(navigation image)
Home American Libraries | Canadian Libraries | Universal Library | Community Texts | Project Gutenberg | Children's Library | Biodiversity Heritage Library | Additional Collections
Search: Advanced Search
Anonymous User (login or join us)
Upload
See other formats

Full text of "Destructive distillation; a manualette of the paraffin, coal tar, rosin oil, petroleum, and kindred industries."

DESTRUCTIVE DISTILLATION 



the 

university of 

Connecticut 

libraries 



iif 



Es''cAt™",5ed.st,uat,on 



11 

3 ^153 OOOBOSbO T 

o ui 



0) 



liJ 
-J 



/ 

OH Z j 

GQ is 



/.^d 



Dook may be k 

TWO WEEKS i 

•3 subjeGt to a f 

ymTS a day ther*- '>? j 

'111 "be due on t , 

.ted below. 1 



OC"^ 



9 ^ V"* 






DESTRUCTIYE DISTILLATION : ' \^ 



A MANUALETTE 



OF THE 



PARAFFIN, COAL TAR, ROSIN OIL, PETROLEUM, 

AND 

KINDRED INDUSTRIES. 



BY 

EDMUND J. MILiS, D.Sc. (Lond.), F.KS, 



FOTJI^TH EilDITIOlSr. 



lo:n"dok': , > 

GUKNET & JACKSON", 1, PATERNOSTEK EOW 
(mr. van yooest's successoes). 



MDCCCXCII. 

All Riyhis Reserved. 




to^ 



LONDON : 
HARRISON AND SONS, PRINTERS IN ORDINARY TO FER MAJESTY, 

ST. martin's lane. 



Sl^'S 



PREFACE TO THE FIRST EDITION. 



Destructive distillation is a very ancient industry, whose 
intricate and numerous problems have been from time to 
time investigated by the ablest chemists. Its study has 
thus had a prominent influence in developing the science 
of Chemistry. 

This little book is the first to present as a whole the 
industry of destructive distillation. Its contents are the 
substance of a course of lectures delivered in Anderson's 
College, Glasgow, in 1875-76, and illustrated by actual 
inspection of many of the processes to which it refers. 
Students will profit most from its perusal who have such 
illustration at command ; and manufacturers will, it is 
hoped, be interested in the modern principles of the 
science that underlies their processes, and reap some 
advantage from learning how others treat the very same 
problems that are presented to themselves. 

The author begs to express his sincere thanks to the 
managers of works and other friends who with much 
kindness, and sometimes with much trouble, have con- 
tributed to his information on this important subject. 



Glasgow, 

November IsL 1887. 



A 2 



•«*'«. / 



'^^^:5 



PREFACE TO T]IE FOURTH EDITIOX. 



Since the last edition of this work was issued, increased 
attention has been bestowed upon the theory and practice 
of destructive distillation. 

It may now be regarded as demonstrated that cellulose 
and its kindred, or its immediate derivatives, tend to break 
up in terms of a Cg unit. 

The output of Russian and American petroleum 
continues to increase very largely, and has adversely 
alfected the economical conditions of the home produc- 
tion. New wells have been found in many parts of the 
world, and are attracting the attention of capitalists. 
Among tliese Peru, Canada, and Galicia contain probably 
the most important. 

Tar and sulphate are now among the regularly 
collected products of blast furnaces, coke-ovens, and gas 
producers. 

1 have again to express my indebtedness to several 
technical friends for information very freely placed at 
my disposal. I have also much pleasure in acknowledging 
valuable literary aid referred to in the terminal Biblio- 
graphy — more especially the classical papers of Messrs. 
Topley and Redwood. 

E. J. M. 



Glasgow, 

October 1st, 1892. 



DESTRUCTIVE DISTILLATION. 



GENERAL CONSIDERATIONS. 

Destructive distillation is the decomposition of a sub- 
stance in a close vessel, in such a manner as to obtain liquid 
products. 

By a product is meant a body not originally present in 
the substance distilled. A body merely extracted with- 
out change by distillation is termed an educt. Manufactured 
ozokerite consists in parts of educts from the native 
mineral, but this is an almost singular case in the industry 
of destructive distillation. 

If an extended list of substances volatile without de- 
composition be examined, it will be found that the nume- 
rical values or "numerics" of their chemical symbols, or 
formulae, are, on the whole, comparatively low; while 
bodies that do not volatiHse without decomposition have, 
on the whole, comparatively high numerics. These laws 
are both comprised in the more general one — that chemical 
activity increases, on the whole, with symbolic value. 

The apparatus employed in destructive distillation con- 
sists essentially of a retort, followed by a condenser and a 
receiver. The substance to be operated on is placed inside 
the retort, to which heat is applied : the volatile products 
pass over and are condensed in long straight or hehcal 
tubes, which are kept more or less cooled. The average 
contraction from heated vapour to liquid may be taken at 
about 1000 : 1. The retort or still has various forms, and 
may be set either in a horizontal or vertical position ; in 



b MANUALETTE OF DESTEUCTIVE DISTILLATION. 

the latter case the bottom may consist of water. Its 
material may be glass, iron, clay, or brick. Heat is apphed 
directly either to the sides or bottom, or both ; or super- 
heated steam alone may be driven in at one end. Steam 
of varied initial temperature, and direct heat, are some- 
times used together. 

The nature of the products depends (a) on the composi- 
tion of the substance heated; (b) on the degree of heat 
applied; (c) on the state of division of the material; (d) 
but not to any serious extent (on the large scale) on the 
material of the retort. A rough surface, however, will not 
unfrequently facilitate chemical change; and, according 
to Ramsay and Young, ammonia is far more completely 
decomposed (at 760°) in contact with iron than with 
copper. 

(a.) If an organic substance contain much infusible 
mineral matter (as, for instance, in the case of ordinary 
bituminous shale, which contains a great deal of aluminic 
sihcate), the latter will hold down the former, and compel 
recourse to a higher temperature. Thus gum-benzoin, 
when distilled alone, yields benzoate; when mixed with 
sand, it furnishes benzol. In cases of this kind, the fine 
state of division or porosity of the earthy constituent con- 
tributes, with the higher temperature, to a change in the 
nature of the prevailing reaction. Thus, the later products 
in the preparation of coal-tar consist in part of dehydro- 
genated fatty hydrides. Again, cannel coke may resist 
a low red heat without loss of nitrogen, while shale coke 
readily parts with it. 

The presence of chlorine, sulphur, oxygen, nitrogen, 
and hydrogen, in carbon compounds, gives rise to chlorides, 
sulphides, oxides, etc., in the distillate. Oxides generally 
precede hydrides in the condenser, as is strikingly seen in 
the destructive distillation of wood. Excepting plants 



GENERAL CONSIDERATIONS. < 

known as Cruciferce and the like, animal compo-imds give 
the most highly sulphm^'ised distillate. 

When shale is mixed with slaked lime, and distilled as 
usual for oil at the most suitable temperature, there is 
little gain in ammonia, but the crude oil is more easily 
refined. According to Beilby, nitrogen is more easily 
steamed out of coal or shale at a high temperature when 
the amount of fixed carbon in the coke is greater. 

