heated 
Pennsylvania, Lima and Ohio residuums with 20 to 25 per cent of 
sulfur, at a temperature somewhat below the boiling-point of sulfur, 
until the evolution of gas ceased. The resulting product is very 
similar in its physical properties to blown asphalt, being only slightly 
susceptible to temperature changes, but it is still further lacking in 
ductility. Thirty years ago, asphalt treated in this manner was 
exploited under the name "Pittsburgh Flux." This was before 
blown asphalts appeared on the market, which on account of their 
smaller cost of production, soon displaced the sulfurized product. 

Processes have been described involving the vulcanization with 
sulfur of the following classes of bituminous products: native 
asphalts; 107 native asphalt (e. g. Trinidad) mixed with vegetable 
oils; 108 native asphalt (e. g- Trinidad) fluxed with fatty-acid 



TABLE XLI. CHARACTERISTICS OF TYPICAL RESIDUAL ASPHALTS 



No. 


Test 


From Semi-asphaltic Petroleum 


From Asphaltic Petroleum 


Mid-continental 


Mexican 


California 


Gulf-coast 


Trinidad 


Venezuela 


Japan 


za 
ib 
3 
4 
5 
6 
7 

9 b 
ge 

9 d 
lob 

n 


Physical Characteristics: 
Homogeneity to eye at 77 F 
Homogeneity under microscope 
Appearing surface, aged 7 days 


Homo. 
Homo. 
Dull 
Conch. 


Homo. 
Homo. 
Dull 
Conch. 


Homo. 

Dull 
Conch. 


Non-horn. 
Lumpy 
Dull 
Concli 


Homo. 
Gritty 
Bright 
Conch. 


Homo. 
Homo. 

Bright 
Conch. 


Homo. 
Gritty 
Bright 
Conch 


Homo. 
Homo. 
Bright 
Conch 


Homo. 
Homo. 
Bright 
Conch 


Homo. 
Homo. 
Bright 
Conch 


Gritty 
Bright 
Conch 


Non-horn. 
Lumpy 
Bright 
Conch 


Homo. 

Bright 
Conch 


Bright 


Homo. 
Bright 


Homo. 
Homo. 
Bright 
Conch 


Bright 
Conch. 


Homo, 
Homo. 
Bright 
Conch. 


Homo. 
Homo. 
Bright 


Fracture 


Lustre 
Streak 
Specific gravity at 77 F 


Bright 
Black 

1.050 


Bright 
Black 

1.078 


Bright 
Black 
1. 1 19 


SI. dull 
Black 
1.145 


Bright 
Black 
1.015 


Bright 
Black 
1.024 


Bright 
Black 
1.036 


Bright 
Black 
1 .065 


Bright 
Black 
1.095 


Bright 
Black 
1.113 


Bright 
Black 
1.127 


Bright 
Black 

1.158 


Bright 
Black 

I .022 


Bright 
Black 
1-033 


'Black' 

1.095 


Bright 
Black 
i . 1 20 


Bright 
Black 

1.082 


Bright 
Black 


'Black' 


Mechanical Tats: 
Penetration at T 1 5 F 
Penetration at 77 F 


88 
37 
9.5 

5.1 

15-2 

66.9 

Si-7 
37 
19 


O.I 

2.7 
15.0 


45 
21 

5 
9.6 

23-5 
81.4 
50.5 
64.5 
IO 


0.35 

4-2 
9-5 


12.5 
3-5 

27.1 
5-5 
107.0 
48.0 


6 

47-9 
88.8 

>100 

> 45 


132 
32 

12 

3-1 


99 

24 
8 

4-5 


84 

7 
6.5 


70 
24 

10 

6.8 


28 
15 
6 
'3-9 


ii -5 
3 



28.8 


8 
i 
o 
38.0 


7 



o 
45-1 


48 
19 
M 

8.2 


4P 
9 
IO 

10.4 


51 

20 
12 

8.8 


12 

2 
O 
27.2 


78 
26 
7 
6.0 

2O. 2 
72.1 
46.5 
42 
2O 


0.8 
4.1 

IO.O 


46 

17 



9-4 
26.6 

>IOO 

> 50 

22 
15 


1.6 

6.2 

13-4 


Soft 
93 
16 

2.8 

6.1 
51.0 
41.9 

IOO 
12 




Consistency at 1 1 5 F 


Consistency at 32 F 
Susceptibility index 
Ductility in cms. at 1 1 5 F 
Ductility in cms. at 77 F 


60.4 

47-3 


68.0 
47-8 


73-0 
46.5 


6 4 .6 
4 6.6 

57 
9 



0.6 

3-5 

10. 


78.3 
44.0 
12.5 



1.65 

6.2 

12.0 


> 42 

8.0 

3-95 
5- 
8.0 


> IOO 

> 40 



o 
3-4 
4.0 

5-2 


>100 

> 45 

o 
4.25 
4.2 

3-7 


56.3 

32.0 
50 
28 

I 

3.8 

5-2 
12. O 


65,1 

29.2 
32 
15 

o 

5.5 

7.0 
18.0 


*8. 7 
43-3 

70 

22 
O 
0.4 
2.8 
8-7 


>IOO 

> 45 
3-5 
o 
o 

4.85 

5-5 

10.2 


o 

7- 


o 

5-5 
4.0 


8 
0.4 

2.8 

8.5 


3-5 



0.8 
4.0 


3 



0.75 
5.0 
10.5 


Ductility in cms. at 32 F 
Tensile strength in kg. at 1 1 5 F 
Tensile strength in kg. at 77 F 
Tensile strength in kg. at 32 F 


5 
15* 
16 

170 
19 


Thermal Tests: 
Fusing-point, deg. F. (K. and S. method). , . 
Fusing-point, deg. F. (R. and B. method). . . 
Volatile, 500 F. in 5 hrs., per cent 
Flash-point, deg. F 


119.5 
131-5 

0.78 
5^5 
13.8 


142 
159 
0.50 
532 
18.5 


167 
184 

I .00 

575 
23.1 


227 

595 
33-3 


121 
I4I.5 

0. 7 6 

520 


'33 

'54 
0.50 

555 


'43 
162 


124 
142 


I 4 6 
I6 3 


168.5 
188 


209 

220 


218 
229 . 5 


150 
167 


187 
205 


"5 
132 


187 

2IO 


142 
1 60 
1.41 

487 


180 
195 
o-75 
525 
36-7 


"5 

133 

6.2 

420 
17-3 


547 




515 
30.2 


535 
34-0 


545 
37-o 


563 
39-7 


530 
25.7 


552 
33-5 


528 
29.1 


56l 
38-4 


' ' * 










21 

22 
23 

28 

33 
34* 
34* 


Solubility Tests: 
Soluble in carbon disulfide 
Non-mineral matter insoluble 
Mineral matter 
Carbenes 


99.15 
0.50 


99.03 

0.70 


96.45 
3.12 


91 .02 
8.20 


97 5 
2.15 


98.22 
1-33 


97-95 
i. 80 


98-93 

1.07 


98.67 
0.9O 


98.64 

I . IO 


98.12 
i. 60 


86.20 
13.48 


99-5 

O.2 


98.3 
o.3 


99-35 

0.48 


98.39 
1.28 


98.7 

O.I 


98-5 

0.2 


99-2 


1.8 
82.5 


80.3 


5-o 
72.3 


12.3 

61 .0 


0.6 
76.8 


1.82 


2.2 


'-5 


2-5 


4.2 


5.6 


28.2 


0.2 


0-3 
66.7 


7 8io 


66.6 


68.5 


O.2 
65.0 


79.0 


Soluble in 88 petroleum naphtha 










52.3 


45-2 






Chemical Tests: 
Sulfur 


0.95 




i-3 


o 6 


6.4 


4.2 
1-7 
42.9 


5.8 
1.4 
30.3 








0.8 








2.8 




2-5 




0.6 


Solid paraffins 
Saturated hydrocarbons 


1.3 


1.25 
60 7 




70.1 


2.6 

38.5 

97 5 


Tr. 


Tr. 
30.6 


o.o 


o.o 

35.8 

98 o 


37-o 


0.2 
38.0 


O. I 

42.3 


o.o 

24.0 


0.0 

28.3 

96.4 


0.0 

27.5 
97.0 


O.O 

32.1 

9 8 tf 


O.I 

35-2 


Sulfonation residue 




95 









































XX RESIDUAL ASPHALTS 453 

pitch ; 109 residual asphalts ; 110 residual asphalt mixed with vegetable 
oils; 111 residual asphalt fluxed with fatty-acid pitch; 112 residual as- 
phalt in combination with aluminium oleate or stearate; 118 sludge 
asphalt; 114 wurtzilite asphalt; 115 gilsonite mixed with vegetable 
oils; 116 gilsonite fluxed with fatty-acid pitch; 117 asphalts fluxed with 
resins; 118 mixture of asphalt, rosin, rubber and vegetable oil; 119 
boiling an aqueous dispersion of asphalt with sulfur/ 20 

In place of sulfur alone, the use of the following agents has 
been proposed for vulcanizing asphalts and mixtures containing the 
same : mixture of sulfur and FeS ; 121 mixture of sulfur and SO 2 with 
a catalyst (e. g., a sulfide or oxide of P, As, Sb, Sn, Mo, V, or 
W); 122 sulfur and lead peroxide; 123 sulfur and calcium oxy- 
chloride; 124 sulfur and sulfuric acid; 125 sulfuric acid alone; 126 spent 
iron oxide (containing sulfur) obtained as a by-product in desulfur- 
izing coal-gas; 127 antimony sulfide, with or without sulfur; 128 sulfur 
in the presence of chlorine; 129 sulfur dichloride ; 130 sulfurylchloride 
or pyrosulfurylchloride ; 131 chlorine in the presence of a u chlorine 
carrier" (e. g. hexachlor ethane) ; 132 cyanide residues; 183 etc. 

RESIDUAL ASPHALTS 

As stated previously, these are derived from the steam distilla- 
tion of semi-asphaltic or asphaltic petroleums. 134 Non-asphaltic 
petroleums are unsuitable for manufacturing residual asphalts, 
although processes have been devised based upon their use. 135 
The distillation is continued until the residual asphalt reaches 
the desired "grade." The temperature of the residue in the still is 
carefully observed, and under no circumstances allowed to exceed 
750 to 800 F,, otherwise excessive decomposition and cracking of 
the hydrocarbons will take place, and result in the production of an 
inferior product 136 This is especially liable to be the case if a resi- 
dual asphalt of hard consistency and high fusing-point is to be pro- 
duced. Mexican petroleums are more susceptible to overheating, 
and great care must be taken not to allo'w the residue in the still to 
exceed a temperature of 575 to 625 F, The distillation must not 
proceed too rapidly, otherwise a certain amount of cracking will 
take place, and the asphalt will have too low a flash-point and con- 
tain a certain amount of free carbon* In the early days of the 



454 PETROLEUM ASPHALTS XX 

industry, the residual asphalts were carelessly manufactured, with- 
out suitable temperature control, and as a result they soon fell into 
disrepute. At the present time, residual asphalts are being mar- 
keted of excellent quality, including products fusing as high as 
225 F M with a hardness in the neighborhood of 100 on the con- 
sistometer scale (Test 9^), but this is due solely to the better 
methods of control. Other things being equal, it is not as easy to 
produce a residual asphalt as a blown product of a given high 
fusing-point. 

A process 137 for removing undesirable constituents of a paraf- 
fin- or vaseline-like character from residual asphalts (12 to 24 
Baume) derived from a mixed-base petroleum, consists in intro- 
ducing large quantities of low-pressure steam superheated to 600 to 
700 F., through a charge of the asphalt heated in a still to 450 to 
700 F., or by distilling the asphalt under vacuum. 138 Any free 
carbon may be removed from the topped petroleum or pressure tar 
or residual oil prior to the final distillation, by precipitation, 139 or by 
centrifuging, 140 or by acid-treatment. 141 The temperature may be 
suitably controlled during the distillation process by supplying heat 
through the medium of a highly-heated mass of so-called "heat- 
carrier" (e. g. asphalt, fused metallic salts, molten lead or tin, 

etc.). 142 

Carelessly prepared residual asphalts may be detected by: 

1 i ) Lack of homogeneity (Test 2 ) . This may be due either to 
over-heating or because the distillation has been continued too far. 

(2) The surface of the material assuming a "greasy" appear- 
ance on aging. This is due to the use of crudes containing too large 
a proportion of paraffin- or vaseline-hydrocarbons, which have not 
been removed during the distillation process. 

(3) The presence of too large a percentage of volatile matter 
(Test 1 6) or too low a flash-point (Test 17), due to the distillation 
not having been carried far enough, or at a temperature sufficiently 
high to remove the low boiling-point constituents. 

(4) A large percentage of non-mineral matter insoluble in car- 
bon disulfide (Test 21). This is due either to overheating or to 
the distillation having been carried too far. Carefully prepared 
residual asphalts should not contain more than 5 per cent 

(5) The presence of carbenes (Test 22), which are produced 
by overheating. Carefully prepared residual asphalts should not 
contain more than 2 per cenLf 



XX RESIDUAL ASPHALTS 455 

Residual asphalts made from semi-asphaltic petroleum are not 
as susceptible to overheating as those derived from purely asphaltic 
petroleum. In both cases the percentage of asphalt recovered in the 
distillation process is greater than that contained in the original 
petroleum, due to the fact that the heavy lubricating oils are polym- 
erized or condensed under the influence of heat into substances re- 
sembling asphalt. In a purely asphaltic petroleum, the quantity of 
residual asphalt formed during the distillation process is propor- 
tionately less than in the case of mixed-base petroleum, but the 
residual asphalt in the former case will not show a greasy surface on 
aging, no matter how carelessly it may have been distilled. 

The effect of continued steam-distillation on the fusing-point, 
specific gravity, specific viscosity, float test, penetration, fixed car- 
bon and percentage insoluble in 88 petroleum naphtha, for Mexi- 
can, Californian and Texas residual asphalts has been described by 
B. A. Anderton. 143 

Residual asphalts in general comply with the following charac- 
teristics : 

(Test i) Color in mass Black 

(Test 2) Homogeneity Variable 

(Test 3) Appearance surface aged indoors i week. Variable 

(Test 4) Fracture Conchoidal in the case of 

hard residual asphalts 

(Test 5) Lustre Variable 

(Test 6) Streak on porcelain Black 

(Test 7) Specific gravity at 77 F i .00-1 . 17 

(Test 9^) Penetration at 77 F 150-0 

(Test 9*:) Consistency at 77 F 5-100 

(Test 9<J) Susceptibility index 40-60 

(Test 10) Ductility at 77 F Variable 

(Test 1 1) Tensile strength at 77 F o. 5-10.0 

(Test 150) Fusing-point (K. and S. method) 80-225 F. 

(Test 15^) Fusing-point (R. and B. method) 100-250 F. 

(Test 16) Volatile matter Variable 

(Test 17) Flash-point 400-600 F. 

(Test 18) Burning-point 450-700 F. 

(Test 19) Fixed carbon 5- 40 per cent 

(Test 21) Soluble in carbon disulfide 85-100 per cent 

Non-mineral matter insoluble o- 15 per cent 

Mineral matter o- i per cent 

(Test 22) Carbenes o- 30 per cent 

(Test 23) Solubility in 88 petroleum naphtha 25- 85 per cent 

(Test 28) Sulfur Tr - 10 per cent 

(Test 29) Nitrogen Tr.- i .o per cent 

(Test 30) Oxygen o- 2j per cent 

(Test 32) Naphthalene None 

(Test 33) Solid paraffins o- 10 per cent 



456 PETROLEUM ASPHALTS XX 

(Test 340) Saturated hydrocarbons 25- 75 per cent 

(Test 34^) Suifonation residue 90-100 per cent 

(Test 37*) Saponifiable constituents o- 2 per cent 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction . . . . No 

Residual asphalts are characterized by the following features: 

(1} Their comparatively high specific gravity, serving to dis- 
tinguish them from blown asphalts. 

(2) Their greater hardness or consistency at 77 F. for a given 
fusing-point, which also distinguishes them from blown asphalts. 

(3) The greater tensile strength at 77 F. for a given fusing- 
point, which similarly distinguishes them from blown asphalts. 

(4) Their lower fusing-point serves to distinguish them from 
the asphaltites. 

(5) The susceptibility index is very much higher than blown 
asphalts. In the case of residual asphalts the susceptibility index is 
greater than 40, whereas with blown asphalts it is always less 
than 40. 

( 6 ) The volatile matter, which for a given fusing-point is lower 
than that contained in the crude native asphalts. 

(7) The flash-point, which for a given fusing-point is higher 
than that of the crude native asphalts. 

(8) The fixed carbon, which for a given fusing-point is greater 
than that of blown asphalts. 

(9) The mineral matter, which runs well within i per cent and 
serves to distinguish residual asphalts from most of the native 
asphalts, 

(10) Carbenes when present in percentages in excess of 5, 
serve to distinguish them from native asphalts. 

( 1 1 ) Solid paraffins when present serve to distinguish residual 
asphalts from native asphalts, although this test is not infallible, for 
as pointed out previously, there are certain residual asphalts which 
do not contain paraffin (i. e., obtained from asphaltic petroleums) 
and conversely, many native asphalts yield small percentages of 
paraffins upon being destructively distilled. 

(12) The saturated hydrocarbons will exceed 25 per cent in the 
case of residual and blown asphalts, whereas they will be less than 
25 per cent in the cases of native asphalts. 144 With asphaltites the 
saturated hydrocarbons amount to less than 10 per cent. 

(13)^ A greater percentage of sulfonation residue is derived 
from residual and blown asphalts than from the various pitches. 

(14) A negative diazo reaction, which distinguishes residual 
asphalts from pitches derived from wood, peat, lignite, coal, shale 
and bones. 



XX RESIDUAL JSPHJLTS 457 

(15) The absence of the anthraquinone reaction, which dis- 
tinguishes residual asphalts from the various pitches derived from 
coal. 

(16) By the percentage of free asphaltous acids (Test 380) 
which run below 2 per cent in residual and blown petroleum as- 
phalts and above 2 per cent in the native asphalts. Similarly, the 
acid value (Test 370) of residual asphalts is usually less than i, 
whereas in the case of native asphalts it is higher than 2 and may 
run as high as 15. Marcusson 145 reports that the saponification 
value (Test 37^) of residual asphalts is usually less than 15, and 
in the case of native asphalts is greater than 25, and may run as 
high as 36.5. 

(17) In the case of natural asphalts, the "oily constituents" 
(Test 38e?) are fluid at 20 C, whereas in the case of petroleum 
asphalts (blown or residual) they are non-fluid, having the consist- 
ency of vaseline. 

There has been much discussion whether or not it is possible to 
distinguish between petroleum asphalts and native asphalts. 146 Vari- 
ous methods have been proposed for the purpose, but the only ones 
which seem to give dependable results are the percentages of satu- 
rated hydrocarbons (Test 340), free asphaltous acids (Test 380), 
acid value (Test 37*0) and the saponification value (Test 37^0, 
referred to in items (12) and (16) above. 

At the present time it is impossible to distinguish blown asphalts 
from combinations of asphaltites with residual oils or soft residual 
asphalts, since their respective properties are very much alike. 

Residual asphalts obtained from California petroleum are cus- 
tomarily designated by letters to differentiate the different grades. 
The so-called "A" grade is extremely hard and brittle, grinds to a 
non-adherent powder between the teeth, and ranges in penetration 
between i and 5 at 77 F. (No. 2 needle, 100 grams, 5 seconds.) 
"B" grade is quite hard and brittle, grinds to an adherent powder 
between the teeth, and ranges in penetration between 3 and 15 at 
77 F. "C" grade chews with difficulty and ranges in penetration 
between 10 and 25 at 77 F. U D" grade chews readily without 
sticking to the teeth, and ranges in penetration from 25 to 75 at 
77 F, "E" grade sticks to the teeth on chewing and shows a pene- 
tration greater than 75 at 77 F. "F" and "G" grades are in 
reality residual oils of high and low viscosities respectively. When 
carefully prepared, "B n grade does not contain more than 2 per 



458 



PETROLEUM ASPHALTS 



cent of non-mineral matter insoluble in carbon disulphide, and the 
softer grades correspondingly less. 147 

Figure 132 shows the hardness, tensile strength (multiplied by 
10) and ductility curves of a typical sample of "D" grade Cali- 
fornia residual asphalt fusing at 124 F. (K. and S. method). 

Table XLI includes the results obtained by the author, and 
Table XLII figures reported by J. Manheimer, 148 on representative 
specimens of residual asphalts. 



33 



77 a 



100 
90 
80 
70 
60 
50 
40 
30 

to 

10 



\ 






too 




















teeEKO 
Hardness 

Tensile 
~ Strength^ 

Ductility 
O Fusing Point 




y 


"' 




s 
\ 

\ 


















- i 


\ 








\ 
> 




















\ 






\ 

V 




















64. & 


\ 




\ 
\ 






















\ 


S 




\ 

V 








s 


7 A 


s > 




















\ 












/ 






\ 
\ 




















\ 


\ 


*fj 


\ 










\ 
























s s 


>5\ 


/ 











\ 
\ 
























>* 
/ 


*. 


^ 








\ 


\ 












o 






- 


-' 








6] 


*fr. 


3^ 


"'V 


X 





10 ^0 30 40 50 60 70 60 30 100 IK) 12^ 130 140 ISO 160 

Temperature, Degrees Fahrenheit 

FiG, 132. Physical Characteristics of D-Grade California Asphalt. 

The weather-resisting property of residual asphalts varies, de- 
pending upon the following circumstances : 

1 i ) The crude petroleum from which they were derived. Other 
things being equal, asphaltic petroleum produces the most weather- 
resisting residues, semi-asphaltic petroleum comes next, and non- 
asphaltic petroleum produces residuals having the least weather 
resistance. 

(2) The care with which the distillation has been performed. 
If the residue is badly decomposed or "cracked," as evidenced by 
the presence of free carbon or carbenes, its weather-resisting prop- 
erties will suffer in proportion. 

(3 ) The extent to which the distillation has been carried. Soft 
grades of residual asphalt carrying a large percentage of oily con- 
stituents (Test 38*) will stand the weather better than those from 
which the oily constituents have been removed by driving the dis- 
tillation to a point where a hard and brittle residual asphalt remains. 



XX 



RESIDUAL ASPHALTS 



459 



w>n N t*o t-cnC 
^.vrn^Ok^xnOy)^.? 



5 H V) *f N 
tOOO O t-. v 
H H nvo t^ 



Q 00 w> O <O O 
^OM*oio 

H H O M M M 



to "* f*5 h- Q O 
)HVOOHOOO 



8 
88 



5 

i 
I 



5 

a 
H 



K^.0' 

-H MNN< 



O^OOO 
. o v>ir> 



m O /> 

* 06 - 



*COO rf oc O 
't '^OiOO 



o cr> o o o o 

_C* rf rf w 5 



fO 1000 W M 00 V)00 



. 

M M M v> JC 



MOOVO\OOOOMCT co O vo t^. " 



V <J 

II 



<t IO ^- M O O 
^1 1000 M O 



>. o M <2 



M t^. O W> O O 00 <JO >0 N.tO 00 OO 
C 00 O H O> O -^VD Oi 

' - 



O f 

- O O> 



O> 

HW 



MHM<Of 



HK Q> O HM 
or>-O mCTis. 



IM^ 

ri 

1 



\OOMi oOOMixOO >000 ooO fi * 
't'VOOO O M rt^DOO fOUSOO O 

+ HHH O M M M O 1&MHMVOVO 

O w 



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*^vo t>. M to *o tooo oo *t 't to 10 o~i <> 
H 1000 M O ' >000 M CO tO Q 

~f HWCI Ow >ThMMC 'o < M fr 



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as 



o wnvH 






460 PETROLEUM ASPHALTS XX 

In general, residual asphalts of the highest quality are inferior 
in weather-resisting properties to native asphalts, blown asphalts, 
wurtzilite asphalts and fatty-acid pitches, upon comparing respective 
products of the same fusing-point and volatility. They are superior, 
however, to corresponding sludge asphalts and pitches derived from 
rosin, wood, peat, lignite, coal and bones. 

SLUDGE ASPHALTS 

Sludge asphalts are produced in much smaller quantities than 
residual or blown asphalts. They are derived from the purification 
of various petroleum distillates by means of sulfuric acid. The 
so-called "sludge asphalt" is present in the sulfuric acid sludge, 
which on cooling forms a black viscous mass. No asphalts are 
obtained from the caustic soda washings in the case of petroleum 
refining. The alkali is merely used to neutralize the sulfuric acid 
retained mechanically by the oil, thus differing from its action in 
the refining of peat and lignite tars. 

The acid sludges obtained from the purification of naphtha, 
kerosene and lubricating oil are combined and digested with water, 
air and steam in a lead-lined receptacle, whereupon the lighter 
oily constituents rise to the surface, the acid settles to the bottom, 
and the tarry matters form an intermediate layer known as "acid 
tar" when it is soft, and "acid coke" when it is solid at ordinary tem- 
peratures. The lighter oils are withdrawn and the boiling con- 
tinued until all the acid separates. The residuum is then washed 
with water, and heated by a spray of superheated steam until it is 
converted into sludge asphalt. The further the distillation is con- 
tinued, the greater will be the fusing-point and hardness of the 
sludge asphalt. The recovered oil is known as the "acid oil distil- 
late." The dilute sulfuric acid (specific gravity of 30 to 50 Be.) 
is concentrated, first in leaden pans, and finally in an iron still until 
it attains a gravity of 66 Be., when it is used over again. 

Another process consists in treating the acid sludge with con- 
centrated sulfuric acid and live steam until the mass separates into 
two layers, the bottom one consisting of concentrated sulfuric acid 
which is used over again, and the acid sludge on top. The latter 
is washed with hot water, which removes most of the acid, but there 
will still remain 3 to 15 per cent of acid mixed with the mass, 



XX SLUDGE ASPHALTS 461 

which is either heated to 250-350 C. so as to decompose the sul- 
f uric acid into SO 2 ; 149 or heated in an autoclave under pressure ; 15 
or heated air or steam blown through the melted mass to remove 
the SO 2 and SO 3 ; 151 or the free acid may be neutralized with a 
residue containing naphthenic soaps; 152 or else neutralized by add- 
ing slaked lime or limestone. 153 Other methods of treating acid 
sludges consist in heating to not exceeding 250 C. with an equal 
weight of residual asphalt under agitation; 154 fluxing with 1-5 per 
cent of light gas-oil, emulsifying with water under agitation, break- 
ing the emulsion by heating, treating the separated asphalt with 
CaO to neutralize all traces of acid, and finally distilling under 
vacuum to the desired consistency. 155 

The process shown diagrammatically in Table XLIII represents 
a method of treating acid sludges derived from heavy hydrocarbon 
distillates, such as lubricating oils. 156 

Acid sludges may be precipitated by salts of alkaline earths or 
of metals (e.g., copper or zinc), and after dehydration may be used 
for impregnating fabrics which are exposed continuously to mois- 
ture, preserving them from decay. 157 

Sludge asphalts test as follows : 

(Test i) Color in mass Black 

(Test la) Homogeneity to the eye at room temperature. Uniform 

(Test 2) Homogeneity under microscope Variable 

(Test 3) Appearance surface aged indoors one week. ... Bright 

(Test 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak on porcelain Black 

(Test 7) Specific gravity at 77 F 1 .05-1 . 20 

(Test 9^) Penetration at 77 F 1 50-0 

(Test 9f) Consistency at 77 F 5~ J oo 

(Test 9</) Susceptibility index ,..,..., 40-60 

(Test 10) Ductility at 77 F o 

(Test i$a) Fusing-point (K. and S. method) 80-225 F. 

(Test 15^) Fusing-point (R. and B. method) 100-250 F. 

(Test 1 6) Volatile matter 500 F. in 5 hours 2- 20 per cent 

(Test ija) Flash-point 300-500 F. 

(Test 19) Fixed carbon 5- 30 per cent 

(Test 21 ) Solubility in carbon disulfide 95-100 per cent 

Non-mineral matter insoluble , . o- 5 per cent 

Mineral matter (See NOTE) o- i per cent 

(Test 22) Carbenes 0-15 per cent 

(Test 23) Solubility in 88 petroleum naphtha 6o~ 95 per cent 

(Test 28) Sulfur 5- 10 per cent 

(Test 30) Oxygen 3- 7 per cent 

(Test 33) Solid paraffins o- } per cent 



462 PETROLEUM ASPHALTS XX 

(Test 340) Saturated hydrocarbons Less than 10 per cent 

(Test 34^) Sulfonation residue. 80- 95 per cent 

(Test 37^) Saponifiable constituents o- 2 per cent 

(Test 380) Free asphaltous acids Less than 2 per cent 

(Test 38^) Asphaltous-acid anhydrides , Less than 2$ percent 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction No 

NOTE. Sludge asphalts all carry traces of lead, derived from the leaden vessels in which they are produced, 
which is carried into solution by the sulfuric acid. The presence of lead will serve to identify sludge asphalts, and 
differentiate them from all other asphaltic substances. The author's investigations revealed lead varying in 
amounts from 0.05 to 0.25 per cent. 

Sludge asphalts are characterized by the following features : 

1 i ) Their intense black streak. 

(2) Their high susceptibility index, which distinguishes them 
from blown asphalts. 

(3) The high percentage of sulfur. 

(4) The high percentage of oxygen, which distinguishes them 
from all other forms of asphalt and constitutes one of the most 
dependable tests for identifying sludge asphalts. 

(5) The very small percentage of paraffin, which distinguishes 
them from residual asphalts obtained from mixed-base petroleum. 

(6) The extremely small percentage of saturated hydrocar- 
bons, which serves to differentiate sludge asphalts from all other 
asphaltic products. 

(7) The comparatively large percentage of sulfonation resi- 
due, which distinguishes them from pitches. 

(8) The negative diazo and anthraquinone reactions, which 
distinguish them from pitches derived from wood, peat, lignite, 
coal, shales and bones. 

(9) The large solubility of the harder grades in 88 naphtha, 
which distinguishes them from residual asphalts of the same hard- 
ness and fusing-point. 

Julius Marcusson 158 states that sludge asphalts may be recog- 
nized by the presence of sulfo-oxonium compounds, which on treat- 
ment with 88 petroleum naphtha will separate in the same manner 
as asphaltenes. They may be distinguished from the latter, how- 
ever, by dissolving in pyridine and adding water. Asphaltenes will 
separate out, but oxonium compounds will remain in solution. They 
may be precipitated by adding mineral acids, ferric chloride, silver 
nitrate, etc. They are not affected by alkalies, but are decomposed 
by hydrochloric acid with the separation of sulfuric acid. A speci- 
men of sludge asphalt examined by Julius Marcusson was found to 
contain 1 7 per cent oxonium derivatives* 



XX 



SLUDGE ASPHALTS 



463 




>n 

, ^ j.tt 

^53 5> 

rsi 

... rt 6 

111 



^ S v 

|2| 



s 



Si 
Jjjj- 

till 



UT3 8 O 

*s! i "3 

M w o -* 

>a bl*l 

-fl 

d-liJ1 



II 
'1- 



404 



PETROLEUM ASPHALTS 



XX 



Attempts have been made to blow sludge asphalts, either with 
air alone or by blowing in the presence of finely ground CaO. 159 
However, the blowing process serves largely to harden the sludge 
asphalt and increase its brittleness, unless it has first been fluxed 
with vegetable oils. 160 Heating with NaClO 3 converts sludge as- 
phalts into resinous products suitable for making molded articles. 161 
Sludge asphalts flux completely with gas-works coal tar, with which 
it may be distilled. 162 

Typical samples of sludge asphalt examined by the author gave 
the results included in Table XLIV. 

TABLE XLIV 
CHARACTERISTICS OF TYPICAL SLUDGE ASPHALTS 



No, 


Test 


From Various Sources, Mostly Mixtures 


aa 
2b 
3 
4 
5 
6 
7 


Physical Characteristics: 
Homogeneity to eye at 77 F . . 


Homo. 
Homo. 
Bright 


Homo. 
Homo. 
Bright 


Homo. 
Homo. 
Bright 
Conch. 
Bright 
Black 
i 068 


Homo. 
Homo. 
Bright 
Conch. 
Bright 
Black 
1.090 


Homo. 
Homo. 
Bright 
Conch. 
Bright 
Black 
1.076 


Homo, 
Homo. 
Bright 
Conch. 
Bright 
Black 
1-155 


Homogeneity under microscope . 


Appearance surface aged 7 days. , , , 


Fracture 


Lustre 






Streak 


Black 

1.057 


Black 
1.052 


Specific gravity at 77 F 




96 
gc 
9<* 

10* 

ii 


Mechanical Tests: 
Penetration at 115 F 


Too soft 
160 
25 
o.o 
3.4 
42.2 
49.7 

7 
38 
1.5 
o o 
o 4 
10. S 


Too soft 
95 

12 
O O 

7-1 
58 8 
59-5 
15 
82 
o 

O.I 
1.4 
4-5 


Too soft 
28 
7 



17-5 
71 8 
61.8 
45 
18 
o 
0.35 
3 85 
30 


Too soft 
20 

3 


19-9 
85 4 
53 4 
3-5 
0-75 
o 

1-3 
5 4 
8 o 


8 

2 

43-1 
87.9 

> IOO 

> 50 
o 




3-0 

7-5 
6 o 


5 
o 
o 
50-7 
95 2 

> IOO 

> So 



o 
o 
3 S 

8 2 

5 5 


Penetration at 77 F 


Penetration at 32 F 


Consistency at 115 F 


Consistency at 77 F 


Consistency at 32 F 


Susceptibility index 


Ductility in cm. at 115 F 


Ductility in cm. at 77 F 


Ductility in cm. at 32 F 


Tensile strength in kg. at 115 F 
Tensile strength in kg. at 77 F 


Tensile strength in kg. at 32 F 




XS 
IS* 
16 
17< 
19 


Thermal Tests; 
Fusing-point, deg. F. (K. and S. method) 
Fusing-point, deg. F.(R. and B. method) 
Volatile, 500 F. in 5 hrs., per cent 
Flash-point, deg. F. 