(b.) The natm-e of the decomposition which takes place 
on heating is indicated by the term cumulative resolution- 
Instances of this are very common in inorganic chemistry. 
Thus, three units of manganic dioxide decompose in 
partnership, yielding a unit of trimanganic tetroxide and 
a unit of oxygen ; 

SMnO^ = Mn3 0, + 0,. 

When glycerin is heated, polyglycerins are formed by 
the union of n units of glycerin, which lose (n— 1) units 
of water ; 

nC3H303 - (n - 1) Efi = C3,H,„^ ,0,„+,. 
This last expression, when divided by w, becomes— 

n n 

so that the ulthnate stage of this accumulation, when n 
becomes indefinitely gi'eat, must be a polymer of glycide, 
CgHgOg. Pursuing the same course with glycide, &c., we 
have the following table of results : — 



Glycerin Alcoliolo'ids. 


Extreme Accumulation. 


c,,HA 


C^Hp, 


C3IIA 


C3H,0 


C,H,0 


C3H, 



8 iMANUALETTE OF DESTEtJCTIVE DISTILLATIOTT, 

The above mode of resolution is common to all poly- 
alcohols. In the important case of Woody fibre (whose 
•minimum formula is CgHj^O^) we have the two series — 



Cellulose Alcoholoids. 


Extreme Accumulation. 


GflA 


. .. C,HA 


c.flA 


■ •• C.H.O, 


CcHA 


C,HA 


Cflfi, 


. .. Cflfi 


Cfifi 


c. 



In this or essentially similar ways, we eA^entually anive 
at carbon as the result of retort operations upon wood; the 
gentler process of nature furnishes coal. 

The theory of cumulative resolution was first proposed 
by the author of this work. 

Most authorities are agreed that coal has been derived 
from more or less impure woody fibre or cellulose, nCfl-^fi^, 
under the influence of heat, pressure, and time. The effect 
of heat is at first to dehydrate cellulose. By interpolation 
among Violette's well-known results on the heating of wood 
(Ann. Ch. Phys. [3], xxxii, 304), it appears that nQ^fi^ 
corresponds to a temperature of about 185°, and nQ^f)„ 
to about 220^, in the absence of pressure ; in presence of 
pressure, the latter temperature corresponds to nOfifi^. 
At a point somewhat below 430°, and without pressure, the 
residue has the composition wCgH^O. The final stage nC^. 
is probably not attained under ordinary experimental con- 
ditions. 

According to these results, the composition and reac- 
tions of coal should turn upon the value of n, the losses of 
HgO, and the collateral kinetic changes wliich, occurring 
in the course of these definite transactions, lead to the 
formation of isomeric (or even of polymeric) coals. The 
organic matter in coal or shale, if we agree to represent its 



GENERAL CONSIDERATIONS. 9 

composition bj a formula, should correspond to an initial 
symbol nC^ or 2nC^, 

In constructing equations to represent the transforma- 
tions of coal and other complex bodies, collocations of 
symbols will be hereafter employed to indicate mean com- 
position ; it will be understood that these collocations are 
not intended to suggest separate chemical compounds. 

The preceding theory is practically modified by the law 
of decomposition already given. The numerical values of 
the cumulative formulae increase nearly by powers of n : 
hence the bodies represented are pro tanto more prone to 
decompose, and to vary in their kind of decomposition. 
Accordingly it is observed, that the number of by-products 
and subsidiary reactions increases, but more slowly towards 
the last, with the degree of heat appHed. Precisely similar 
considerations hold good for hydrides, chlorides, and all 
other bodies susceptible of cumulative resolution. Hence 
the presence of homologous series in tars. 

The process of decomposition by means of heat is most 
completely realised in the sun's atmosphere, which consists 
of the resolved weights of our common elementary, and 
perhaps some more simple, bodies. At the next lower 
temperature, that of the voltaic discharge, hydrogen unites 
with carbon to form acetylene, and with oxygen to form 
water, i^'rom these two products most organic bodies can 
be obtained by synthesis ; benzol, for instance, by keeping 
acetylene for a long time just below a red heat; naphthalin, 
by passing a stream of benzol or one of its homologues 
through a red-hot tube ; ethylene, by hydrogenating acety- 
lene ; alcohol, by hydrating ethylene. Hence naphthahn, 
hydrogen, and acetylene, with less benzol, are found in 
coal-tar products when a very high temperature is used; at 
a red heat they are absent, more benzol and chrysene 
being found. At a very high temperature the products 



10 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

from coal and shale are carbon and carbonised gases of 
low illuminating power, with but little liquid distillate, 
much ammonia, and few bases ; at a low temperature there 
is much liquid product (rich in bases, but poor in ammonia), 
and gas of high illuminating power. The greatest amount 
of liquid product of low boihng-point is found in American^ 
Russian, and Persian petroleums, which have probably 
been produced by the long-continued application of a very 
gentle natural heat. 

When coal is slowly heated (as must be to a great 
extent the case when it is broken fine or when a large 
retort is used), its oxygen is chiefly converted into water; 
when rapidly heated the oxygen is expelled as carbonic 
oxides. 

(c.) In the case of bituminous or caking coals, compara- 
tively large lumps are usually distilled, so that heat may 
freely traverse their interspaces. If the coal were in very 
fine powder, with all the particles in close contact, there 
would be very imperfect conduction and a low temperature 
product. Thus, in an experiment upon 30 grammes of 
coal by the present writer, particles 3"75 millimetres wide 
gave off with great freedom 9,437 cubic feet per ton ; par- 
ticles -375 millimetre wide gave off only 3,280 cubic feet, 
and that with much slowness. 

The retort was doubtless originally derived from the 
clay bottle, which in its turn was modelled on an animal 
skin or vegetable seed-case. In the sixteenth and seven- 
teenth centuries destructive distillation came to be the 
principal work in chemical laboratories. Most animal 
substances — sometimes the entire body (as, for instance, of 
the viper) — as well as plants, were so examined, or, as it 
was termed, "analysed." It was, however, seldom that 
any detailed investigation was made of the products. 
These were classified, according to L emery (1686), into 



GENERAL CONSIDERATIONS. 11 

five groups ; three active : " spirit " or " mercury " (most 
volatile), "oil" or "sulphur" (less volatile), and "salt" 
(least volatile, or even fixed), soluble in water ; tioo passive : 
" water " or " phlegm " (passing over before the spirits 
when they are fixed, after them when volatile), and 
" earth," " terra damnata " or " caput mortuum," a dry unin- 
flammable residue. From this epoch the terms " oil " and 
" spirit " still survive in their ancient sense. 