5 

IOI 

3 o 

47S 
8.8 


99 
H3 

2.2 
500 
12.3 


116 
134 
7-9 
430 
16,1 


1 60 
178 
2.5 

480 

22.0 


203 
225 
4-8 

482 

30.2 


210 
230 

S.o 

486 

25.4 


Fixed carbon, per cent 




ai 

22 
33 


Solubility 1 ests: 
Soluble in carbon disulfide 


98.98 
0.90 

0.12 
0.0 
93-2 


99 72 
o 20 
0.08 

0.2 

94 o 


99-51 
o 38 

II 
2 3 

78 7 


99.23 
0.72 
0.05 
I O 

74.6 


99.50 

0.40 

O.IO 
X.2 

66.8 


97.50 

2.43 

o 07 

13.2 
62.2 


Non-mineral matter insoluble ......... 


Mineral matter ........ 


Carbenes 


Soluble in 88 petroleum naphtha 


28 

33 
34 

346 


Chemical Tests: 
Sulfur 


8.7 
o.S 
9.0 
82.1 


7.8 
o 4 
8.9 
88.0 


5-4 

O.2 

7.2 


7S 
0.25 

5.5 


6.2 

o.z 
4.8 


8.3 

O.I 

3.9 
93-2 


Solid paraffins 


Saturated hydrocarbons 


Sulf onation residue 











XX SLUDGE ASPHALTS 405 

Sludge asphalts do not withstand the action of the weather as 
well as native asphalts, blown asphalts, residual asphalts, wurtziiite 
asphalt or fatty-acid pitch, comparing respective products of the 
same fusing-point and volatility, or of the same hardness and vola- 
tility. They are substantially equal in weather-resistance to the cor- 
responding grades of pitch derived from coal and bones, and are su- 
perior to those derived from rosin, wood, peat and lignite. In 
practice, they are usually fluxed with other forms of petroleum 
asphalt, rather than marketed in their pure state. 

A product has been marketed in the United States consisting of 
a mixture of sludge asphalt and pressure tar, which is decidedly 
inferior in weather-resisting properties. In some cases the sludge 
asphalt is mixed with other grades of petroleum asphalt, but with 
little benefit to the latter. It is claimed that the ductility of residual 
as well as blown asphalts at low temperatures may be improved by 
adding acid sludge to the topped oil prior to the distilling or blow- 
ing operation. 108 



CHAPTER XXI 
PARAFFIN WAX, WAX TAILINGS AND RESINS 

PARAFFIN WAX 
The commercial sources of pyrogenous paraffin wax are: 

(1) Peat tar; 

(2) Lignite tar; 

(3) Shale tar; 

(4) Paraffin-bearing petroleums. 

The peat-distilling industry is comparatively unimportant and 
does not form a factor in the production of paraffin. The lignite 
industry has only attained commercial importance in Germany, and 
the shale industry in Scotland. The treatment of paraffin-bearing 
petroleums for the recovery of paraffin is important the world 
around. The methods for recovering paraffin wax from lignite tar, 
shale tar and petroleum are substantially the same. In the case of 
lignite tar, the paraffin wax is obtained from the distillate fractioned 
after the crude oil, known, as the "paraffinaceous mass." With 
shale tar the paraffin wax is obtained from the distillate known as 
"heavy oil," distilling after the "intermediate or gas-oil" With 
paraffin-bearing petroleums, the paraffin wax is obtained from the 
fraction known as the "paraffin distillate." 

For a description of the methods of refining and purifying par- 
affin wax, the reader is referred elsewhere. 

Paraffin wax, including commercial "refined paraffin wax" and 
"refined scale wax" tests as follows: 

(Test i) Color in mass Pure white to yellowish 

(Test la) Homogeneity to the eye at room temperature. Uniform to slightly crys- 
talline 

(Test ic) Homogeneity when melted Uniform and transparent 

(Test 4) Fracture Conchoidal to hackly 

(Test 5) Lustre Dull and "waxy" 

(Test 6) Streak White 

(Test 7) Specific gravity at 77 F o. 85- 0.95 

(Test 9^) Penetration at 77 F 5-50 

466 



XXI WAX TAIUNGS 467 

(Test gc) Consistency at 77 F ij-8o 

(Test gd) Susceptibility index > 100 

(Test 10) Ductility at 77 F o 

(Test 15$) Fusing-point (R. and B. method) 105-160 F. 

(Test is/) Fusing-point (Special method) 100-150 F. 

(Test 16) Volatile at 325 F. in 5 hours 20-40 per cent 

Volatile at 500 F. in 5 hours 33-60 per cent 

(Test 170) Flash-point Comparatively low 

(Test 18) Burning-point Comparatively low 

(Test 19) Fixed carbon o- 2 per cent 

(Test 21) Solubility in carbon disulfide 99-100 per cent 

Non-mineral matter insoluble Trace 

Mineral matter Trace 

(Test 22) Carbenes o per cent 

(Test 23) Solubility in 88 petroleum naphtha 99-100 per cent 

(Test 30) Oxygen Trace 

(Test 33) Solid paraffins 95-100 per cent 

(Test 340) Saturated hydrocarbons 90- 99 per cent 

(Test 34^) Sulfonation residue 95-100 per cent 

(Test 37*) Saponifiable constituents o per cent 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction No 

Three grades of paraffin wax are specified by the U. S. Gov- 
ernment, having fusing-points (Test I5/) of 130-132 F., 124 
127 F. and 117120 F. respectively. Normal "slack wax" has a 
fusing-point of 125 F. Various fusing-points are demanded by 
the trade. 

Paraffin wax is remarkably resistant to the action of chemicals, 
but on exposure to the weather, the oily constituents soon evaporate, 
leaving a pulverulent and but slightly coherent mass behind. This 
is not due to oxidation, but merely to volatilization of the oils 
present in the wax. 

Paraffin wax withstands the continuous action of water very 
well and finds a ready market for preparing waterproof papers, for 
manufacturing candles, for household purposes, in miners' lamps, 
manufacture of matches, drinking cups, bottle caps, cartridge con- 
tainers, dry cells, wax figures, molds, crayons, etc. 

WAX TAILINGS 

This product is obtained during the dry distillation of non- 
asphaltic or semi-asphaltic petroleum. The residuum left in the 
retort at the end of the first distillation is subjected to a second 
process of dry distillation, whereupon the wax tailings distils over, 
just prior to the formation of coke. Wax tailings is sometimes 



468 PARAFFIN WAX, WAX TAILINGS AND RESINS XXI 

termed "still wax," although both these names are misnomers, since 
it contains only small quantities of paraffin wax. It consists largely 
of decomposition products, including chrysene, picene and anthra- 
cene, and has a decided yellow color, by which it is recognized 
during the process of distillation. Upon cooling it forms a very 
viscous semi-liquid to sticky semi-solid of a characteristic light yel- 
low to yellowish brown color. It complies with the following tests : 

(Test i) Color in mass Yellow to yellowish 

brown 

(Test 20) Homogeneity to the eye at room temperature Uniform to very 

slightly granular 

(Test 2#) Homogeneity under microscope Uniform to gritty 

(due to the crys- 
talline constitu- 
ents present) 

(Test 3) Appearance surface aged indoors Variable 

(Test 5) Lustre Waxy 

(Test 6) Streak Pale yellow 

(Test 7) Specific gravity at 77 F i .00-1 . 10 

(Test 9^) Penetration at 77 F 10-150 

(Test 9*) Consistency at 77 F 5-20 

(Test gd) Susceptibility index 20-40 

(Test 10) Ductility at 77 F Usually quite high 

(Test i$a) Fusing-point (K. and S. method) 60-100 F. 

(Test 15^) Fusing-point (R. and B. method) 65-110 F. 

(Test i6a) Volatile matter at 500 F., 5 hours 5-10 per cent 

(Test 170) Flash-point 300-450 F. 

(Test 19) Fixed carbon 2-8 per cent 

(Test 21) Solubility in carbon disulfide 98-100 per cent 

Non-mineral matter insoluble 0-2 per cent 

Mineral matter o-Trace 

(Test 22) Carbenes o-Trace 

(Test 23) Solubility in 88 petroleum naphtha 95-100 per cent 

(Test 28) Sulfur o-Trace 

(Test 30) Oxygen 0-2 per cent 

(Test 32) Naphthalene Absent 

(Test 33) Solid paraffins Tr.-5 per cent 

(Test 340) Saturated hydrocarbons 4O~?o per cent 

(Test 34*) Sulfonation residue 90-100 per cent 

(Test 37*) Saponifiable constituents Trace 

(Test 39) Diazo reaction No 

(Test 40) Anthraquinone reaction Yes 

Wax tailings is an exceedingly good flux, and will thoroughly 
amalgamate with the various pitches, likewise with the harder as- 
phalts and asphaltites, including even grahamite. 1 It forms a better 
flux than the residual oils derived from asphaltic petroleum. A 
very small percentage will often serve thoroughly to flux materials 



XXI WAX TAILINGS 469 

which are otherwise incompatible, and at the same time increase 
the ductility of the mixture. Certain asphalts, although they may 
flux together at high temperatures, will separate partially on cool- 
ing, forming a very finely granular condition, which is particularly 
noticeable when the surface of the mixture is freshly disturbed, or 
upon drawing a small pellicle into a thread. The presence of a 
small percentage of wax tailings will often prevent this, and it 
therefore enjoys a unique position among the fluxes. Large quan- 
tities, however, should be avoided, as wax tailings is extremely sus- 
ceptible to changes in temperature and lacks weather-proof prop- 
erties. The presence of wax tailings will increase the solubility of 
asphaltic substances in petroleum distillates, and accordingly be- 
comes useful for manufacturing certain types of bituminous paint. 
A representative sample of wax tailings tested by the author gave 
the following results: 

(Test 9$) Penetration at 165 F Too soft 

Penetration at 77 F too 

Penetration at 32 F 51 

(Test 9<:) Consistency at 115 F o.o 

Consistency at 77 F 5.9 

Consistency at 32 F 22, 9 

(Test gd) Susceptibility index 25 . o 

(Test io) Ductility at 115 F i . i 

Ductility at 77 F 3.9 

Ductility at 32 F 13.5 

(Test 11) Tensile strength at 115 F o.o 

Tensile strength at 77 F 0.5 

Tensile strength at 32 F 9.5 

(Test i $a) Fusing-point (K. and S. method) 90 F. 

(Test 15^) Fusing-point (R. and B. method) 98 F. 

(Test 170) Flash-point 382 F. 

A process has been proposed for coloring wax tailings for use 
as a saturant in the manufacture of saturated fabrics, felt-base floor 
coverings, paints, etc., which consists in distilling the wax tailings 
with superheated steam to a semi-solid or solid consistency and then 
combining with a soluble dye such as rhodamine, malachite green, 
etc. ; or else forming a mechanical mixture with a colored mineral 
pigment. 2 Wax tailings may also be vulcanized by heating with 
sulfur. 3 The production of wax tailings is not large, and hence it 
is not of great importance to the asphalt industry. 



470 PARAFFIN WAX, WAX TAILINGS AND RESINS XXI 

PETROLEUM RESINS 

These have been produced by distillation of certain crude petro- 
leums (e.g., Miri) which are free from asphaltenes, or by the action 
of anhydrous aluminium chloride (about 2 per cent) on an unsat- 
urated distillate obtained by cracking at a high temperature and low 
pressure, having a specific gravity at 20 C. of 0.840.86 and a 
boiling range of 23-180 C. The reaction mixture is treated with 
NaOH to precipitate the aluminium from the aluminium chloride 
polymer, whereupon the resin remains in solution and is recovered 
by distillation under reduced pressure, at as low a temperature as 
possible. The resin is a hard, amber-colored product, having a 
fusing-point of 230240 F. (R. and B.), which is soluble in prac- 
tically all hydrocarbon solvents, but insoluble in methanoi, ethyl 
alcohol and acetone. It dissolves readily in drying oils, and has an 
acid value between o.i and 2. When a film is baked at 220 F. 
for i hour, it becomes insoluble in its original solvents. Petroleum 
resins are claimed to accelerate the drying properties of linseed 
and china-wood oils. 4 

ASPHALTIC RESINS 

A process has recently been commercialized for producing light- 
colored asphaltic substances falling within the chemical classifica- 
tion of "asphaltic resins" (see, Test 38^), by removing the as- 
phaltenes in accordance with the following procedure : ( i ) precipi- 
tating the asphaltenes with an agent, such as gasoline, pentane, etc. ; 

(2) treating with chemicals, such as sulfuric acid or sulfur trioxide, 
which converts the asphaltenes into an insoluble modification; and 

(3) treating with decolorizing agents, such as fuller's earth or 
carbon, with or without diluting agents. An example consists in 
dissolving residual asphalt derived from Java petroleum in twice 
its weight of light petroleum naphtha, then adding 2 per cent by 
weight of sulfuric acid, removing the acid tar and enveloping sub- 
stances by settling, adding 3 per cent by weight of bleaching earth, 
and finally filtering. The naphtha is thereupon removed from the 
filtrate by evaporation and the resulting light-colored asphalt steam- 
distilled to the required consistency. 5 Its physical characteristics 
are quite similar to wax tailings. It is characterized by a specific 



XXI ASPHALTIC RESINS 471 

gravity at 77 F. of 1.02-1.04, fusing-point (R. and B.) of 100- 
130 F., high ductility, brittleness at low temperatures, great sus- 
ceptibility to temperature changes, low viscosity when liquefied, and 
high adhesiveness. It may be fluxed with low-grade asphalts to 
improve the qualities of the latter. 6 The product has been recom- 
mended for use in preparing aqueous dispersions suitable for paints 
in combination with colored pigments, for impregnating fabrics, and 
for other purposes where the light color will prove an advantage. 
Another process consists in precipitating the asphaltenes from a 
solution of the asphalt in gasoline or petroleum naphtha, by the 
addition of colloidal silicic acid, whereupon the solution is decanted 
and evaporated; 7 also a process of distilling pressure tar with steam 
under vacuum (with or without the addition of A1C1 3 ) collecting a 
distillate having a specific gravity of 1.084-1.126, a fusing-point 
(R. and B.) of 93-150 F., and a ductility at 77 F. of over 100 
cm,, said product being a substantially solid resin at ordinary tem- 
peratures. 8 This product has been recommended for the manufac- 
ture of pigmented paints and lacquers. 9 



CHAPTER XXII 
WURTZILITE ASPHALT 

Wurtzilite asphalt or wurtzilite pitch, marketed under the name 
of "kapak," is produced by cracking or depolymerizing wurtzilite. 
It is similar to the latter in its physical characteristics with the ex- 
ception of: 

1 i ) The hardness, which is very much reduced. 

(2) Its fusibility. Treated wurtzilite is fusible whereas crude 
wurtzilite is not. 

(3) Its solubility. Treated wurtzilite is readily soluble in car- 
bon disulfide, and moderately so in 88 petroleum naphtha, whereas 
the crude product is practically insoluble in both. 

The process consists in heating the wurtzilite in a closed vessel 
or still to a temperature of 500 to 580 F., under more or less 
pressure. Vapors are evolved during the process that are con- 
densed and returned to the still, and in turn attack the wurtzilite, 
first reducing it to a plastic mass, which after heating is converted 
into a fusible substance. If the vapor pressure becomes too great, 
some is allowed to escape. The process which takes place is vir- 
tually a "depolymerization." * 

Another process consists in grinding together wurtzilite and gil- 
sonite and then heating together for some time at 350 C. until 
readily fusible, whereupon the mass is fluxed with petroleum 
asphalt. 2 

In practice, the wurtzilite is first run through a crusher to break 
up any coarse lumps, and then fed into a horizontal cylindrical still 
through two charging hoppers, one at either end, provided with 
tightly fitting covers which are fastened into place before the fires 
are started. The bottom of the still is protected by a fire-brick 
arch, and the products of combustion after passing underneath the 
arch, are returned in three fire-flues running through the still (one 

io in, in diameter and two 6 in.), and thence back again in the space 

472 



XXII TREATMENT OF WVRTZILITE 473 

surrounding the still, above the arch. The vapors generated from 
the wurtzilite pass upward through two pipes joined to the top of 
the still, near the ends, and connected with a single water-cooled 
coil, which condenses the vapors and returns most of the condensate 
to the still. Not all the condensate is returned, however, for prac- 
tice has demonstrated that the optimum results are obtained if 2 to 
5 per cent of the distillate (based on the weight of wu^ilite 
charged into the still) is drawn off. This may be used as fuel 
under the still. 

The longer the wurtzilite is heated in its process of manufacture 
the greater will be the quantity of oils produced, which act in the 
same manner as a flux, and hence the fusing-point and hardness of 
the resultant product will be lower. 

It takes six to eight hours to raise the temperature of the charge 
to 400 F., then four to six hours to reach the maximum tempera- 
ture (580 F.), which is maintained from twenty-four to thirty-six 
hours. The contents are then allowed to cool to 450 F., and finally 
drawn off through a valve at the bottom. 

According to the author's investigations, Nova Scotia albertite is 
also amenable to this process, although up to the present time it has 
not been thus treated commercially. 

The wurtzilite asphalts are marketed under various arbitrary 
numbers ranking from "o" to "16," each of which is recommended 
for a specific purpose, including the manufacture of paints and var- 
nish, insulators, for manufacturing insulated wire, for weather- 
proofing conduits and cables, as a filler for mechanical and hard 
rubber compounds cured by the press or open steam method, for 
coating prepared roofings, for manufacturing carriage drills and 
similar compositions applied by the calendar process and cured by 
the dry-heat method, etc. Certain of these compounds represent 
mixtures of wurtzilite asphalt and gilsonite, with or without the 
addition of asphaltic fluxes (e. g., residual oil), and vegetable oils 
(e. g., linseed oil, palm oil, etc.). 

Wurtzilite asphalt complies in general with the following char- 
acteristics : 

(Test i) Color in mass Black 

(Test la) Homogeneity to the eye at room temperature. Uniform 

(Test ib) Homogeneity under microscope Uniform 

(Test 3) Appearance surface aged indoors one week. ... Very bright 



474 



WVR.TZIL1TE ASPHALT 



XXII 



(Teat 4) Fracture Conchoidal 

(Test 5) Lustre Bright 

(Test 6) Streak Brown to black 

(Test 7) Specific gravity at 77 F i .04-1 .07 

(Test gb) Penetration at 115 F 15-25 

Penetration at 77 F 5-20 

Penetration at 32 F 0-15 

(Test 9^) Consistency at 1 1 5 F 10-25 

Consistency at 77 F 20-50 

Consistency at 32 F 50-120 

(Test gd) Susceptibility index 30-40 

(Test io) Ductility at 115 F 1-5 

Ductility at 77 F o-i 

Ductility at 32 F o 

(Test H) Tensile strength at 115 F 1-4 

Tensile strength at 77 F 5-10 

Tensile strength at 32 F 8-15 

(Test 15*) Fusing-point (K. and S. method) 150-300 F. 

(Test 15^) Fusing-point (R. and B. method) 170-325 F, 

(Test i6a) Volatile at 500 F., 5 hours Less than 5 per cent 

(Test 170) Flash-point 450-600 F. 

(Test 19) Fixed carbon 5-25 per cent 

(Test 21) Solubility in carbon disulfide 98-100 per cent 

Non-mineral matter insoluble o-J per cent 

Mineral matter Tr.-2 per cent 

(Test 22) Carbenes 0-2 per cent 

(Test 23) Solubility in 88 petroleum naphtha 50-80 per cent 

(Test 28) Sulfur 4-6 per cent 

(Test 30) Oxygen 0-2 per cent 

(Test 33) Solid paraffins o-Trace 

(Test 340) Saturated hydrocarbons 5-12 per cent 

(Test 34^) Sulfonation residue 90-95 per cent 

(Test 37*) Saponifiable constituents Trace 

(Test 39) Diazo reaction . . No 

(Test 40) Anthraquinone reaction No 

Specimens of the unfluxed wurtzilite asphalt examined by the 
author tested as follows i 



No.o 



No. i 



No. 6 



No. 16 



(Test gb) Penetration at 115 F 

Penetration at 77 F 

Penetration at 32 F 

(Test gc) Consistency at 115 F 

Consistency at 77 F 

Consistency at 32 F 

(Test gd) Susceptibility index 

(Test i$a) Fusing-point (K. and S, method) 

(Test io) Ductility at 1 15 F 

Ductility at 77 F 

Ductility at 32 F 



16 
6 
o 

22.9 
45.6 

IIO.O 

3*-4 
269 

2 
O 
O 



19 

7 
I 

18.5 

41.8 
92.2 

33-4 

220 

3 
o 

o 



9 

4 

15.0 

38.5 
80.6 



200 

3 
o 
o 



34 

12 

7 
11.7 

71.1 

31-2 
190 

4 



XXII PROPERTIES OF WURTZILITE ASPHALT 475 

These figures indicate that the extent of softening and lowering 
of the fusing-point is dependent upon the extent to which the proc- 
ess of depolymerization has progressed. It is interesting to ob- 
serve in this connection that the susceptibility index remains prac- 
tically unchanged 

Wurtzilite asphalt is characterized by its low specific gravity, 
high fusing-point, low susceptibility index, extreme toughness and 
rubber-like properties (i. e., resiliency), high-tensile strength, small 
percentages of oxygen and non-mineral matter, large percentage of 
sulfonation residue, and absence of saponifiable constituents. 

It is quite similar in many respects to blown asphalts (particu- 
larly in regard to its susceptibility index), but may be differentiated 
from these by : 

(1) A greater hardness or consistency at 77 F. for any given 
fusing-point. 

(2) A greater tensile strength for any given fusing-point 

(3) Smaller percentages of oxygen. 

(4) Smaller percentages of saturated hydrocarbons. 

Wurtzilite asphalt is also similar in many respects to the fatty- 
acid pitches, especially in its toughness (resilience) and its low sus- 
ceptibility index. It is distinguished from these, however, by the 
following : 

(1) Its solubility in 88 petroleum naphtha, which is smaller 
than in the case of fatty-acid pitches. 

(2) The presence of sulfur, which is absent in the fatty-acid 
pitches. 

(3) The smaller percentage of oxygen. 

(4) The larger percentage of sulfonation residue. 

(5) The absence of saponifiable constituents. 

In other respects they are apt to test pretty much alike. 

Wurtzilite asphalt shows remarkable weather-resistance and 
finds its greatest use in manufacturing asphalt paints, for coating 
prepared roofings, 8 and for coating cotton-covered wires for elec- 
trical insulation. 4 Its use is limited by the small quantity produced, 
and the comparatively high price at which it is marketed. 



PART V 
MANUFACTURED PRODUCTS AND THEIR USES 



CHAPTER XXIII 

COMPOUNDING OF BITUMINOUS SUBSTANCES 
GENERAL CONSIDERATIONS 

One of the most important questions which confronts the bitu- 
menologist is that of blending the various substances at his disposal, 
to produce mixtures best adapted for the special purposes for which 
they are intended. This requires an intimate knowledge of the 
nature and behavior of the various materials, and can only be thor- 
oughly acquired by years of experience. Two shipments of any 
given member of the bituminous family are likely to fluctuate widely 
in their physical properties and composition, even when procured 
from the identical source. A native bituminous substance emanat- 
ing from the same deposit will vary, depending upon the degree of 
exposure and amount of metamorphosis. It has been shown that 
all native bituminous materials are in a constant state of transition, 
depending upon their age and environment. Scarcely any two de- 
posits of native asphalt are alike in their properties or chemical 
composition. The same applies to petroleum, which varies in dif- 
ferent localities and very often in wells side-by-side in the same field. 

The pyrogenous bituminous materials also show a marked varia- 
tion in their properties, depending upon the raw materials used in 
their production and the exact conditions to which they have been 
subjected in their process of manufacture, including the tempera- 
ture, length of treatment, etc. 

Bituminous materials should not therefore be compared to vege- 
table and animal fats or oils, which in the case of any one material 
runs fairly uniform in composition and physical properties. 

The consistency of the available raw bituminous materials is 

476 



XXIH GENERAL CONSIDERATIONS 477 

either fixed and definite, or it is controllable. Each native bitumi- 
nous substance has a predetermined consistency in other words, it 
is endowed by nature with certain fixed and definite physical prop- 
erties, and over which man has no control. On the other hand, the 
consistency of pyrogenous bituminous substances, with three excep- 
tions (i.e., wax tailings, tars and rosin pitch), is largely controllable, 
and depends upon the treatment to which they are subjected in the 
course of their production. In the majority of pyrogenous sub- 
stances, it is a comparatively easy matter to alter their consistency 
at will, by regulating the duration of the process, its temperature, 
or some other condition. In the three exceptions noted, the con- 
sistency is predetermined, and has no definite bearing upon the 
variable factors of the process. 

Table XLV will serve to give a general idea whether the hard- 
ness and fusibility of the various bituminous substances are definite 
or controllable, whether the substances are naturally soft, medium 
or hard at room temperature ; also their approximate comparative 
volatility, weather-proof properties, and efficiency in fluxing. 

In interpreting Table XLV, it should be distinctly noted that 
the "Hardness at Room Temperature," "Volatility/' "Weather- 
proof Properties" and "Efficiency in Fluxing" are listed in a com- 
parative sense, and must not therefore be regarded as a definite 
exposition of the characteristics of any single substance, without 
taking into consideration the other substances cited. 

In addition to the bituminous substances, there are included 
three groups of non-bituminous substances commonly used for pur- 
poses of blending; viz., rosin, animal and vegetable oils or fats, and 
wool grease. 

In preparing mixtures of bituminous materials, the following 
points should be borne in mind : 

( I ) Bituminous materials which give the diazo reaction (Test 
39) (containing phenols), should not be mixed with bituminous 
substances not giving this reaction. In other words, native asphalts, 
asphaltites and pyrogenous asphalts should not be blended with tars 
or pitches (excepting fatty-acid pitch), since it has been found by 
experience that such mixtures, although they may melt together per- 
fectly, are not durable or weatherproof, although such mixtures 
have been used successfully for sub-soil waterproofing purposes and 
certain types of pavements. 



478 



COMPOUNDING OF BITUMINOUS SUBSTANCES 



XXIII 



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itf P< 



XXIII CHARACTERISTICS OF BITUMINOUS SUBSTANCES 



479 



rat 



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t& 

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^frills 

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480 COMPOUNDING OF BITUMINOUS SUBSTANCES XXIII 

(2) Native and pyrogenous waxes will not remain permanently 
blended with other bituminous materials, but will crystallize at low 
temperatures, gradually separating from solid mixtures on standing. 
This manifests itself by the wax "sweating" from the surface. In 
certain cases this feature is desirable, since the admixture of a small 
percentage of wax imparts wax-like properties to the entire com- 
position. 

(3) Grahamite does not flux with native or pyrogenous waxes, 
residual oils derived from non-asphaltic petroleum, fatty-acid pitch 
or wool grease. 

(4) If the bituminous material contains a percentage of "non- 
mineral matter insoluble in carbon disulfide," the act of fluxing with 
other bituminous substances, rosin, animal or vegetable oils and fats 
will only dilute this ingredient, without eliminating it. The calcu- 
lated proportion will still be present in the mixture. 

(5) The percentage of carbenes may be reduced by fluxing or 
blending, as the carbenes themselves are fluxed by other bituminous 
substances, rosin, animal or vegetable oils and fats. 

(6) The thoroughness with which bituminous materials blend 
may be ascertained by finding the fusing-point of the components, 
ana comparing the calculated fusing-point of the mixture with its 
actual fusing-point. If the actual fusing-point is ecjual to, or 
greater, than the calculated fusing-point, then the blending has been 
thorough. On the other hand, if the actual fusing-point is less than 
the calculated fusing-point, then the components do not amalgamate 
thoroughly. 

(7) The microscopic test may also be used to good advantage 
to ascertain the thoroughness with which the components blend. A 
separation of particles in the mixture is evidence that perfect amal- 
gamation does not occur. 

Where the hardness and fusibility of the bituminous substance 
are "controllable," it is often a simple matter to continue the dis- 
tillation, blowing, depolymerization (in the case of wurtzilite as- 
phalt), etc., until a product is obtained having the desired physical 
characteristics. Where conditions permit, it is more convenient and 
economical to turn out a product of exactly the proper grade, than 
to flux or harden it afterwards. It is accordingly customary 1 to 
market residual asphalts of exactly the right hardness and fusing- 
point for paving purposes, etc. Blown asphalts are similarly mar- 
keted in various grades, having different fusing-points (and hard- 
nesses), so that the manufacturer may pick out one best adapted to 
his particular purpose. Coal tar is likewise distilled to a predeter- 



XXIII 



BINARY MIXTURES 



481 



mined extent to obtain pitches suitable for use as such in connection 
with waterproofing, roofing work, road purposes or briquette mak- 
ing, whichever the case may be. 

Binary Mixtures. It is not always possible to use a single bitu- 
minous material, since it is sometimes found that the exact charac- 
teristics required are lacking, and can only be obtained by blending 
together two or more substances in suitable proportions. The sim- 
plest mixtures, containing two constituents, are known as "binary 
mixtures." In this case it is often possible to predict with a fair 
degree of accuracy what the characteristics of the mixture will be. 
That this is not always a simple matter is indicated by the following 
figures. The same blown asphalt was used in both cases, whereas 
the steam-refined asphalts A and B differed slightly: 1 

TABLE XLVI 



Per Cent of Blown 
Asphalt Combined 
with: 


Penetration 
at 7 7F. 
(Test ?*) 


R. and B. Fu sing- 
Point deg. F. 
(Test 15^) 


Ductility 
at 77 F. 
(Test loa) 


Steam-refined Asphalt "A": 


o 


30 


131 


"5 


10 


34 


130 


H5 


20 


49 


129 


"5 


3 


65 


124 


"5 


40 


73 


126 


"5 


45 


77 


127 


"5 


50 


67 


134 


57.5 


60 


60 


U5 


12.5 


100 


37 


270 


i.J 


Steam-refined Asphalt "B": 





30 


13* 


"5 


10 


35 


132 


"5 


00 


44 


129 


"S 


30 


54 


136 


78 


40 


56 


. M3 


19.5 


5 


57 


151 


9.5 


70 


50 


173 


4.25 


100 


37 


270 


-S 



The purpose of preparing a mixture is to soften the substance 
and lower its fusing-point, harden the substance and raise its fusing- 
point, render the mixture less susceptible to temperature changes, 
effect a more perfect union or blending of the constituents, improve 
its weatherproof properties, increase the tensile strength, render the 



482 



COMPOUNDING OF BITUMINOUS SUBSTANCES 



XXIII 



mixture wax-like, or unctuous to the feel, lessen the tendency to- 
wards stickiness, etc. 

Softening the Substance and Lowering Its Fusing-point. This 
process is ordinarily known as "fluxing." When the bituminous 
material, as it occurs naturally or results from a manufacturing 
process is too hard in consistency or fuses at too high a temperature, 
it is customary to mix it with a softer substance, termed a "flux," 
to impart the necessary characteristics. The fluxes may be classi- 
fied in three groups as follows : 



GROUP I 

For Softening Asphaltic 
Materials and Asphaltites 


GROUP II 
For Softening Pitches 


GROUP III 
Used Indiscriminately for 
Softening Asphaltic Materials, 
Asphaltites and Pitches 


Soft native asphalt 
Residual oils 
Pressure tars 
Soft blown asphalt 
Soft residual asphalt 
Soft sludge asphalt 


Medium wood tar pitch 
Medium peat-and lignite-tar 
pitches 
Medium water-gas-tar pitch 
Medium oil-gas-tar pitch 
Medium coal-tar pitch 
Medium bone-tar pitch 


Wax tailings 
Soft and medium fatty-acid 
pitches* 
Animal and vegetable oils and 
fats 
Wool grease* 



* Not suitable for fluxing grahamite. 

The fluxes listed in Group II should not be used for softening 
asphaltic materials and asphaltites, or those in Group I for soften- 
ing pitches (excepting rosin- and fatty-acid pitches), for reasons al- 
ready explained. The fluxes listed in Group III will answer satis- 
factorily for softening asphaltic products, asphaltites and pitches, 
without injuring their weather-resisting qualities. 

Of Group I fluxes: residual oils, soft blown asphalt and soft 
residual asphalt are ordinarily used, on account of their weather- 
resisting properties, their efficiency in fluxing, the absence of vola- 
tile constituents and their comparative cheapness. 

Of Group II fluxes : water-gas-tar pitch and oil-gas-tar pitch are 
ordinarily used for preparing "cut-back" coal-tar pitches for use 
as dust-laying oils, road surfacings, etc. 