The phlogistic, oxygenic, and atomic periods in 
chemical history have not been specially characterised by 
attention to destructive distillation. Much light, however, 
has been incidentally thrown upon it by the gi-eat modern 
revival in organic chemistry. By a study of the reactions 
of a number of individual definite substances, a skeleton 
theory of the process has at least been rendered possible. 
It is in the systematic researches of Reichenbach, Runge, 
Stenhouse, and Anderson, in connection with destructive 
distillation, that the basis of all our exact knowledge is to 
be found ; while the investigations of Gerhardt and Wiirtz 
into the behaviour of polyacids and polyalcohols have 
furnished the lucid superstructure. For much suggestive 
work on synthesis and inverse reactions we are indebted 
to Berthelot. 

Coal-gas came into use in about the year 1820 as an 
illuminating agent. Paraffin was discovered by von 
Reichenbach in 1830, in beech-tar. The low-temperature 
industry was commenced, as such, by James Young, in 
1851. 

In the process of refining crude distillates, advantage 
is taken of the fact that the diff'erent constituents of such 
mixtures boil and pass over at diff'erent temperatures. 
This process of separating is termed "fractional distilla- 
tion/' for the theory of which we are chiefly indebted to 
Wanklyn. In 1863, that author showed that " the quantity 



12 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

of eacli ingredient whicli distils will be found by multiply- 
ing its tension at the boiling-point of the mixture by its 
vapour-density." Thus, methylic alcohol boils at 6Q°, 
methylic iodide at 72° ; but from a mixture of the two the 
latter distils even in greater quantity. The liquid with 
the highest vapour-tension will thus not necessarily distil 
the quickest ; for what the accompanying liquids want in 
tension they may make up by the greater density of the 
vapom-s they give off. If t represent tension, and d density, 
then for various liquids ic — 

^j = kjt^d^ ; .2?2 = ^^^2*^2 5 -^3 = ^'3^3^3 ; &c. ; 

k being a constant of condition, calculated from the experi- 
ments. If the vapour-densities and tensions are inversely 
proportional, and the values of k equal, the products kj^d^ 
will all be equal, and the mixture will remain unchanged 
in composition while distilling. Homologous bodies, that 
is, those members of the same series whose common dif- 
ference is CH^, are thus difficult to separate; because, 
though the tension sinks with each increment of CHg, the 
vapour- density rises. Many oils distil over more rapidly 
in a current of steam (one of the lightest vapours) because 
their vapours are usually heavy; hence one reason for 
the introduction of steam into paraffin retorts. Under 
diminished pressure, the differences between the vapour- 
tensions of liquids are increased, and their separation is so 
far facilitated ; to this principle the use of exhausters in 
gas-works is for the most part due."^ 

In a recent memoir (Phil. Mag. [5] xvii, 173) it has 
been shown that the boihng-points of all known normal 

* For a further development of the theory of fractional distillation, see 
Wanklyn, Philosophical Magazine (4), xlv, 129 ; Glashan, ibid., 273 ; Brown, 
Chem. Soc. Journ., 1879, i, 547 j and KonovalaflF, ibid., 1881, ii, 1093. 



GENERAL CONSIDERATIONS. 13 

parafiSns having an even coefficient ^ of C are comprised 
in the equation 

_ 39'3156r - 3-94) 
^ ~ 1 + •070753(^ - 3-94) 

Similarly, when the coefficient of C is uneven, the equation is 
38•992(.^^ - 3-92) 



y 



1 + •070564(.c - 0-92) 



When X is made exceedingly large in these equations, y 
(the boiling-point) becomes 555-t37° and bb2'b%° respec- 
tively. These values very nearly agree ; and we may 
take their mean, 554°, as a working number. The normal 
paraffins have the highest boiling-points of any substances 
which it is the object of the shale-distilling industry 
to attain. Tliis number represents the highest or limit- 
ing temperature required in the interior of a shale retort 
during the evolution of paraffins. 

The course of destructive distillation admits of quan- 
titative admeasurement in various ways. The usual 
method is to determine gravities ; but no chemical method 
has ever been systematically followed at works. 

The destructive distillation of rosin furnishes an excel- 
lent illustration of the ineffectiveness of the physical, as 
compared with the chemical, examination. While the 
extreme range of gravities in the distillate is only from 
•90968 to 1*03038, the range of bromine absorptions is 
from 32*02 to 142*48. A distinguished firm of Glasgow 
distillers very kindly placed at the author's disposal a 
series of samples representing a complete distillation from 
one of their smaller stills. The samples were carefully 
sealed, and allowed to rest in a warm place for about 
eight months, at the end of which time the separation of 
the water was regarded as practically at an end. Two 



14 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



bromine absorptions (by the titration method) were then 
made for each sample, and the gravities determined 
at 9° C. 

The rosin used for distillation was American. It 
was blackish-brown in colour. Specific gravity at 
15° C = 1*065; bromine absorption (determined colori- 
metrically) 101-66 per cent. [Pure rosin absorbs nearly 
112-96 per cent] 

The following table contains the whole of the results: — 



No. of 
Sample. 


Hours. 


Sp. ar. 


Bromine 
Absorption. 


Eemarks. 








per cent. 




1 


0-5 


•90968 


142 -48 


Spirit begins. 


2 


10 


•92308 


131-56 




3 


1-5 


•92890 


128 -70 




4 


2 


•92342 


119-24 




5 


2-5 


•93863 


109 ^62 




6 


3-25 


•951U0 


107 -18 


Spirit ends. Oil begins. 


7 


4-0 


•98400 


85-31 


Not quite clear. More 
viscous. 


8 


4-75 


•98429 


77-27 




9 


5-50 


•99601 


71^20 




10 


6-25 


•99792 


63-37 




11 


7-00 


•99820 


60^74 




12 


7-75 


•99621 


63-50 




13 


8-50 


•99621 


61-28 




14 


9-25 


•99621 


61^62 


Darker coloured. 


15 


10-00 


•99332 


59-61 


StUl darker. 


16 


10-75 


•99241 


57-28 


» j> 


17 


11-50 


•99181 


52-60 


Less dark. 


18 


12-25 


•99920 


43-46 


Dark layer at sui-face. Less 
viscous. 


19 


13-00 


•99880 


50-76 


Darkest of all. 


20 


13-75 


1 ^03038 


38-83 


Dark and turbid. 


21 


14-50 


1 -01731 


41-89 


j> j> 


22 


15-25 


•99122 


32-30 


Verv dark. 


23 


16-00 


•96960 


32-02 


Nearly as dark as 19. 



From these experiments some interesting inferences 
may be drawn. In the first place, it is evident that 
neither the specific gravity nor bromine absorption follows 
a perfectly regular course ; this is very possibly due to 



GENERAL CONSIDERATIONS. 15 

unavoidable errors in firing, and to some superheating at 
the sides of the still, which did not contain more than 
about 1,000 gallons. On the whole, however, the bromine 
absorption quite evidently decreases as the specific gravity 
increases, and from sp. gr. -90968 to 1*03038 (the 
extreme range) 1 per cent, of bromine corresponds to 
about -00058563 sp. gr. There is some indication of a 
break in the series, where spirit ends and oil begins. The 
extremely heavy bodies formed towards the close of the 
distillation split up at last into lighter ones ; but as shown 
by the bromine absorption, these are probably of nearly 
the same chemical order as the heavy ones. As the course 
of the distillation proceeds from a great to a small bromine 
absorption, it involves the formation of more and more 
saturated bodies; in other words, an approximation is 
continually in progress towards the composition of the 
paraffin series. 