Of Group III fluxes: animal and vegetable oils or fats are most 
generally employed, owing to their abundance and uniformity. 
They are only used in special cases (e.g., manufacturing certain 
bituminous lacquers, varnishes and japans, rubber substitutes, coat- 
ing compositions for high-grade prepared roofings, etc.), in view of 
their comparatively high price, although they are without question 
the fluxes par excellence ror bituminous materials* 



XXIII BINARY MIXTURES 483 

Augmenting the Adhesive Properties of the Substance. Bitu- 
minous substances may have their adhesiveness enhanced by fluxing 
with a small percentage (e.g., o.i to 2 per cent) of the following 
materials: an aromatic or aliphatic alcohol (e.g., fusel oil) ; 2 cyclo- 
hexanone, CO.Et.C 5 H n , Bu 2 C 2 O 4 , etc.; 3 naphthalene or hydro- 
naphthalene dissolved in alcohols or ketones ; 4 naphthenic acids ; 5 
solid fatty acids (e.g., stearic), resin acids or oxidized paraffin 
wax; 6 polymerized vinyl chloride; 7 crude phenols; 8 "rubber oil" 
obtained in the destructive distillation of rubber; 9 etc. 

Increasing the Fluidity of the Substance When Melted. An- 
other group of materials is of interest in connection with saturants. 
They have been termed "introfiers" (i.e., impregnation accelera- 
tors), 10 and when added to an impregnating material in relatively 
small quantities will jesult in a marked change in its fluidity and 
wetting properties towards the material being impregnated, increas- 
ing the speed of penetration. This group of materials includes sub- 
stances of the type of naphthalene (e.g., naphthalene, naphthols, 
naphthylamines, hydronaphthalenes, chloronaphthalenes, etc.); py- 
ridine bases (e.g., pyridine, picolines, lutidines, quinoline, quinal- 
dine, acridine, or similar compounds); 11 nitrogenous distillation 
products (e.g., dipped oil, bone oil, shale oil, etc.); 12 also of the 
type of diphenyl (e.g., diphenyl, diphenylmethane, dibenzyl, phenyl 
ether, fluorene, etc.) ; also of the type of triphenyl (e.g., triphenyl- 
methane, triphenylchloromethane, triphenylphosphate, etc.); like- 
wise paracumarone ("cumar") resin; 13 etc. 

Effecting a More Perfect Union or Blending of the Constituents. 
At times the components of a bituminous mixture do not amalga- 
mate thoroughly. This is detected by a lack of homogeneity (Test 
2), i.e., by distributing the surface and observing whether it becomes 
duller, or else by drawing out a pellet into a thin thread, and noting 
whether any dulling occurs. Certain fluxes when combined with the 
mixture, often in a small proportion, serve to overcome this ten- 
dency, and result in a more complete amalgamation of the compo- 
nents. Such fluxes in the approximate order of their efficiency are 
as follows: 

Rosin Animal or vegetable oils and fats 

Rosin pitch Wax tailings 

It will be understood that these fluxes do not influence the per- 



484 COMPOUNDING OF BITUMINOUS SUBSTANCES XXIII 

centage of non-mineral matter insoluble in carbon disulfide (free 
carbon), or any dullness due to this constituent. 

In general it may be stated that petroleum asphalts and coal-tar 
pitch do not readily amalgamate except in restricted proportions. 1 * 

Gilsonite has been recommended as an addition to asphalts for 
the purpose of "correcting" heterogeneity. 15 Waxy substances (e.g., 
paraffin wax) are better tolerated by some asphalts than by others, 
but may be combined in nearly all proportions with gilsonite selects, 
and without danger of subsequent separation, which fact is taken 
advantage of in the insulated-wire industry. 

A greater percentage of natural asphalts (e.g., Trinidad as- 
phalt) may be blended with coal tar and coal-tar pitch without 
coagulating the free carbon present in the latter, than proves to be 
the case with petroleum asphalts. 18 

Asphalts having the highest surface-tension flux best with tars, 1T 
and homogeneous mixtures are favored through the use of soft tars 
and hard asphalts. 18 The addition of the following substances will 
promote the fluxing of coal-tar pitches and petroleum asphalts: 
rosin or wax tailings; 10 anthracene oil; 20 Dippel's oil or shale oil, 
and nitrogenous bases; 21 organic compounds of heavy metals (e.g., 
lead oleate or lead resinate) ; 22 certain forms of colloidal mineral 
matter (e.g., A1 2 S1O 3 or A1 2 O 3 ). 

Coal-tar pitches will flux in all proportions with vegetable oils 
(plain or vulcanized) and fatty-acid pitches, 23 and coke-oven tar 
will blend in all proportions with pressure tars derived from pe- 
troleum. 24 

Mixtures of coal tar and asphalt are favored for road construc- 
tion in Europe and Great Britain, it being claimed that such mix- 
tures have the following advantages over the use of tar alone: 

1) Have increased viscosities at elevated temperatures. 

2 ) Are less susceptible to temperature changes. 
; Possess greater adhesive qualities. 

4) Have greater weather-resistance. 

Up to 20 or 25 per cent petroleum asphalt or coal-tar pitch respec- 
tively may be incorporated in the mixture and form a homogeneous 
composition. If more than 25 per cent asphalt is fluxed with coal- 
tar pitch, or conversely, if more than 25 per cent of coal-tar pitch 
is fluxed with asphalt, a separation of the constituents will take 



XXIII 



BINARY MIXTURES 



485 



place, as may be observed by a visual examination of the material 
under the microscope (Test 2&), or sometimes even by the naked 
eye (Test ^a]. 

German practice favors the use of 1 5-30 per cent by weight of 
petroleum asphalt (31-35 C. fusing-point by K. and S, method) 
and 85-70 per cent by weight of coal-tar pitch. 25 

The effect of successive additions of petroleum asphalt to coal 
tar generally results in the following changes : 

Up to 10 per cent Slight improvement. 

15 to 25 per cent Marked improvement. 

30 to 50 per cent Segregation and precipitation. 

50 to 70 per cent Increased homogeneity. 

70 per cent upwards Homogeneous and stable. 

In preparing the mixture, the asphalt is added to the tar, both 
being maintained at about 120 to 130 C. The mixture is kept well 
stirred, while the temperature is gradually increased to 150 C. 

In an extreme instance we learn that pulverized oil shale (e.g., 
Colorado oil-shale) will flux with coal-tar pitch or heavy coal-tar 
distillates when heated to 300-400 C. until the shale disintegrates 
and the "kerogen" dissolves. 26 A similar process has been de- 
scribed for fluxing bituminous (i.e., "coking") coal which consists 
in first pulverizing the coal and then digesting it in a closed retort 
with coke-oven tar, water-gas tar, or the like. 27 The fluxed mix- 
ture may be used for impregnating felt, 28 or for preparing molding 
compositions. 29 

Hardening the Substance, Raising Its Fusing-point and Increas- 
ing Its Stability. Where the bituminous substance is too soft for 
the purpose intended, it is customary to harden it either by distilla- 
tion, 30 or by adding one or more of the following materials : 



GROUP I 

For Hardening Asphaltic 
Materials 


GROUP II 
For Hardening Pitches 


GROUP III 
May Be Used Indiscriminately 
for Hardening Asphaltic 
Materials or Pitches 


Hard native asphalt 
Asphalti tes 
Hard residual asphalt 
Hard sludge asphalt 
Hard wurtzilite asphalt 


Hard wood- tar pitch 
Hard peat- and lignite-tar 
pitches 
Hard water-gas-tar pitch 
Hard oil-gas-tar pitch 
Hard coal-tar pitch 
Hard bone- tar pitch 


Rosin pitch 
Rosin 

Hard fatty-acid pitch 
Blowing with air 
Combining with sulfur 
Fillers, etc. 
Dispersions of colloidal solids 



486 COMPOUNDING OF BITUMINOUS SUBSTANCES XXIII 

Of Group I hardeners, hard native asphalts, hard residual as- 
phalts and asphaltites are most -frequently used; and similarly of 
the Group II and Group III hardeners, hard coal-tar pitch and 
fillers respectively are most generally employed. The fillers may 
be of vegetable or mineral origin, and will be discussed in greater 
detail later. It is not customary to harden bituminous mixtures by 
blowing with air after they are once blended, although this pro- 
cedure would increase the hardness and particularly the fusing- 
point All bituminous substances may be hardened by heating with 
a small percentage of sulfur after the manner of vulcanization in 
the rubber industry. 31 This is only used to a limited extent, owing 
to the difficulty of controlling the degree of hardening, also because 
of the fact that it tends to reduce the ductility of the product. 
Other methods for hardening asphalts consist: in heating them with 
i per cent concentrated H 2 SO 4 ; 82 heating natural or petroleum as- 
phalts with i-io per cent, or pitches with 5 per cent HNO 3 ; 33 treat- 
ing pitches (e.g., naphthol pitch) with mineral acid and formalde- 
hyde ; * 4 heating asphaltites or asphaltic pyrobitumens under pres- 
sure with nascent hydrogen; 35 etc. 

Rendering the Mixture Less Susceptible to Temperature 
Changes. It is difficult to lay down any definite rules in this con- 
nection. In general, it may be stated that the suitable addition of 
the following substances will tend to make mixtures more resistant 
to temperature changes, viz. : 

Asphaltites Fatty-acid pitch Rubber 

Blown asphalt Animal or vegetable oils and fats Chlorinated rubber 

Wurtzilite asphalt Fillers (mineral and vegetable) 

The first three, of course, should only be used in connection with 
asphaltic mixtures, whereas the next three are applicable either to 
asphaltic mixtures or pitches. Animal or vegetable oils and fats 
which have been thickened or "boiled" by heating to a high tem- 
perature until they polymerize, are more efficient in this respect 
than oils or fats in their crude state. Rubber (vulcanized or unvul- 
canized) or chlorinated rubber 36 may be incorporated in asphalts, 
coal tars or coal-tar pitches, by: (a) dissolving "crum" rubber in 
asphalt flux-oil or low-temperature tar-oils, and removing the latter 
by steam-distillation, and thereupon employing the mixture thus ob- 



XXIII BINARY MIXTURES 487 

tained for cutting back harder asphalts or coal-tar pitches; (b) by 
homogenizing tar with latex, or latex treated with sodium nitrite, 
and removing the water; (c) by heating asphalt or coal-tar pitch 
with a mixture containing equal parts by weight of rubber and 
sulfur. Rubber, when thus incorporated without overheating, will 
increase the elasticity, hardness and fusing-point of the mixture. If 
overheated, the rubber will be decomposed and exerts a harmful 
effect on the product. 37 Rubber may be fluxed with coal-tar pitch 
in the presence of stearic acid. 88 Other procedures consist in mixing 
asphalt, coal-tar pitch with cumar (i.e., paracumarone) resin; 89 or 
phenol-aldehyde resin; 40 incorporating an aqueous mixture of 
wheat glutin and glycerin and expelling the water under heat; 41 
etc. 

Increasing the Tensile Strength of the Mixture. For some pur- 
poses it is important that a bituminous mixture shall have the maxi- 
mum tensile strength, to enable it to withstand the stresses and 
strains to which it may be subjected in usage. This is of special 
importance in the case of certain forms of bituminous pavements. 
Two general methods are used for the purpose, viz. : 

1 i ) Incorporating mineral fillers. 

(2) Increasing the hardness, by blending with harder bitumi- 
nous substances. 

The tensile strength of a soft bituminous mixture increases to a 
certain point upon being blended with harder bituminous substances, 
but these have a tendency to reduce the strength when the mixture 
reaches the hard and brittle stage. 

Making the Mixture More Weatherproof. This is another 
question which cannot be decided by any hard and fixed rules, as it 
depends largely upon what materials are present in the mixture, and 
how badly it may lack weatherproof qualities. There may be cases 
where the bituminous substance is so deficient in weatherproof 
properties that it would be impracticable to attempt improving it, 
on account of the extremely large proportion of material which 
would have to be added to overcome this defect. In general, it 
may be stated that the addition of the following products tends 
to overcome the non-weatherproof properties of bituminous mix- 
tures : 



488 



COMPOUNDING OF BITUMINOUS SUBSTANCES 



XXIII 



GROUP I 

For Augmenting the Weatherproof Properties 
of Asphaltic Materials Only 



GROUP II 

For Augmenting the Weatherproof Properties 
of Pitches as Well as Asphaltic Materials 



Asphahites 

Certain native asphalts 
Certain residual oils 
Blown asphalt 
Wurtzilite asphalt 
Certain fatty-acid pitches 



Animal or vegetable oils and fats 
Wool grease 
Fillers (mineral only) 
Dispersions of colloidal solids 



Of the products included in Group I, the asphaltites, wurtzilite 
asphalt and certain fatty-acid pitches (of the saponifiable type) will 
most effectively improve the weather-resisting properties of the mix- 
ture, due to the fact that these materials of themselves are highly 
weatherproof. Among the asphaltites, grahamite is most weather- 
resisting, gilsonite and glance pitch ranging next in efficiency and 
being about equal in this respect Wurtzilite asphalt is extremely 
weatherproof, and the same also applies to the saponifiable varieties 
of fatty-acid pitch. Only certain native asphalts and residual oils 
are included in this category, for it is impossible to lay down any 
definite rules to differentiate between the non-weatherproof and 
weatherproof varieties, since this can only be determined as the 
result of experience or by an actual exposure test. The physical and 
chemical tests fail to determine definitely whether a native asphalt 
or residual oil will display the optimum weather-resistance in actual 
service. Certain tests (e.g., large percentages of volatile matter 
and non-mineral constituents insoluble in carbon disulfide), may defi- 
nitely pronounce the material to be non-weatherproof, but if these, 
by chance, prove negative, the court of final appeal is an actual 
exposure test under service conditions. 

Both fluxes enumerated under Group II are equally efficient 
from the standpoint of weather-resistance, although the first named 
is superior in its fluxing properties. The use of drying oils com- 
bined with metallic oxide driers has also been recommended; 42 
also "factice" and cholesterol derivatives; 48 likewise the addition 
of a small percentage of wood-tar pitch. 44 

Mineral fillers when added in a finely divided state, or in the 
form of graded particles, proportioned to show the minimum per- 
centage of voids, tend to improve the weather-resistance of all bitu- 



XXIII TERTIARY AND COMPLEX MIXTURES 489 

minous substances. Those fillers which are impermeable to light 
are most efficient in this respect. The same rules apply in this con- 
nection as with mineral pigments in linseed oil paints. 45 It is claimed 
that the weather-resistance of bituminous substances may be im- 
proved by subjecting a warm solution in a solvent to the influence of 
ultraviolet light, while ozone is being blown through/ 6 

Rendering fFax-like, Unctuous to the Feel, or Lessening the 
Tendency towards Stickiness. For certain purposes, it is desirable 
to impart the foregoing properties to bituminous mixtures, espe- 
cially in manufacturing insulating compounds, rubber substitutes, 
coating compositions for papers, etc. The addition of a small per- 
centage of the following waxes (usually less than 10-15 per cent) 
will serve to accomplish this result: 

Ozokerite Montan wax Pyrogenous waxes 

These will not amalgamate permanently with bituminous ma- 
terials, but will work their way to the surface in time, forming a 
thin waxy film which will modify the characteristics of the mixture, 
imparting certain of the physical properties of waxes. In the case 
of ozokerite and pyrogenous waxes, only a small percentage should 
be added, otherwise the separation will be sufficiently great to de- 
stroy the integrity of the mixture. Montan wax may be added in 
large quantities, as it constitutes a better flux and shows but a slight 
tendency towards separation. The stickiness and tackiness of bitu- 
minous mixtures may be decreased by incorporating: a mixture of 
paraffin wax and phenol; 47 a synthetic resin; 48 resinates, sulfonates, 
naphthenates, or linoleates of heavy metals (e.g., Mn, Co, Pb, 
etc.). 49 

Tertiary and Complex Mixtures. In the case of binary mix- 
tures, the characteristics of the blended product may be predicted 
with a reasonable degree of certainty, but with tertiary or quater- 
nary mixtures this is extremely difficult, and in many cases impos- 
sible to do, even by one highly skilled in the art We must bear in 
mind that the native asphalts, for example, occur in hundreds of 
varieties, each differing in certain respects from the others, or as 
one authority on the subject aptly expresses it: "No two deposits 
of native asphalt or petroleum on the face of the earth are exactly 



400 COMPOUNDING OF BITUMINOUS SUBSTANCES XXIIi 

alike." Similarly, blown asphalts, residual asphalts, coal-tar pitches, 
etc., are produced in hundreds of grades, depending upon the na- 
ture of the crude materials, the temperature to which they have 
been subjected, the length of blowing, the duration of the distilla- 
tion process, and many other factors. These result in the produc- 
tion of a whole series of products from any particular raw material, 
varying in fusibility, hardness and other physical and chemical char- 
acteristics. Since each class of raw material is available in hundreds 
of varieties, it will be apparent that the number of possible combi- 
nations in tertiary mixtures is infinite. 

In color matching, a given shade may be produced in a dozen 
different ways, each starting with totally different colors, and simi- 
larly, a given bituminous substance may be exactly duplicated in 
physical characteristics (i.e., fusing-point, hardness, ductility, tensile 
strength, volatility, etc.), by numerous mixtures, each containing 
different combinations of different materials. 

The only way to match a given bituminous substance is by the 
"cut and try method." This applies with more force when it comes 
to tertiary and complex mixtures. To duplicate exactly a complex 
bituminous mixture is one of the most difficult and at the same time 
one of the most fascinating problems in bitumenology* At the 
present stage of the science, a chemical analysis of the material to 
be duplicated will tell nothing. It is only an intimate knowledge of 
the physical properties of the available bituminous raw materials, 
and an inference of their behavior in combinations, that will assist 
the expert in synthesizing a mixture having substantially the same 
properties as the one to be duplicated. 

The problem is made still more complicated by the fact that 
although we may apparently succeed in duplicating the physical 
properties of a given bituminous mixture, yet there is no way of 
telling other than from an actual service test whether or not it will 
behave the same on aging or upon exposure to the elements. 

Classes of Bituminous Mixtures. Bituminous substances and 
their mixtures may be roughly divided into three general classes 
based on their physical properties, characterized by being "soft," 
"medium" and "hard" at room temperature. The following table 
will show which of the commercial products belong to the respec- 
tive classes: 



XXIII CLASSES OF BITUMINOUS MIXTURES 491 

Soft (liquid) Bituminous Products: 

Dust-laying oils. 
Binders for road surfacings. 

Impregnation for wooden paving blocks, railroad ties, etc. 
Tars and oils for the flotation process. 

Saturating compounds for prepared roofing, flooring, waterproofing, sheath- 
ing and insulating papers, electrical insulating tape, etc. 
Waterproofing compounds for Portland-cement mortar and concrete. 

Medium (semi-liquid to semi-solid) Bituminous Products: 

Binders for bituminous surfacings, bituminous macadam and bituminous 

concrete pavements. 
Asphaltic cement for sheet asphalt pavements, asphalt-block pavements and 

asphalt mastic foot-pavements and floors. 
Fillers for wood, brick and stone pavements. 
Bituminous expansion joints. 
Coatings for prepared roofing, waterproofing, sheathing and insulating 

papers. 
Adhesive compounds for built-up roofing and waterproofing work; plastic 

compounds for repairing roofs, etc. 
Pipe-dips and pipe-sealing compounds. 
Electrical insulating compounds. 
Rubber substitutes and fillers. 
Molding compounds. 
Bases of bituminous lacquers and cements. 

Hard (solid) Bituminous Products: 

Certain forms of electrical insulating compounds. 

Molding compounds. 

Binders for briquettes. 

Certain forms of pipe dips. 

Bases of varnishes, enamels, japans and certain bituminous lacquers. 

Processes of Compounding Bituminous Substances. The types 
of apparatus for this purpose fall into two groups, viz. : 

1 I ) Open vessels of semi-cylindrical or rectangular form, as 
described for dehydrating semi-solid and solid native bituminous 
substances. 

(2) Closed horizontal cylindrical vessels provided with an agi- 
tator in the form of a horizontal shaft carrying short stout blades 
or paddles usually set at an angle. This type is mounted on a 
masonry foundation over a solid or perforated fire-brick arch, and 
the heating effected by burning coal or gas underneath it The 
vessel is provided with a manhole at the top, through which the bi- 
tuminous substances are charged, and closed with a cap during the 
melting process to keep out air and prevent the vapors from igniting. 



492 COMPOUNDING OF BITUMINOUS SUBSTANCES XXIII 

The first type is used where the bituminous substance is heated 
below the flash-point of the constituent flashing at the lowest tem- 
perature, and the second where it is necessary or desirable to heat 
the mass above the flash-point Since the mass can safely be heated 
in the second type to higher temperatures and agitated at a greater 
speed without danger of the melted mixture splashing out of the 
vessel, it follows that with its use the process of amalgamation will 
take place more rapidly. 

The dehydrated bituminous substances are introduced into the 
melting-tank, preferably in the melted condition, either by gravity or 
by means of pumps. Where this is not practical, as with/ high 
fusing-point products, such as the asphaltites or native asphalts con- 
taining a large percentage of mineral matter, they may be added 
cold in the solid state, but in this case it takes longer to melt up 
the charge. 

The higher the temperature to which the materials are heated, 
the more rapidly will the combination take place. It is not neces- 
sary, or in fact desirable to raise the heat to the fusing-point of the 
ingredients melting at the highest temperature, as these will be dis- 
solved by the constituents fusing at lower temperatures, due to their 
inherent solvent action combined with mechanical agitation. Thus, 
a grahamite fusing at 550 to 575 F. (K. and S. method) will 
readily combine with mixed-base or asphaltic residual oils brought 
to a temperature of 400 F., particularly if the mixture is kept well 
agitated. The grahamite should be introduced in the form of lumps 
about the size of hickory nuts, in preference to a fine powder, as the 
latter will sinter together if the charge is not agitated, and in addi- 
tion will make it difficult to tell when the amalgamation is completed. 

Great care should be taken not to overheat the bituminous sub- 
stances, as they are all affected either by a prolonged heating at a 
moderately high temperature, or upon subjecting to a comparatively 
high temperature for a short time. There are no general rules 
regarding the behavior of bituminous substances under the influence 
of heat. Each will act differently, and resist heat to a greater or 
lesser degree. It is rarely safe to raise the temperature higher than 
450-500 F, in any of the manufacturing processes involving the 
use of bituminous substances. 50 Overheating will manifest itself by: 



XXIII METHODS OF BLENDING 493 

1 I ) Increasing the specific gravity, viscosity, hardness and con- 
sistency, fusing-point, flash-point, burning-point, non-mineral matter 
insoluble in carbon disulfide (free carbon), and carbenes. 

(2) Decreasing the ductility, volatile matter, solubility in car- 
bon disulfide and in 88 petroleum naphtha. 

On fluxing native asphalts carrying a substantial percentage of 
mineral matter, it is important to keep the mass well agitated, other- 
wise the mineral matter will settle out and carbonize against the 
bottom of the tank, retarding the ingress of heat, and causing the 
bottom plates to burn out rapidly. 

When the mixture is to be heated to a high temperature for 
other than a comparatively short time, it is inadvisable to effect the 
agitation by means of air, as this will increase the fusing-point in 
the same manner as in the production of "blown asphalts," Me- 
chanical stirrers or dry steam jets are preferable under these 
conditions. 

Based upon the uses to which they may be put commercially, 
bituminous substances may be classified according to their purity 
(i.e., freedom from constituents insoluble in carbon disulfide) as 
follows : 

97-100 per cent purity. . Base of lacquers and varnishes 

Saturants for composition roofings and shingles 

Impregnation for wood, etc. 
67- 97 per cent purity. . Coating compositions for roofings 

Adhesive compositions for roofings 

Binders for road surfacings 

Asphaltic cement for sheet-asphalt pavements 
18-67 per cent purity, . . Molding compositions 

Bituminous expansion joints 

Electrical insulating compounds 

Pipe dips and sealing compounds 
12- 1 8 per cent purity. . Mastic pavements 
9- 1 2 per cent purity. . Sheet-asphalt pavements 
5-11 per cent purity. . Bituminous concrete pavements 
Less than 5 per cent For enrichment with purer forms of asphalt, etc. 



CHAPTER XXIV 

BITUMINOUS SUBSTANCES ADMIXED WITH DISCRETE 

AGGREGATES 

Methods of Incorporating Discrete Aggregates. Since dis- 
crete aggregates are incorporated after the bituminous mixture has 
been dehydrated and fluxed to the proper consistency, a steam- 
heated mixing apparatus of small capacity is best adapted for the 
purpose, constructed to mix the charge with great rapidity. Two 
forms of steam-jacketed agitators provided with mechanical mixers 
are used, viz. : 

1 i ) A rectangular tank with a semi-cylindrical steam-jacketed 
bottom, commonly provided with two horizontal shafts revolving 
in opposite directions, each carrying two sets of short strong blades 
or paddles set at different angles, to work the bituminous mixture 
from the ends of the vessel towards the centre. The completed 
mixture is discharged from the bottom through a power-operated 
slide-valve. 

( 2 ) A vertical vessel of cylindrical form provided with a steam- 
jacketed semi-circular bottom, enclosing a vertical shaft carrying 
blades, geared to an auxiliary shaft, offset at one end and provided 
with smaller blades which revolve within the larger ones. 1 The 
principle of this type is similar to that of a common "egg-beater." 
The inner shell is cast from a single piece of metal to avoid danger 
of leakage. This form of apparatus is intended only to mix in such 
quantities of fillers as will not destroy the fluidity of the mixture or 
prevent it discharging by gravity through a spout at the bottom. 
When fillers are used, such as silica, earth-colors, or the like, mix- 
tures may be prepared containing 60 to 65 per cent of the mineral 
constituents. 

It has also been proposed to introduce finely divided fillers in 
conjunction with a blast of air or steam which is passed through, or 
directed against the surface of the melted substance ; 2 or by intro- 
ducing the pigment or filler and distilling the mixture to the desired 
consistency; s or by mixing the filler with soft asphalt or flux and 

494 



XXIV 



DISCRETE AGGREGATES 



495 



then incorporating same with hard asphalt, rock asphalt or as- 
phaltite; * or by introducing a slurry of the filler and kerosene and 




Courtesy of J. H. Day & Co. 
FIG. 133. Mixer for Incorporating Large Percentages of Fillers in Asphalt. 




PIG. 134. Mixer for Incorporating Coarse Aggregates. 

then distilling the mixture ; 5 or by mixing the filler with an aqueous 
dispersion of asphalt and then expelling the water by means of 



496 DISCRETE AGGREGATES XXIV 

heat; 6 etc Various devices have been proposed for drying and 
preheating the mineral fillers and aggregates to facilitate mixing 
them with the melted bituminous constituents. 7 

When it is desired to incorporate light-weight fillers, such as 
cork, wood-flour, or vegetable, animal or mineral fibers, a type of 
mixer may be used similar to the foregoing But mounted on trun- 
nions, so that after the mixing is complete, the entire apparatus may 
be tipped bodily, and the contents hoed over the rim while the mass 
is hot in a type of apparatus as illustrated in Fig. 133. For incor- 
porating heavier or coarser form of aggregate, such as used in 
paving mixtures, a form of batch-mixer, known as a twin-plug mill 
is used as illustrated in Fig. 134. 

The following constitute the more important types of discrete 
aggregates which have been proposed for use in conjunction with 
bituminous substances: 

(A) COLLOIDAL PARTICLES 
I. ADMIXED MECHANICALLY: 

(a) Inorganic. The following agents may be incorporated in 
the dry state with the melted bituminous substance by mechanical 
agitation: colloidal clay; 9 slaked lime or lime sludge (CaOH 2 ); 10 
whiting; 11 Ca(OH) 2 and glauber's salt (Na 2 SO 4 ); 12 chalk and 
alum; 13 limestone derived from fresh-water springs; 14 limestone 
mixed with the melted substance under vacuum; 15 magnesium or 
barium carbonate; 16 lime soaps (e.g., calcium oleate); 1 ' 7 calcium 
cyanamide; 18 lampblack or the like added to asphaltic petroleum 
prior to its distillation. 19 The following substances in the form of 
an aqueous suspension, may be incorporated with the melted bitu- 
minous substance, and the water then evaporated: clay; 20 powdered 
limestone or magnesium carbonate ; 2X calcium or magnesium hy- 
droxide, calcium sulfate or iron hydroxide; 22 magnesium oxide, 
aluminium oxide, iron oxide, or silicates of magnesium and alumin- 
ium; 23 zinc oxide with acetic acid; 24 etc. In the foregoing con- 
nection, it has been found that bituminous mixtures consisting partly 
of aromatic hydrocarbons (e.g., coal-tar creosote) and partly of 
paraffins (e.g., semi-asphaltic residual asphalts) act as the best dis- 
persoids, and moreover, the use of all aromatic or all paraffin hy- 
drocarbons will not effect a satisfactory dispersion. 

() Organic, Mixing with soaps (e.g., sodium stearate) ; 
or aluminium soap; 26 mixing a hard bituminous substance (e.g., 
hard coal-tar pitch or peat) with a soft bituminous substance (e.g., 



25 



XXIV FILLERS (POWDERS) INCLUDING PIGMENTS 497 

coal tar) in the presence of a synthetic resin, by means of a colloid 
mill; 27 etc. 



2. LIBERATED U IN SITU" : 



(a) Inorganic. Treating the melted bituminous substance with 
metallic salts, which under the influence of heat break up into dis- 
persions and either polymerize the bituminous substance, or in some 
instances combine chemically with same, as manifested by an in- 
crease in fusing-point, tensile strength, elasticity, ductility and re- 
sistance to fracture. The substances recommended for this purpose 
include: sulfates or selcnates (e.g., ammonium, copper, iron, chro- 
mium, manganese, aluminium, sodium, potassium, rubidium, caesium, 
thallium, etc.) ; 2S a mixture of copper sulfate and colloidal clay; 29 
metallic chlorides (e.g., zinc, aluminium, tin, copper, cobalt, iron, 
magnesium, titanium, arsenic, antimony and bismuth the first 
three giving the best results); 30 metallic oxides and peroxides 
(e.g., Fe 2 O 3 , PbO, MnO 2 , Ni 2 O 3 , SnO 2 , ZnO, TiO 2 , Cep 2 , Cr 2 O 3 , 
Pb 2 O 3 , CuO, BaO 2 , etc.) ; 81 borax and borates; 32 metallic acetates 
(e.g., aluminium, zinc, mercury or sodium); 33 metallic tartrates 
(e.g., potassium); 34 phosphoric acid; 35 a mixture of boracic and 
oxalic acids; 36 metallic nitrates; etc. 

(/3) Organic. Decided rubber-like properties may be imparted 
to bituminous substances, and their fusing-point materially increased, 
or if desired they may be rendered quite infusible so that they can- 
not be melted without carbonizing, by incorporating the following 
mixtures with the melted bituminous substance : casein dissolved in 
a sulfonated oil, followed by adding formaldehyde ; 8 * animal glue 
dissolved in gas-oil; S8 "wrack" dissolved in creosote oil; 89 glycerin- 
gelatine composition in conjunction with camphor and sulfur ; 40 a 
vegetable phosphatide (i.e., vegetable albumin, such as lecithin) ; 41 
etc. 

(B) FILLERS (POWDERS), INCLUDING PIGMENTS 
(a) Inorganic 

i. Oxides: 

(a) Silica (SiO 2 ) in its various forms, including: meta-colloidal 
silica (e.g., tripoli, trass, volcanic ash, etc.), also hydrated silica 
(e.g., geyserite) ; 42 infusorial earth (diatomaceous earth or "Kiesel- 
guhr"); 43 powdered silica; 44 powdered sandstone; 45 fine sand; 46 
waste sand (e.g., from glass works, foundry cores, sandblasting 
operations, etc.). 41 

(b) Calcium and magnesium oxides (CaO and MgO), in- 



498 DISCRETE AGGREGATES XXIV 

eluding: powdered burnt lime; 48 spent lime sludge (e.g., refuse 
from sugar-refining operations); 49 magnesia oxide; 60 etc. 

(c) Aluminium oxide (A1 2 O 3 ), including bauxite and emery 
(carborundum). 51 

2. Silicates: 

There are almost infinite varieties of silicates that have been 
suggested from time to time for use as fillers, including: kaolin or 
clay; 52 fuller's earth (including spent fuller's earth obtained as a 
by-product in refining oils); 68 powdered slate; 54 powdered shale, 
marl or loam; 55 powdered lava; 56 powdered pumice (pumicite) or 
rottenstone ; 57 sillimanite (2CaO.B 2 O 3 .2SiO 2 ) ; 5S aluminium silicate 
or Ca.Na.Al.SiO 3 ; 59 Portland cement; 60 calcareous sandstone; 61 
loess; 62 talc or soapstone; 03 asbestos sand, floats and asbestine; 64 
microasbestos ; 65 mica fines; 66 sea-water mud; 67 soil or earthy 
matter; 6S etc. 

3. Carbonates: 

In this group there may .be mentioned: limestone, chalk or 
marble dust; 69 crushed sea shells; 70 powdered bones; 71 tufa 
(tuff); 72 magnesium carbonate; 78 also zinc carbonate. 74 

4. Sulfates: 

Principally: gypsum (plastcr-of-paris or u terra alba") 76 and 
barium sulfate (blanc fixe). 76 

5. Phosphates: 

Including: calcium phosphate ("Brewster dust"). 7T 

6. Miscellaneous Rock Products : 

This group includes: stone powder ("flour") and dust recov- 
ered from crushing operations by air flotation; 78 also electrically 
precipitated stone-dusts. 79 

7. Pyrogenous Products: 

In this we find reference to: ground cinders (coal ashes); 80 
"fly ash n (recovered from pulverized-coal furnaces) ; 81 powdered 
slag; 82 and brickdust, 83 

8. Black Pigments: 

These include : graphite ; 84 graphitic slate ; 85 and copper slag 
(hydrated ferrous silicate). 86 



XXIV GRANULAR MATTER 499 

9. Colored Pigments: 

Heat-resisting mineral pigments are generally used, including: 
strong red iron-oxide; 8T micaceous iron-oxide (hematite) ; 88 yellow 
ochre; 89 cadmium yellow; green oxide of chromium; ultramarine 
blue; cobalt blue; titanium oxide; sublimed white lead; lithopone; 90 
metallic bronzes (e.g., copper, brass, aluminium, iron, etc.); 91 and 
mixtures of the foregoing. 