The relations of bromine absorptions to time are — 

y = 158-5('86406)^ and 

y = 62-4 - 2-2657(l-3689)^-^ 

t being the number of hours, and y the bromine absorption. 
The first curve is in fair agreement with the actual work, 
and indicates that the bromine absorption could not exceed 
158'5 per cent. This cm^ve terminates at about the 
seventh horn-, after which the absorption alters very little 
imtil the tenth hour, when it decidedly begins to fall. 
The exact position of the second curve is much more 
difficult to find, and lies less close to the experimental 
points. This, indeed, might have been reasonably expected 
from the diminished content of the still, the increasing 
eff'ect of the heat, and the consequent magnifying of every 
irregularity that occurred. Better results could, doubtless, 
be attained with a still of greater capacity. 



IG 



MANUALETTE OF DESTEUCTIVE DISTILLATION. 



PARAFFIN INDUSTRY. 



Paraffin oil can be prepared from coal, bituminous shale, 
cannel, lignite, wood, peat, Kimmeridge clay, and the like, 
on the one condition that a very low red heat is employed. 
It is certain that the greater part of the decomposition 
and distillation takes place below 427° C. The highest 
possible boiling-point of any normal paraffin is 554° C ; 
and Rowan's investigations have rendered it probable 
that this is the extreme limit practically required in a 
shale retort. The material originally used in this country 
was boghead coal, or the Torbanehill mineral, exhausted 
in 1872 ; this jdelded 33 per cent, of crude oil, and 1-1^ 
per cent, of crude paraffin. At present, selected mid-vein 
shales are used, which furnish about 13 per cent, of crude 
oil, somewhat above the average yield of good foreign 
shales. Certain authorities quoted by Wagner {Technology, 
pp. 687-8, 1872), give the results of the examination of 
forty different kinds of coal, peat, &c., as treated for low- 
temperature tar. The means are, omitting boghead : — 



— 


Oil per cent. 


Sp. Gr. 


Paraffin. 


23 kinds 

17 „ 


8-1 


0-79 


"6 per cent. 



The kerosene shale in New South Wales covers a vast 
area. It is found at Lake Macquarie and Greta, in Cum- 
berland County; at Mount Magallon and Mount York, 
in Cook County; at Joadga Creek, Cambewarra Ranges, 
Broughton Creek, and Toenail River, Burragorang, in 
Camden County, and at Blackheath, the Vale of Hartley, 
and other places in the Blue Mountains. The mineral 



PARAFFIN INDUSTRY. 17 

was known to exist in New South Wales as early as 
1827. It has no characteristic lamellar or fatty structure, 
but the reverse ; being very compact, and breaking with 
large, smooth conchoidal surfaces with equal readiness in 
every direction, and without any tendency to follow the 
planes of stratification. The mineral does not differ very 
widely from cannel coal and torbanite. Sp. gr. 1*098. The 
seams are from 1 foot to 2^ feet in thickness. It is much 
more difficult to mine than coal, and is usually won with 
iron picks and pointed rods. It does not run down 
readily into blocks, but has to be separated piece by piece, 
and splintered off into sharp thin pieces. It is easily 
lighted with a match, and burns with a steady flame like 
a candle, and emits a strong odour of kerosene. AVhen 
mixed with ordinary coking coal, 3 per cent, will yield 
gas of 18 candles, and 6 per cent, with the same coal 
22 candles. 

The New South Wales shale is said to yield 100-150 
gallons of crude oil per ton, and 18,000 cubic feet of 
39-candle gas. The oil yields more than 60 per cent, 
of refined kerosene, in addition to gasoline, benzoline, 
phenoids, and lubricants. 

The composition of the shale is approximately : — 



Water 


.. 0-5 


Hydrocarbides 


.. 81-0 


Fixed carbon 


. . 10-0 


Ash 


.. 8-0 


Sulphur 


.. 0-5 




100-0 


Coke . . 


. . 18-0 



The subjoined table shows the quantity and value of 
shale produced in the colony of New South Wales for 
each year, from 1865 to 1884 inclusive : — 

B 



18 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



Year. 


Quantity. 


Value. 




tons. 


dols. 


1865 . . 




570 


11,750 


1866 . . 




2,770 


40,770 


1867 . . 




4,079 


76,244 


1868.. 




16,952 


240,080 


1869 . . 




7,500 


93,770 


1870 . . 




8,580 


137,850 


1871 . . 




14,700 


170,250 


1872 . . 




11,040 


253,275 


1873 . . 




17,850 


143,500 


1874 . . 




12,100 


136,500 


1875 . . 




6.197 


77,500 


1876 . . 




15,99S 


229,970 


1877 . . 




18,963 


232,620 


1878 . . 




24,371 


286,055 


1879 . . 




32,519 


334,650 


1880 . . 




19,201 


223,620 


1881 . . 




27,894 


203,740 


1882 . . 




48,065 


420,570 


1883 . . 




49,250 


454,315 


1884 . . 




31,618 


360,380 



The following table shows the quantity and value of 
the export of kerosene shale from the colony of New 
South Wales, for each year since 1875 : — 



Year. 


Quantity. 


Yalue. 




tons. 


dols. 


1875.. 




3,527 


51,915 


1876 . . 






8,154 


106,570 


1877 . . 






4,667 


70,815 


1878 . . 






12,202 


117,105 


1879 . . 






11,436 


141,375 


1880 . . 






10,880 


120,845 


1881 . . 






17,846 


191,155 


1882 . . 






35,975 


398,575 


1883 . . 






22,657 


236,925 


1884 . . 






12,804 


119,870 



The value of this shale raised in 1889 was 1,234,449/., 
and the amount 536,682 tons. Much of it is imported 
into England for gas- making. 



PARAFFIN INDUSTRY. 19 

The gas occluded in cannel coal is chiefly carbonic 
dioxide, with which members of the paraffin series are 
associated. 

The presence of 40 — 50 per cent, of low-pressm'e steam 
increases the yield of crude oil by about 10 per cent. ; 
much superheated steam burns the shale, and converts the 
ordinary alkaline into an acid distillate. The bog-head 
oil was found comparatively difficult to purify; the more 
recent, or 13 per cent, oil, is easier to purify,' because the 
hot porous shale in the retort has itself done work of 
purification. 

Sulphur is well known to decompose paraffins. Shales 
such as the Kimmeridge clays, containing 5 — 15 per cent, 
of sulphur, yield scarcely any paraffin wax (the kind of 
paraffin most easily thus attacked) on distillation. Irvine 
has therefore proposed (1884) to pass ammoniated steam 
through the retort ; this, he states, protects the paraffins 
and so increases their yield. 

It is an inference from Irvine's result, that highly nitro- 
genised shales are likely to yield well in solid paraffin. 

Paraffin shale, when found in contact with igneous 
rock, is almost black; it then yields more hght oil and 
ammonia, but less total oil. 

Scottish oil shale occurs below the coal measures 
generally in the neighbourhood of marls, limestones, or 
sandstones. It contains, on the average, about 73 per 
cent, of ash. 

According to Cadell, avIio has reported in detail upon 
the oil shale in West Lothian, the calciferous sandstone, a 
lower carboniferous series, as developed along the great 
anticline of Mid-Lothian, consists at the base of a series 
of red sandstones with thin shales and marls, and occa- 
sional interbedded volcanic rocks at the top. Above the 
red rocks come the white and gray sandstones of Granton 

B 2 



20 MAXTJALETTE OF DESTRUCTIVE DISTILLATION. 

and Craigleith, which are in turn overlaid by the black shales 
of Wardie and the sandstones and shales of Hailes and 
Redhall. Each of these tAvo great divisions has, accord- 
ing to the measurements of Mr. John Henderson, a thick- 
ness of over 3,000 feet. The oil shale gi'oup, which 
comes next, apparently begins with the Pumpherston 
shale, situated some 780 feet below the Burdiehouse 
limestone. It occupies the remainder of the calciferous 
sandstone series, and has in AVest Lothian a thickness of 
about 3,100 feet, so that the whole thickness of lower car- 
boniferous rocks in West Lothian probably exceeds 9,000 
feet. The Dunnet shale is the lowest member of the upper 
group of oil shales, and lies about 400 feet above the 
Burdiehouse or Camps limestone. About 450 feet higher 
up comes the Broxburn shale, which is perhaps the most 
important of the West Lothian oil shales. The strata 
intervening between the Dunnet and Pumpherston shales, 
and including the limestone, are chiefly argillaceous 
shales, with thin calcareous bands and occasional sand- 
stones. Above the Dunnet shale they become more 
arenaceous, and thick sandstone beds are developed, one 
of which has long been quarried at Binny, near Uphall, 
for building and ornamental purposes. The Broxburn 
shale, which is several fathoms above the Binny sand- 
stone, forms a well-marked horizon, as it underlies a 
group of marls and thin limestone bands, varying in thick- 
ness from 80 to 270 feet. This calcareous zone, locally 
known as the "Broxburn Marl," passes under the Fell 
shale, above which comes another series of sandstone 
beds, about 240 feet thick, Avhich underhe the Houston 
coal. This is, perhaps, the oldest coal seam in Britain, as 
in the Broxbm-n district it is situated about 1,000 feet 
below the base of the carboniferous limestone series. 
The Houston coal is covered by about 200 feet of pale- 



PARAFFIN INDUSTRY. 



21 



green and red amorphous marl, sometimes containing 
pieces of volcanic ash, and is apparently a fine volcanic 
mudtone. A thin coal seam and some oil shale occur just 
above the Houston marl, and two other oil shales have been 

GENEfffiL SECTION OF THE BROXBURN DISTRICT. 



HUPLET uMEsrxms 

DO • COAL 



R/KBUffhIi SHALE. 



MUNML9 SMUi. 

CREY SHALE. 
r*io FBET CO/91.. 

//ouJJSk PTarl. 
6RCr SHALK, 
Houston coal 

/a/Icy ^ancia/on^ 
Feu.^ SHALC. 

^/WL^rn, /ffca-/ 
BftOXBUPN SHALE. 

Sum Awo nun 0/1 



StASS At 
/ft/A/AtCr SHALE- 



Smjiy Sait^J/Snc 



Butsi, Lihutr fftea. 
Bahwkks SH/iLe. 

3u/90ieHOUSB on ctiMn 

LtmesroNE 



Chie,ffu /3/ttcS. 



\,.ffy 



Pt/**p/rek5roN Shales 



2S 








^S. 


0. 


0. 


3Z 





0. 


22 


0. 


0. 


^0 





0. 


/o 








^ 









-^5. 



7^ 



6S o. 



Bi> 



/o. 



worked still higher up, the highest of which — Raeburn's 
shale — is some 400 feet below Ihe carboniferous limestone. 
The oil shales and underlying parts of the calciferous 



90 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



sandstone series have no regular strike, but are bent 
about into troughs, domes, and anticlines, and are dis- 
located by large faults, besides which there is great 
irregularity in the thickness and character of the rocks, 
so that to work out the geological structure of the 
ground without the aid of mining information would be 
an impossible task. The shales were evidently deposited 
extremely sloAvly in a large gradually subsiding estuarine 
or fresh- water area inhabited by numerous fishes, lamelli- 
branchs, and small crustaceans, whose remains, along 
with those of plants, were constantly being deposited on 
the sea-floor when mud did not dilute the organic preci- 
pitate too much. 

The section on page 21 of the shales in the Broxburn 
district is due to Mr. D. R. Steuart. 

The following results, for which the author is indebted 
to Mr. Snodgrass, are of interest as showing the changes 
that may occur in the value of a shale with its depth : — 



Results of ExpeinmeMs upon 


Dannet Shale from 


Bore. 










Strength 




Section No, 


Thickness. 


Oil per 
ton. 


AVater 
per ton. 


of water 
in lbs. 
of Am. 


Am. 

Sulph. per 

ton. 










Sulph. per 










100 galls. 






ft. in. 


galls. 


galls. 




lbs. 


] 


1 6 


25-62 


12-89 


116-91 


15-07 


II. .. 




11 


25-55 


10-64 


70-21 


7-47 


III. .. 




6 


18-49 


12-00 


85-08 


10-21 


IV. .. 




1 


19-26 


10-88 


105-97 


11-53 


V. .. 




1 


24-39 


12-59 


140 -90 


17-74 


VL .. 




1 


24-06 


13-76 


135 -32 


18-62 


Vll. .. 




1 


31-91 


12 83 


73-73 


9-46 


Till. .. 




11 


27-07 


12-90 


82-48 


10-64 


IX. .. 




7 


23-71 


11 -C2 


50-86 


5-91 


Average 




•• 


25-15 


12-33 


102 -19 


12-60 



PARAFFIN INDUSTRY. 23 

No steam was used in distilling. 

The amnionic sulphate obtained cannot, of course, be 
accepted as what would be got in actual practice, as 
the quantity varies greatly with the conditions of distil- 
lation. 

The retort is of varied form and capacity. It is con- 
structed of thin cast-iron, and may be either elliptic or 
circular, or semicircular in section ; horizontal or upright ; 
narrow and tall, narrow and long, or wide and short. 
Preference has been given in very large works to the 
narrow, elliptic, upright kind. The retort is either closed 
by a door, screwed down and rendered tight by moist 
clay, or, if vertical, closed at the bottom by mere immer- 
sion in water. The latter method allows the spent shale 
to be cooled and removed very conveniently. The 
charging is intermittent. The charge fills the retort, 
and weighs from 1 — 3 cwt. ; in a vertical retort it is 
introduced through a hopper, closed by an iron valve, 
which is rendered tight by sand. 25 cwt. are generally 
worked off in about 24 hours; the retorts are charged 
every three hours, and drawn every hour. 