(3) Organic 

1 . Vegetable Products : 

Including: starch; 92 dust recovered in milling grain; 98 sac- 
charine matter; w beet-sugar residues (calcium pectates and calcium 
carbonate) ; 95 powdered cork; 96 manure; 97 etc. 

2. Black Pigments : 

Under this sub-division we find : ground peat, lignite or cannel 
coal; 98 ground oil shales; 99 powdered coal ("culm"); 100 pulver- 
ized natural rock asphalts; 101 ground coal-tar pitch; 102 lamp- 
black; 103 carbon black and bone black; powdered charcoal; 104 pow- 
dered coke (coke breeze) ; 105 etc. 

(C) FIBERS 
(a) Inorganic 

In this group are included: asbestos; 106 glass wool; 107 slag 
wool ; 108 rock or mineral wool. 109 

(3) Organic 

Including: ground or shredded wood (wood wool, wood flour, 
or cellulose wool), saw-dust, wood shavings, etc.; 110 shredded 
rag or paper fibers ; U1 cotton linters, cotton flock or cottonseed 
hulls; 112 straw (raw or cooked) ; 113 flax, ramie, hemp or sisal; 114 
wheat bran; 115 rice husks and hulls; 116 corn stalks and sugar-cane 
fibers; 117 cfocoanut fibers; 118 ground tanbark; 119 shoddy and wool 
waste; hair; 120 ground leather; 121 ground peat; 122 ground roofing 
scrap and waste; 128 etc. See also "Premolded Expansion Joints," 
"Fibrated Bituminous Compositions" and "Felt-Making Fibers." 

(D) GRANULAR MATTER 
(a) Inorganic 

Include various groups of "Fillers" given under sections B--i 
to B-a-7 inclusive, in the granular state ; likewise any of the "Inor- 
ganic Surfacings Uncolored Granules" for prepared sheet roofings. 

(3) Organic 

Include corresponding products referred to under "Premolded 
Expansion Joints" and "Bituminated Cork Mixtures." 



500 



DISCRETE AGGREGATES 



XXIV 



(E) COARSE MINERAL AGGREGATES 

1. Crushed Rock, Stone, Gravel or Slag. See "Mineral Ag- 
gregates*' under Paving Materials. 

2. Graded Aggregates. 

(F) COMBINATIONS OF THE FOREGOING 

The effect of mineral fillers (Type B-a-j) on the physical char- 
acteristics 124 is shown in Table XLVII, based on the mixture of a 

TABLE XLVII 



Soft residual asphalt (from Mexican oil) 
Precipitated calcium carbonate 


100% 
o% 


85% 
15% 


?o% 
30% 


55% 
45% 


40% 
60% 














(Test 9^) Penetration at 1 1 5 F ... 


Too soft 


Too soft 


Too soft 


i6< 




Penetration at 77 F 


185 


1-7 <; 


QO 


41 




Penetration at 32 F 


60 


C2 


46 


19 




(Test 9*r) Consistency at 115 F 


o o 


O.O 


o o 


1 I 




Consistency at 77 F 


1. 1 


4.6 


6.5 


11. Q 




Consistency at 32 F 


18.4 


22.2 


24 I 


IO 4 




(Test 9<^) Susceptibility index 


19.8 


22.6 


10 C 


14. < 




(Test io<) Ductility at 1 15 F 


14.0 


11, o 


IO.O 


2. C 




Ductility at 77 F , . ... 


4O O 


11 O 


11. O 


o 6 




Ductility at 32 F 


2.7 


2.6 


o.S 


o. < 




(Test n) Tensile strength at 115 F 


o.o 


O.O 


.0.0 


O. 1 




Tensile strength at 77 F 


0.4 


I . I 


i .7 


2 4 




Tensile strength at 32 F 


c. c 


7. 5 


9 5 


n.o 




(Test 15^) Fusing-point (K. and S. method) 


91 F. 


98 F. 


106 F. 


161 F. 




(Test 15^) Fusing-point (R. and B. method) 


iioF. 


ii5F. 


124 F. 


i88F. 
















Medium residual asphalt (from Mexican oil) 
Precipitated calcium carbonate 


100% 
0% 


85% 

IC% 


?o% 

10% 


55% 
45% 


40% 
60% 














(Test 9^) Penetration at 1 1 5 F 


240 


170 


80 


27 


20 


Penetration at 77 F 


60 


47 


12 


18 




Penetration at 32 F 


iq 


16 


11 


9 


r 


(Test 9^) Consistency at 1 1 5 F 


2. 1 


2 7 


r 75 


11.6 


17. 1 


Consistency at 77 F 


IO O 


12.4 


17. 6c 


26.2 


36.6 


Consistency at 32 F 


47. 1 


<I .Q 


?4. 1 


66. Q 


80.4 


(Test 9*/) Susceptibility index 


38 2 


1Q-7 


1C. 


28.0 


26.2 


(Test io) Ductility at 115 F 


27.O 


22. 


II. O 


0.8 




Ductility at 77 F 


38.0 


IJ.O 


I.I 


0.25 




Ductility "at 32 F 


O.O 


O.2 


O. I 


O.O 




(Test n ) Tensile strength at 1 1 5 F 


o.o 


O.2 


0.8 


1.8 




Tensile strength at 77 F ... 


i 6 


2 2 


A i 


6.7 




Tensile strength at 32 F. 


9 6 


IJ..O 


20 < 


27. 2 




(Test 15*) Fusing-point (K. and S. method) . 
(Test 15^) Fusing-point (R. and B. method). 


u8F. 
136 F. 


124 F. 
145 R 


135 F. 
158 F. 


190 F. 
216 F. 


242 F. 
269 F. 



* Does not Sow when heated. 



XXIV EFFECT OF MINERAL FILLERS 501 

straight run residual Mexican asphalt with o, 15, 30, 45 and 60 
per cent of precipitated calcium carbonate. 

It will be noted that the fusing-point, hardness, and tensile 
strength increase, whereas the susceptibility index and ductility de- 
crease in proportion to the quantity of filler added. When the per- 
centage of filler is sufficient to destroy the fluidity of the mixture, 
as in the case of the surface course of sheet asphalt pavements 
(where the filler exceeds 80 per cent by weight), the physical prop- 
erties of the mixture depend largely upon the pressure to which the 
mass has been subjected. The greater the compression, the greater 
will be the hardness, tensile strength and density. 

Mixing increasing percentages of fillers with coal-tar pitch has 
the following effects : 

1 i ) The percentage loss on evaporation (figured on the weight 
of coal-tar pitch in the mixture) is progressively decreased. 

(2) The fusing-point of the mixture is increased in direct pro- 
portion to the degree of fineness of the filler, irrespective of its 
chemical composition. 

(3) The difference between the fusing-point of the mixture, 
before and after the evaporation test, is progressively decreased. 

(4) The Ubbelohde dropping-point (Test i$h) of the mixture 
is progressively increased. 

(5) The difference between the dropping-point of the mixture, 
before and after the evaporation test, is progressively decreased. 

(6) The "breaking-point" (Test 13) of the mixture is pro- 
gressively decreased. 

(7) Different fillers influence the characteristics of the mixture 
to a greater or lesser extent, depending upon their physical charac- 
teristics, degree of subdivision, etc. 

(8) Mixtures of two different fillers often give results superior 
to the use of either filler alone. 

Tests for load characteristics, compressibility and mechanical 
strength, show the fillers named in the order of their superiority 
for use in tar-concrete pavements: limestone, copper slag, sand- 
stone, Portland cement, volcanic slag, slate, etc. 125 

The effect of inorganic colloidal particles liberated "in situ" 
(Type A-2-a) is shown in the following figures, obtained upon heat- 
ing i kg. of residual oil at 400 F. for one hour with the metallic 
salt named : 



502 



DISCRETE AGGREGATES 
TABLE XLVIII 



XXIV 



Fu sing-point 
(K. and S.) 
(Test 



Penetration 
at 77 F. 
(Test 9^) 



Hardness 
at 77 F. 



Semi-asphaltic Residual Oil: 

Untreated 102" 

With 2 per cent ferrous sulfate 105 

With 2 per cent aluminium chloride 114 

With 2 per cent copper sulfate 1 1 8 

With 2 per cent copper carbonate 118 

With 2 per cent zinc chloride 130 

With 3 per cent zinc chloride 142 

With 4 per cent zinc chloride 162 

With 5 per cent zinc chloride 168 

Asphaltic Residual Oil: 

Untreated 105 

With 2 per cent copper sulfate 128 

With 3 per cent copper sulfate 131 

With 4 per cent copper sulfate 141 

With 5 per cent copper sulfate 155 

With 2 per cent zinc chloride 140 

With 3 per cent zinc chloride 176 

With 4 per cent zinc chloride 205 

With 5 per cent zinc chloride 217 



120 

108 

81 

74 

70 

44 
3* 

20 

'9 



68 
60 

5i 
43 

50 
39 



4-93 

5-57 
7-37 
8.09 
8.48 
13.2 

17-4 
24.1 
24.7 



5-0 

8-9 

10 o 

11.7 

13 7 
11.9 
15 o 
18 o 



5 



After treatment, the first series showed a bright lustre and the 
second series a dull lustre. 



CHAPTER XXV 
BITUMINOUS SUBSTANCES DISPERSED IN WATER 

Types of Bituminous Dispersions 

These include bituminous-aqueous emulsions and suspensions. 
A bituminous-aqueous emulsion consists of a dispersion of a liquid 
or semi-liquid bituminous substance throughout water, and a bitumi- 
nous-aqueous suspension consists of a dispersion of a semi-solid or 
solid bituminous substance throughout water. A bituminous emul- 
sion constitutes two liquid phases a bituminous phase and an 
aqueous phase a "phase" being regarded as a physically distinct, 
mechanically separable part of the system. A bituminous suspen- 
sion constitutes a non-fluid or solid bituminous phase and a liquid 
phase. Systems in which either a solid or a liquid is dispersed in a 
liquid medium, are termed "sols," and if the liquid medium is 
aqueous, the colloidal system is termed a "hydrosol," whereas if 
the liquid medium is an oil, the system is termed an "oleosol." 
The agglomeration, coalescing and deposition of the disperse phase 
is termed "coagulation" or "peptization." The coagulation of sols 
may be in the form of more or less definite particles, or of a jelly, 
or of a flaky mass, usually termed "flocculcnt." The precipitate 
formed is called a "gel." The dispersed particles are termed "mi- 
celles" if they have absorbed another constituent on their surface, 
with which they combine as the disperse phase. A substance which 
renders dispersions stable, once they are formed, as well as to facili- 
tate their formation, is termed a "dispersing agent," or a "defloccu- 
lating agent," or a "peptizing agent." This is known as a "protec- 
tive colloid" if a solid, and an "emulsifying agent," or "suspending 
agent," or "stabilizing agent," if a liquid. The bituminous-aqueous 
dispersion is said to have the bituminous constituent in the "exter- 
nal" or "continuous phase" and the water in the "internal" or "dis- 
crete phase," when the dispersion will mix readily with more of the 

603 



BITUMINOUS SUBSTANCES DISPERSED IN WATER AAV 

bituminous constituents but not so readily with water. The bitu- 
minous constituent is said to be in the "internal" or "discrete phase," 
and the water in the "external" or "continuous phase," when the 
converse is true. However, it is possible to produce bituminous- 
aqueous dispersions which will mix with either water or more of 
the bituminous constituents with equal facility. 

Certain colloids, when desiccated, will become re-dispersed upon 
the addition of the dispersion medium, without any special manipu- 
lation being required. Such colloids are termed "reversible," and 
when the continuous phase is aqueous, are said to be "hydrophile" 
or "lyophile" (i.e., water-loving) because of their ready re-disper- 
sion in water. On the other hand, other colloids, on desiccation, do 
not manifest this property, and are termed irreversible and are said 
to be "hydrophobe" or "lyophobe" (i.e., water-fearing) when the 
continuous phase is aqueous. 

When a suspension and an emulsion are mixed, the non-fluid or 
solid particles in the former coalesce with the liquid globules of the 
latter, and viscous liquid or semi-solid globules are formed which 
are prevented from coalescing by the protective colloid or emulsi- 
fying agent, and thereby form a stable dispersion. Thus, although 
the dispersing agent prevents the viscous globules from coalescing 
with each other, it does not prevent the solid or non-fluid particles 
from coalescing with the fluid globules. 

Investigations on surface- and interfacial-tension enable us to 
understand how dispersing agents effect a stabilization of aqueous- 
bituminous dispersions. For example, at 20 C, the interfacial 
tension between water and benzol is 35.0 dynes per cm. If, how- 
ever, the water contains 0.4 per cent NaOH and the benzol 2.8 
per cent of oleic acid, the interfacial tension is reduced to 0.04 dyne 
per cm., or about o.ooi of the initial value. As an empirical rule, 
it has been shown that dispersions are stabilized by substances form- 
ing colloidal solutions or suspensions in water. The majority of 
dispersions contain globules of varied dimensions, with the smaller 
globules squeezed into the spaces between the larger ones. The 
dispersing agent serves to inhibit the coalescence of the internal 
phase and does not necessarily determine the degree of dispersion 
attained. After evaporation of the water, the dispersing agent re- 
mains in the bitumen as a "filiform," or honeycomb structure, which 



XXV FORMS OF APPARATVS USED 505 

serves to modify the physical properties of the film (i.e., fusing- 
point, gloss, weather-resistance, etc,). 1 

Forms of Apparatus Used. Two types of apparatus are em- 
ployed to produce bituminous-aqueous dispersions : -* 

(1) Agitators or "homogenizers." 

(2) High-speed disintegrators, termed "colloid mills.' 1 

Agitators are adapted to treating liquid or semi-liquid bitumi- 
nous substances which may be readily broken up in the cold into 
minute globules. Semi-solid or solid bituminous substances may 
also be dispersed by means of agitators, if treated in the heated 
state, and provided they melt below the boiling-point of water. 
Similarly, solid bituminous substances may be dispersed in this type 
of apparatus, provided they are first comminuted by grinding, atom- 
izing, 2 or the like, and the powder agitated in the cold with cold 
water containing the dispersing agent. A typical form of apparatus 
consists of a jacketed vessel in which is suspended a metal cylinder 
open at both ends, enclosing a vertical shaft carrying propellers 
adjustable to varying heights on the shaft. By reversing the pitch 
of the lower propeller, a powerful pull is created from the bottom 
of the mixing vessel, while the upper propeller creates a downward 
flow. The two opposing streams are thus forced against each other 
and then thrust against the sides of the vessel with great force. In 
this case the dispersion is the result of violent turbulence. A varia- 
tion consists in using a revolving cylinder fitted with hollow trun- 
nions carrying a horizontal, revolving shaft with a number of 
beaters arranged to run in the opposite direction to that of the 
cylinder and its contents. In all cases, it is desirable to run the 
disperse phase into the external phase, so as to assist mechanically 
the promotion of the dispersion. The dispersing agent is prefer- 
ably carried in solution or suspension in the external phase. The 
water containing the dispersing agent is first introduced through a 
pipe, and while the propellers are in motion, the bituminous con- 
stituents are gradually run in through another pipe, either in the 
cold (if sufficiently fluid), or else in a molten condition. 8 The fin- 
ished emulsion is drawn off at the completion of the operation and 
cooled rapidly to room temperature. 4 Thus, in the case of an as- 
phalt having a fusing-point of 150 F. (R. and B.) and a penetra- 



506 BITUMINOUS SUBSTANCES DISPERSED IN WATER XXV 

tion of 28 at 77 F., and with the use of clay as dispersing agent, 
the following procedure is recommended: 30 parts of clay and 70 
parts of water are introduced at 120 F.; J:hen the asphalt at 
220 F. is gradually added under continuous stirring. The com- 
pleted emulsion will consist of 6 per cent clay, 14 per cent water 
and 80 per cent asphalt. 

Other forms of agitators may consist of masticators, agitators, 
ball-mills, pug-mills, chasers or Chilean mills, etc., 5 in which me- 
chanical agitation is coupled with a certain amount of grinding or 
trituration. These forms of apparatus are no longer used, as they 
are comparatively inefficient. It may be stated in general, however, 
that the efficiency of the agitator will depend upon the amount of 
power or energy expended on the mixing operation. 