Rolle's retort consists of a vertical cyhnder, 16 feet 
high and 6 feet wide. This contains a number of very 
short and very open funnels, having the narrow end upper- 
most, and separated from the cylinder by a distance of 
two or three inches. Through this interspace the shale or 
coal falls, touching on its way the red-hot walls of the 
cylinder. The volatile products are removed by two 
large conduits, one near the base, the other at about the 
middle of the cylinder. Holmes's retort is in principle 
similar. In some horizontal retorts, more especially 
adapted to utilise " small " material, a hollow rotating 
screw is used to urge the shale forward ; in others a chain 
is employed ; and some retorts are revolved. On account 



24 MANU ALETTE OF DESTEUCTIVE DISTILLATION. 

however, of the difficulty with which heat traverses small 
shale, such processes, especially when mechanical power 
is used, must involve considerable expense. Hollow 
cylinders, moreover, suddenly expose the whole of the 
shale to great heat, and the jield of solid paraffin is then 
materially reduced. 

Horizontal retorts yield lighter oil (sp. gr. '84 — '86) 
but less paraffin than vertical retorts (the oil from which 
is of about •H9 sp. gr.). 

Much attention has been devoted in recent times to 
the improvements of retorts. Henderson, for example, 
constructs retorts of cast-iron, 1:^ inch thick, holding about 
18 cwt. of shale, and makes them in groups of four. 
Somewhat superheated steam is led in at the top, and the 
distillate removed at the bottom. When the distilla- 
tion is complete (ordinarily in 16 hours), the spent shale 
is, by the disengagement of a catch, dropped into a fii'e. 
This shale, together with the scrubbed gas, is adequate 
fuel for the distillation, excepting in cases where the 
retorts are much exposed, as in corner sites. This 
method of working leads to a great economy in fuel. 
The result in ammonia is about 16 lbs. of sulphate per 
ton. In this retort the temperature averages about 360° ; 
the temperature of the exit gases is about 290°. The 
yield of sulphate corresponds to one-fourth of the nitrogen 
of the shale. The permanent gas amounts to 2,000 cubic 
feet per ton. On the other hand. Young and Beilby take 
off their distillate from a chamber near the top of the 
retort. As this portion is only moderately hot, the dis- 
tillate cannot practically exceed a certain gravity ; a con- 
dition amounting to much the same thing as redistillation. 
So great, in fact, is the improvement in the oil produced 
in this way, that the ordinary first distillation can be dis- 
pensed with. Such oil, as might be expected, is about 



PAEAFFIN INDUSTRY. 25 

•02 sp. gr. ligliter than ordinary tar. The retort itself is 
compound, consisting in its lower portion of firebrick, in 
its upper portion of cast-iron ; in the lower the charge is 
heated white-red, and superheated steam mixed with car- 
bonic oxide from a contiguous coal-tower (" gas pro- 
ducer ") is drawn in. The retort is charged on the top, 
and the spent shale and scrubbed gas are employed 
to heat it. From the gas-producer, a rather " dry " coal- 
tar and ammonic sulphate are obtained as by-products. 
The effect of the superheated steam is to convert the 
final portions of shale nitrogen into ammonia and pre- 
serve it after formation.* It may be questioned, however, 
whether a very high temperature is ever really required 
for this. This method of treatment has been tried, and 
yielded promising results, with ironstone shale; and the 
skilful handling it requires should be more tlian compen- 
sated by the large return (stated as sometimes a hundred- 
weight per ton, and ordinarily 65 per cent, of the possible 
ammount) of ammonic sulphate.! 

In the Couper-Rae retort, steam injects air into a large 
brick fire-chamber which receives spent shale. On this 
chamber an oval iron retort is set, in which the distillation 
takes place ; the retort is heated externally by the gases 
resulting from the injection, aided by a little extraneous 
firing. About 80 — 90 gallons of water are usually steamed 
through a ton of shale, as is the case with other retorts. 
The distillate is removed from the top of the retort. 

The Henderson retort and Young or Young and Beilby 
retort are noAv in extensive use. Both with these and 

* This important discovery is claimed by Grouven, nf Leipzig (1877). 

t Tervet (1883) finds that as much as 83 lbs. of sulphate per ton can be 
obtained by passing hydi'ogen over coke ; the ammonia thus made having 
the gi'eat advantage of being dry. Hydrogen sufficiently pure for the 
purpose can be obtained in the later stages of the distillation of the coal 
itself. 



26 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

the older forms an exhauster is invariably employed. 
\_See Appendix A.] 

Heat is applied directly and laterally from below, to six, 
fonr, or fewer retorts at the same time ; four being the usual 
number. The exit-tubes from the retorts are 4 — 8 inches 
in diameter, and feed into a main ; this may or may not 
be cooled, and may or may not be connected with a tar- 
tower to condense very volatile products. From some 
position in this main the gas always formed is led off; 
from 13 per cent, shale about 3,000 cubic feet per ton are 
obtained. The order observed in the distillation is (I) 
gases, (2) light oils, (3) oils containing solid paraffins, 
(4) dark and tarry alkaloidal oils. The liquid distillate 
is collected in large tanks which are sometimes steam- 
jacketed, sometimes not ; the latter is the English practice. 
Here the ammoniacal water settles to the bottom. In 
order to accelerate the process of separation, various salts 
have been tried {e.g., sodic chloride and sulphate), as in 
the extrusion of essential oils from plants ; but these have 
been abandoned on account of their cost aud the cost of 
recovery. A temperature of 50° C, imparted by a steam- 
jacket, answers very well ; or the distillate may be im- 
perfectly cooled. As a rule, the operation is left to itself. 

{a.) Gas. — Under the influence of extreme cold and 
pressure, Mr. Coleman has proved that the 3,000 cubic feet 
of gas which a ton of shale yields can be made to furnish 
three gallons of gasoline of sp. gr. -670. Rather less than 
this quantity is now cheaply obtained by passing the gas, 
preferably much cooled, through a coke tower down which 
heavy oil is trickling. This oil absorbs the light hydro- 
carbides of the gas, which are afterwards (but perhaps 
never completely) steamed out. Crude gasoline is rich in 
polysulphides ; it is reined by treatment with strong 
sulphuric acid and caustic soda of sp. gr. 1*36, followed by 



PAEAFFIN INDUSTRl:, 27 

distillation, in which process much free sulphur is observed 
to accompany the lighter portions. 

(fi.) Watery Liquor. — This, which constitutes about one- 
third to one-half of the bulk of the crude distillate, but 
much more (say 120 gallons per tonj when steam is led 
into the retorts, is pumped out as a lower layer after coohng 
and subsidence ; it is maintained at a uniform sp. gr. of 
1*03 (6° Tw.) by passing through the gas-scrubber, distil- 
lation, another transit throngh the scrubber, and conversion 
into steam for the retorts, thus never requiring to be 
discharged from the works, so as to pollute a contiguous 
stream. The liquor contains, in addition to ammonia, 
pyridine and similar amines in the caustic state (probably 
derived from shale nitriles, paracyanogen, or allied bodies), 
and as carbonate, sulphide, cyanide,* and sulphocyanide.* 
It is introduced into horizontal cylindrical stills, capable of 
holding 1,000 — 3,000 gallons, and is heated either directly 
or by means of an interior steam-coil, so as to fractionally 
distil off the ammonia. Lime (5 per cent.) is sometimes 
added before boiling, sometimes after partial boiling, but 
often not added at all ; it should, liowever, be, as a rule^f 
employed, so as to prevent the appearance of cyanides in 
the distillate. Amnionic cyanide, in presence of air, rapidly 
corrodes iron fittings, and the sulphate afterwards prepared 
has a distinct blue colour, owing to the presence of ferric 
ferrocyanide (Prussian blue). Olive oil and charcoal have 
both been used aspimfiers of the gaseous ammonia ; but the 
former absorbs ammonia, the latter oxidises it to nitrate ; 
the proper purifier is lime placed in the still. Very great 
advantage also is derived from distilling the ammonia in 
some form of the Avell-known Coffey's still (long used in 

* Not in the Broxburn liquor (Steuart), • 

t An exception to this is when the spent liquid has to be afterwards 
passed through scrubbers, which lime is apt to foul. 



28 MANUALETTE OF DESTKUCTIVE DISTILLATION. 

the manufacture of alcohol) ; or by passing it through a 
tall tower filled with coke or pebbles, into the bottom of 
which steam is introduced (steam at 10 lbs. pressure will 
frequently sufiice). The gaseous ammonia, with sulphide 
and carbonate and some steam, passes onward, in some 
works, through a condenser and wash-bottle to a lead- 
lined or copper trough, the back of which is screened by a 
curtain inside : the ciu'tain is parallel to the front of the 
trough, which is closed behind it, but open in front of it. 
The bottom of the trough slopes somewhat towards the 
front. The ammonia and steam enter behind the curtain, 
through a perforated pipe or " cracker," and encounter oil 
of vitriol of sp. gr. 1*4 (80° Tw.) ; crystals of amnionic 
sulphate soon form, and are removed in perforated ladles. 
The steam is kept hot by a coil, and returned* to the retorts. 
The vitriol, which is preferably prepared from pure sulphur 
is renewed from time to time, as soon as a smell of 
ammonia is perceived, or the scum becomes brown. If 
pyrites vitriol be used, it must be kept more acid, and the 
crude solution retamed above crystalhsing point for a few 
hours, in order to deposit impurities. 

Sometimes this vitriol is at first only partially saturated 
with the ammoniacal sulphide vapours, in order to throw 
down arsenious sulphide, which can be removed by skim- 
ming; the acid is afterwards completely saturated, in 
order to remove iron, which settles out. Acidity is gained 
dui'ing the evaporation of the aqueous sulphate, which 
loses some ammonia by dissociation. 

The crystals are dried by mere draining ; they then 
contain a little free hydric sulphate, with traces of un- 
crystallisable pyridinic sulphates, and some water. They 
could undoubtedly be decidedly improved by the use of 
the centrifugal machine. Rigorously pure ammonic salts 
cannot be prepared by any direct process from the watery 



PARAFFIN INDUSTRY. 29 

liquor. Sulphate prepared from liquor obtained in the 
low- temperature process is less liable to organic impurities 
than that which is similarly prepared from ordinary gas- 
liquor. 

The hydric sulphide which escapes from the crystal- 
lising or receiving boxes is generally burned under a tall 
chimney ; sometimes it is collected in a " purifier " con- 
taining ferric oxide. 

The amount of sulphate obtained in a Young and 
Beilby retort averages about twice as much as in the 
Henderson retort ; in highly carbonaceous shales the 
proportion is very much greater. 

(7.) Oily liquor^ " crude oil,'^ or tar proper. — This (which 
is of sp. gr. -89 from the old forms of retort, and -87 from 
the new kiuds) is pumped into cast-iron stills holding 
250 — 2,000 gallons^ and protected beneath by perforated 
biick arching, so that the heat plays round the side of the 
still rather than on its base. The stills are short upright 
cylinders, whose bases are convex upwards. Gaseous 
hydi'ides first come off, and are caught in a tar-tower: 
some amnionic sulphide generally accompanies them. At 
or near 100° some strong ammoniacal liquor and light oil 
pass over; after this the temperature rises rapidly, and 
may exhibit an approximately stationary point. The 
operation is pushed to dryness, and furnishes a vesicular 
coke, from 7 — 12 inches thick; it is very free from sulphur 
and ash, and worth on those accounts about 30s. per ton. 
During the earlier part of the process, the condenser, 
which, like most large condensers, is separated from the 
still by a wall, is cooled by a stream of cold water ; but as 
soon as the distillate becomes so rich in paraffin as to 
Sulidify, the worm is allowed to heat up. The worm is 
made of lead. Water comes over during nearly the whole 
of the distillation, but especially towards the close, when 



30 MANUALETTE OF DESTEUCTIVE DISTILLATIOX. 

a new destructive distillation of oxygenous pitch occurs. 
The residual coke amounts to 5 — 10 per cent, of the tar, 
its amount being less from purer tars.* This contains 
3 per cent, of nitrogen. 

The operation is not unfrequently aided by introducing 
from the commencement steam at 12 — 30 lbs. pressure — 
a pressure which ought not to be exceeded in steaming 
paraffin, that substance being much more easily " burned " 
than is usually supposed. [After this operation Henderson 
interposes a continuous distillation through three stills ; 
he has also of late applied the principle of continuous 
distillation to the stills for crude oil. Very clean distillates 
are thus obtained.] 

The mixed distillates (for the paraffin magma is gene- 
rally added) have now lost about '016 in gravity and 
possess a green colour. They were formerly stirred with 
2 per cent, by volume of caustic soda solution, in order 
to take up phenol and its analogues (" kreasote "), acetic 
bodies, and perhaps some terpenes.; the sodic extract was 
drawn off beloAv, and the supernatant fluid, sometimes 
after washing with water, agitated with 5 per cent, of 
oil of vitriol of sp. gr. 1-7 (14° Tw.). [A metal stirrer, or 
an air current, produces the required agitation.] 

This latter liquid has but little action on the fatty 
hydrides proper ; but on hydrides containing less hydrogen 
it acts powerfully, resinifying and polymerising them as it 

* Eeilby distilled a litre of the crude oil, weighing 882 grammes, to 
dryness in a glass flask (a current o£ low-pressure steam being passed 
through the oil during distillation), with the following results : — 

Kesidue in the flask lO'SS grammes. 

Oil distilled in the condenser . . . . 860'00 „ 

Gas 7-93 

Unaccounted for . . . . . . . . 3'49 „ 

882-00 grammes. 
The gas consisted mainly of parafllns without hydrogen. 