Colloid mills have now supplanted the mechanical type of agita- 
tors, since they not only form a better dispersion, but also consume 
a smaller amount of dispersing agent, or even it is claimed, without 
necessitating the presence of any dispersing agent whatever. 6 In 
this form of apparatus, the dispersion is obtained by providing ad- 
ditional mechanical energy in substitution of part, or all of the 
dispersing agent. They are adapted to treating liquid or commi- 
nuted solid substances in the cold, as well as all the types of bitu- 
minous substances in the heated state, provided they melt at, or 
near, the boiling-point of water. The colloid mill consumes con- 
siderably more power than agitators, which accounts for its greater 
efficiency in breaking up the bituminous substance into small globules 
or particles. 

Colloid mills effect a dispersion resulting in particles rarely less 
than IM in diameter, which are actually larger than what is gener- 
ally accepted as collodial dimensions, involving a particle diam- 
eter not exceeding 200 m|j. Hence it is more accurate to refer to 
this type of apparatus as a "dispersion mill'' rather than a colloid 
mill. Furthermore, a sharp distinction exists between a "homo- 
genizer" which operates under a pressure of 2000 to 3000 Ib. per 
sq. in. and the colloid or dispersion mill, since the homogenizer is 
not adapted for dispersions of solids or heavy liquids. Although 
some pressure is utilized in the colloid mill, the main effect depends 
upon the hydraulic shearing forces exerted upon the particles in the 
presence of a fluid by the rotating surfaces. In the case of asphalts, 



XXV 



FORMS OF APPARATUS USED 



507 



the size of the dispersed particles is rarely less than ip; usually 
about 3-6|j; the upper limit being about 15^ in diameter. The par- 
ticles in the neighborhood of IM show Brownian movement, which 
is absent in the larger particles. In the presence of a stabilizing 
agent, the dispersions carrying the larger particles will remain 
stable otherwise they are apt to "break" if the particles average 
greater than 5^ (i.e. in the absence of a suitable stabilizing agent). 7 

There are two general types of colloid mills, 8 viz. : beater-type 
mills, in which the particles are subjected not only to hydraulic 
shearing stresses, but also to impact stresses produced by revolving 
blades operating between fixed blades. This operates on the batch 
system and includes the original 
Plauson machine and its subsequent 
modifications, including the Hur- 
rell mill. 10 

The second consists of the 
smooth-surfaced type, in which two 
smooth surfaces in fairly close con- 
tact are rotated at a peripheral 
velocity of 2 miles per minute up- 
ward, and a low-pressure pump 
feeds the mixture between the dis- 
integrating elements which consist 
either of a truncated cone rotating 
within a fixed cone, as illustrated in Fig. I35, 11 or two flat discs rotat- 
ing in opposite directions, positioned either vertically, or horizontally 
as illustrated in Fig. 136. In the latter type of machine, the ma- 
terial is introduced through the shaft attached to one of the discs, 
being thrown off the periphery of the discs into a chamber where it is 
removed by gravity. In some cases the discs are roughened, so as to 
augment the hydraulic shearing action. The moving elements have a 
clearance of o.oo2-in. upwards and are operated at speeds of 3500 
r.p.m. upwards. For each type of mill there exists an optimum speed, 
or degree of agitation or mixing, and an optimum period of running- 
time, whereby the most stable dispersion may be obtained for a 
given system. In general, there is a speed above which the stability 
of the dispersion decreases. The practical significance of this is 
obvious, since an excessive expenditure of power is unnecessary. 




FIG. 135. Smooth-surface Type of Col- 
loid Mill -with Truncated-cone Work- 
ing Surfaces. A Material inlet; B 
Working surfaces; C Material outlet. 



508 



BITUMINOUS SUBSTANCES DISPERSED IN WATER 



XXV 



Solids should always be subjected to a preliminary grinding to not 
less than 80 mesh, and generally finer, depending upon the clear- 
ance at which the mill operates. A form of mill has been proposed 
to accomplish this, consisting of a pair of rotating discs with pro- 
jecting vanes or pins. 13 

Among the factors which influence the dispersion are tempera- 
ture, hydrogen-ion concentration and the 
protective colloid or dispersing agent 
used. 

The effect of rise in temperature is in 
general to make the dispersion easier. 
For non-miscible liquids, rise in tempera- 
ture is accompanied by a decrease in the 
interfacial tension, a condition favorable 
to dispersion. A colloid mill will effect 
the dispersion with a smaller amount of 
dispersing agent than if merely agitated 
mechanically, as may be illustrated by 
the following figures: 100 parts of water 
are heated to 90 C. and 3.5 parts caus- 
tic soda and 25 parts oleic acid are 
added. The resultant mixture, contain- 
ing 20 per cent by weight of sodium 
oleate is diluted with 9 times its volume 
of water heated to 90 C and then run 
through a colloid mill with an equal 
amount of asphalt heated to not exceed- 
ing 1 00 C. The resulting emulsion con- 
tains equal parts of asphalt and water, 
with i per cent by weight of soap, or in 
other words 50 times as much asphalt as soap. 14 On the other hand, 
by using an agitator of the average efficiency, the best that may be 
accomplished with the same ingredients is to form an emulsion with 
about 25 times as much asphalt as soap, even though the former is 
introduced in installments. 15 

Character of the Bituminous Substance. They may either be 
soft or hard. Soft substances may be dispersed at room tempera- 
tures, or with the application of a moderate amount of heat Hard 




FIG. 136. Smooth-surface Type 
of Colloid Mill with Opposed- 
disc Working Surfaces. A 
Material inlet ; B Working sur- 
faces; C Material outlet; JD 
Cooling-water inlet ; E Cool- 
ing-water outlet. 



XXV ORGANIC SUBSTANCES 509 

substances may either be pulverized and dispersed at room tem- 
perature, or else melted and dispersed in the fluid state. Prac- 
tically every form of bituminous substance has been proposed for 
dispersions, including: natural and artificial asphalts; coal tar and 
coal-tar pitch; various mixtures, such as asphalt fluxed with low- 
temperature tar. 16 

Character of the Dispersing Agent. The following constitute 
the principal types of dispersing agents which have been proposed 
from time to time for use with bituminous substances. 17 

(A) INORGANIC SUBSTANCES 

(1) Hydroxides. Including: FeOH 3 , A1OH 3 , CaOH 2 , 
BaOH 2 , etc. 18 

(2) Oxides. Including: Fe 2 O 3 , Al a O 3 , CaO, MgO, BaO 2 , 
ZnO, CuO, Pb 3 O 4 , etc.; 19 various forms of silica, such as silica gel 
(i.e., hydrated silicic acid) ; 20 infusorial earth; 21 sand. 22 

(3) Silicates. Including: soluble silicates (e.g. Na 2 SiO 3 ); 23 
insoluble silicates (e.g. Fc, Al, Ca or Mg such as talc, soapstone, 
hydrous magnesium silicate, etc.); 24 colloidal clays 25 inclusive of 
bentonite; 26 spent fuller's earth; 2T Portland cement; 28 soil or earthy 
matter; 29 etc. 

(4) Sulfates. Including gypsum (plaster-of-Paris). 80 

(5) Phosphates. Such as tri-sodium phosphate or sodium- 
hydrogen phosphate. 81 

(6) Sulfides or Polysulfides. Such as Na 2 S or K 2 S (with or 
without Na 2 CO 3 ) ; 32 arsenious sulphide; 83 etc. 

(7) Alkalies. These form "soaps" with bituminous substances 
containing saponifiable constituents (e.g., wood tar, rosin pitch, lig- 
nite tar, montan wax, fatty-acid pitch, certain coal tars, certain as- 
phalts, etc.) , and include : NH 4 OH, KOH, NaOH, K 2 CO 3 , Na 2 CO 3 , 
borax, etc.; 34 alkalies plus an asphalt solvent (e.g., benzol). 86 

(8) Miscellaneous. Including calcium arsenate, basic cad- 
mium sulfate, etc. 

(B) ORGANIC SUBSTANCES 

(1) Fats and Oils. Such as cholesterol alone; 86 sulfonated 
cholesterol ; ar cholesterol with H 3 BO 3 or H 3 PO 4 ; 88 stearic acid with 
diethylene or triethylene glycoL 80 

(2) Resins. As for example synthetic resins (e.g. phenol- 
aldehyde, or cumarone) with or without alkali. 40 



510 BITUMINOUS SUBSTANCES DISPERSED IN WATER XXV 

(3) Soaps. Including combinations of NH 3 , K t Na, Mg, and 
Ca, with fatty acids or resin acids (e.g., fats, fatty-acids, saponi- 
fiable oils, cholesterol, fatty-acid pitch, wood tar, wood-tar pitch, 
rosin, rosin pitch, montan wax, lignite tar, etc.) ; 41 ammonium lino- 
leate or trihydroxy-ethylamine stearate, sulfates, etc.; 42 triethanol- 
amine oleate; 43 glycerinmonostearic-acid ester and amino-ethylene- 
amido-chlorhydrate ; 44 soap and cyclohexanol ; 46 crude lignite wax 
and alkali; 46 etc. 

(4) Sulfonated Vegetable Oils. Including turkey-red oil; 47 
metal sulfonates (with glycerin, etc.), 48 

(5) Sulfite Liquor (derived from alkali-cellulose manufacture). 
Includes the use of sulfite liquor alone; 49 with slaked lime; 50 with 
Fe, Al or Cr sulfate; 51 also sulfite-cellulose pitch. 52 

(6) Mineral-Oil Derivatives. These include polymerides of 
olefin (i.e. alkaline oxides) ; 53 naphthenic acids and their salts (i.e. 
sulfo-derivatives, acid sludges, oxidation products, etc.) ; 54 aromatic 
sulfo-derivativcs (e.g. "kontakt") ; 55 oxidized paraffin wax with or 
without NaOH; 56 oxidized mineral oil products (e.g. blown with 
Na 2 CO 3 and NH 4 -stearate) ; 67 chlorinated mineral oil derivatives; 58 
residues from cracking processes (e.g. "Dubb's Sludge") ; 59 etc. 

(7) Carbonaceous Matter. Such as powdered hard bitumi- 
nous substances; 60 powdered lignite, brown-coal or oil shale; 61 pow- 
dered bituminous coal; 62 carbon black; 63 etc. 

(8) Alkaline Bases. Including pyridines, amines (e.g. tri- 
ethanolamine), cresylates, piccolin, quinolin, etc.; 64 resorcinol, pyro- 
gallol, a or 0-naphthol, carbazol, etc. 65 

(9) Proteins or Proteids. Include alkaline caseinates, albu- 
min, lecithin; 66 vegetable proteins (e.g. soya-bean flour); 67 muci- 
laginous extract from linseed or flaxseed hulls. 68 

(10) Albumenotds. Such as glues and gelatines. 69 

( 1 1 ) Pectins. Include the various gels. 70 

(12) Gums and Algae. Such as gum-Arabic (acacia), traga- 
canth, various seed-gums, agar-agar, Irish-moss (carrageen moss) 
etc.; 71 algin; 72 alkaline alginates (e.g. seaweed and alkali); 73 etc. 

(13) Polysaccharides and Hemicelluloses. Such as starch, 
dextrine, glucose and soluble carbohydrates, with or without alkali ; 74 
molasses residues with CaOH 2 ; 75 etc. 

(14) Tannins. Include tannic acid, alkaline tannates, heavy 
metal tannates, various bark extracts, saponin (soap bark), lignins, 
humic acid and alkaline humates (from turf, peat, brown-coal, de- 
cayed vegetable matter, etc.). 78 

(15) Miscellaneous. Include glycerin residues obtained on 
distilling glycerin; 77 viscose ; bile salts (e.g. oxgall) ; r9 0-tetra- 
hydronaphthalene ; 80 etc. 



XXV VARIOUS COMBINATIONS 511 

(C) VARIOUS COMBINATIONS 

1 I ) Clay in Combination With : Inorganic hydroxides ; 81 alka- 
line silicates or metal fluosilicates ; 82 Portland cement; 83 alum or 
sodium-hydrogen phosphate; 84 phosphoric, chromic, oxalic or ben- 
zoic acid; 85 alkalies; 86 soaps of various kinds; 87 sulfite liquor; 88 
alkaline casemates; 89 glue or gelatine; 90 starch paste; 91 tannic acid 
or alkaline tannates ; 92 tri-cresyl phosphate ; 93 etc. 

(2) Sodium Silicate in Combination With : Slaked lime 
(CaOH 2 ) ; 94 or rosin. 95 

(3) Soaps in Combination With: Alkaline silicates; 96 sodium- 
hydrogen phosphate; 07 borax; 08 sulfonated vegetable oil; 99 phenol- 
sulfonic acid; 100 alkaline casemates; 101 glue or gelatine; 102 gums 
(e.g. algae jelly or carrageen moss) ; 103 starch paste (or farina- 
ceous protein) ; 104 tannic acid or alkaline tannates; 106 etc. 

(4) Sulphonated Vegetable Oils in Combination IVithi Alka- 
line casemates ; 106 glue. 107 

(5) Alkaline Caseinates in Combination With\ Agar-agar ; 108 
alkaline tannates; 109 the latter it is claimed will form exceedingly 
fine-grained dispersions which will not "break" readily even when 
ferrous sulfate is added. 

(6) Glue or Gelatine in Combination With\ Aluminium salts 
(e.g. A1OH 3 or aluminium acetate) ; 110 molasses; 111 etc. 

(7) Tannic Acid or Alkaline Tannates in Combination With: 
Starch paste; 112 tri-sodium phosphate; 113 etc. 

Slow-setting, "stabile" dispersions are prepared with the use 
of inorganic hydroxides, clay, and other water-insoluble dispersing 
agents. Such dispersions will not break upon adding electrolytes, 
inorganic fillers (e.g. sand, silicates, asbestos, Portland cement, pig- 
ments, etc.), or organic fillers (e.g. wood flour, cork powder, etc.). 
Quick-setting, "labile" dispersions are prepared with the use of 
soaps and other water-soluble dispersing agents. Such dispersions 
will break rapidly upon adding inorganic or organic fillers. The 
speed of setting may be regulated by mixing together water-insolu- 
ble and water-soluble dispersing agents in suitable proportions; or 
by mixing together a rapid-breaking dispersion with a slow-breaking 
variety. 114 The use of dispersing agents in verious combinations 
(Group U C") not only gives better results than the use of one agent 
alone, but also effects a saving in the quantity required to accom- 
plish a given result. Water-soluble dispersing agents are known as 
"stabilizing agents." 116 



512 BITUMINOUS SUBSTANCES DISPERSED IN WATER XXV 

The addition of the following materials is claimed to retard 
the breaking of dispersions: an acid in the presence of Na or K 
fluoride, oxalate, tartrate or fluosilicate ; 116 an acid dye-stuff with 
potassium f errocyanide ; w basic dyes; 118 sodium zincate or sodium 
aluminate ; 119 dissolved gases (e.g. acetylene) ; 120 etc. 

The addition of the following substances is claimed to induce 
bituminous dispersions to break more rapidly: electrolytes, such 
as H 2 SO 4 , HC1, HaPCX, H 3 CrO 4 ; likewise CaCl 2 , NaCI, Na 2 SO 4 , 
etc. 121 

The mobility of bituminous dispersions may be increased by 
adding a small percentage of citric or mineral acids. 122 On the 
other hand, the viscosity may be increased by adding: a carbohy- 
drate, a phenol, or a colloid capable of swelling and forming a 
gel. 123 

A previously-formed dispersion may act as dispersing agent for 
additional bituminous ingredients, with or without the addition of 
dilute alkali as the external phase. 124 

Asphalt-solvents may be incorporated with bituminous disper- 
sions, especially in preparing emulsion paints (see "Bituminous 
Emulsion Paints n ). In certain cases tar dispersions are prepared 
with 10-20 per cent by weight of hydrocarbon solvents in addition 
to 40-50 per cent by weight of water. 

To prevent bituminous dispersions from congealing at low tem- 
peratures, the addition of the following agents has been suggested 
for the purpose of lowering the freezing-point of the aqueous phase : 
methyl alcohol; 125 aliphatic monohydric alcohols; 126 polyhydric alco- 
hols ; 127 acetone ; 128 glycerine ; 120 glycol, aniline, f urfurol, etc. ; 130 alka- 
line thiocyanates; 131 etc. 

Uses of Bituminous Dispersions. Dispersions of bituminous 
substances with water are utilized commercially for the following 
purposes : 

(1) Paving, including dust-laying, road-surfacing, cold patch- 
ing and in certain cases as the binding medium for bituminous mac- 
adam pavements. 

( 2 ) Impregnating paper, felt and their respective pulps, and in 
certain cases for coating the same. 

(3) As a substitute for coal-tar pitch or asphalt as the cement- 
ing medium for constructing built-up roofs. 



XXV USES OF BITUMINOU