PAEAFFIN INDUSTRY. 31 

does turpentine. AYeak acid, sometimes used at this stage, 
is comparatively inefficient for the purpose. Schorlemmer 
has isolated three of these polymers from cannel paraffin 
oil; he finds them to have the formulse C^^B.^^^, ^u^q^^ 
and CjgH2g respectively, corresponding to a range of 210° 
— 280° in boiling-point. These are polymers of acetylene 
(C^H2n_2).2 ; before the action of the oil of vitriol, they have 
half the above formulae. Now, fatty hydi'ides or paraffins 
proper have the general formula CJi^^ + ^. It may fairly be 
presumed that crude paraffin oil contains several orders of 
degraded paraffins ; the wliole of them are summarised in 
the general expression C^Hgn-x-* ^^ being or an even 
number. They should evidently be treated Avith some 
hydro geniser, not with oil of vitrei. 

The mixture of soda or vitriol ^dth crude oil 
generally takes only a few minutes ; but the subsequent 
separation of the lower layer may take several hours, 
especially when the oil is heavy. The action of the soda 
is sometimes aided by a steam jacket, or steam coil. 

In modern practice the soda and vitriol are added in 
three successive alternate portions with intervening dis- 
tillations, and ultimate washing with water; the vitriol 
treatment coming first, as this plan involves considerably 
less loss. The first liquids are weak, and the last strong. 
Thus the vitriol ranges from sp. gr. 1-3 to 1*83, the soda 
from 1-05 to 1*3. The first vitriol treatment is generally 
effected (by acid tar from a later stage) at about 43°, an 
account of the setting point of the oil ; but the tempera- 
tures in acid treatment should always be as low as possible. 
Soda treatment is generally carried out at 3G°. 

Crude light oil and blue oil are treated with acid at 
about 13°. A temperature of 22°, however, does not injin*e 
the blue oil, and the tar then separates more easily ; but 
the acid is then of less value for treating the crude oil. 



32 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

Ill finishing both illuminants and lubricants the tempera- 
tnrs should always be low with acid. With soda, it is the 
practice— after stming the oil with 3° — 4° Tw. soda — to 
steam the mixture to 54° ; the oil keeps colour better in this 
Avay than when finished cold. 

The mixing tanks are of varied capacity, and have 
been constructed to hold as much as 8,000 gallons; mix- 
ture is efi*ected by means of rotating vanes, carried on a 
vertical axle. The necessary degree of fluidity may be 
imparted by a steam coil, giving a temperature of about 
50° C. It is usual to separately refine the illuminating 
and lubricating oils. 

For some kinds of crude oil, the small propoi-tion of 
2 per cent, of vitriol sufiices throughout the purification. 

The " soda-tar " is treated with carbonic dioxide under 
pressure: this sets free the "kreasote," and the heavier 
aqueous hydrosodic carbonate is run off and recausticised 
with lime : or it may be merely heated and " settled." The 
" vitriol-tar," rich in leucoline bases, may be distilled with 
lime or chalk, or even with the soda-tar, to recover the 
acetylenic polymers and the like above referred to ; or, as 
is more usual, diluted with hot water, and steamed open, 
whereby those polymers are raised to the surface, the 
lower layer of weak vitriol being used for making super- 
phosphate, or, more usually, ammonic sulphate. The 
steamed tar contains about 7 per cent, of vitriol. The 
polymers are also to a great extent contained in the later 
soda-tars, and have a green colour on distillation. Like 
most imperfect hydrocarbides they combine with alkaline 
bodies, forming in this case a grease. \_See RosiN Oil.] 
Sonstadt recovers quinoline and its homologues, and 
acridine, from the acid tar by addition of potassic ferro- 
cyanide. 

It may be observed that the treatment of crude light 



PARAFFIN INDUSTRY. 33 

oil and blue oil produces certain sulphonic acids, which 
are removed by the subsequent action of soda. And when 
the resulting soda tar is used — as it frequently is — to 
neutrahse crude oil after its acid-tar treatment, some of 
these are set free, and so return to the crude. 

Probably most of the phenoids are removed by the 
acid treatments. 

Rave treats the acid tar with scrap iron (which removes 
the vitriol as ferrous sulphate), washes, and distils. When 
half the substance in the retort has distilled over, the 
residue consists of an elastic bitumen suitable for varnish- 
making. The distillate contains a considerable quantity 
of Hght oils. The products of Rave's process may have 
been partly influenced by nascent hydrogen. 

According to Beilby's researches, the nitrogen in the 
" alkaloidal " (" vitriol ") tar is constantly about one-fifth 
of the total present in the original shale. 

The refined tar is fractionally chstilled. The more 
volatile portions ('6 — '68) are chiefly used for carburating 
air, thereby making an illuminating gas ; the naphtha (sp. 
gr. -68 — -76) is used by painters as a substitute for turpen- 
tine, by indiarubber manufacturers as a solvent, by parafiin 
manufacturers themselves as a medium from which to 
crystallise parafiin, and as " benzoline " for sponge lamps. 
The succeeding fractions (-800 — -820) are sold as illumi- 
nating oil (" paraffin oil ") ; but in some cases — as, for 
instance, in hot localities — the sp. gr. taken is "845. 

Lubricating oils succeed these ; the author has met 
with them of gravities ranging from 'Sij5 — '900. 

The next distillate solidifies on cooling, yielding brown 
crystals of hard paraffin, whose mother-liquid, removed by 
a filter press and hydraulic press, is "blue-oil," whence 
more, but soft, crystals can be obtained by artificial 
refrigeration. This is always conducted sloAvly, so as to 

C 



34 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

yield large crystals. The motlier-liquid of these is again 
treated with vitriol and soda, and distilled : the earlier 
fractions constitute heavy illuminating oil, the later lubri- 
cating oil. As the press rooms are seldom artificially 
cooled, summer-made lubricant is apt in colder weather to 
deposit solid paraffin. 

The normal paraffins are unsuitable for use as lubri- 
cants. The lubricating properties belong to one or more 
series of iso-paraffins. 

It has frequently been observed that products of 
destructive distillation are improved in coloiu' by re- 
distillation over lime, soda-lime, or soda. Lubricating oils 
are distilled over 1 — 2 per cent, of caustic soda with good 
eff'ect. This reagent removes acid and sulphonates. The 
addition of zinc dust would be of further advantage. 

Crude paraffin may be purified by two meltings with 
10 per cent, of oil of vitriol (more heat, but under 60°, 
being applied on the second occasion) ; there is an inter- 
vening pressure of the cake, and it is finally melted with 
aqueous caustic soda, which must be entirely removed, 
on account of the greasiness it imparts to the wax. The 
more general process consists in dissolving the paraffin in 
about an equal bulk to as little as 10 per cent, of the light 
paraffin oil, crystallising, and pressing very strongly; this 
is done thrice at least, with a pressure after each crystal- 
lisation, the solution being sometimes filtered through 
3 — 5 per cent, of animal charcoal (and paper), fuller's 
earth, spent shale, or magnesic silicate, and finally steamed. 
Lundy (1850) and A. Taylor (1864), used prussiate char- 
coal with considerable success, and it is still employed in 
Scottish works. White clay, dried at 350° and used 
immediately, has also been employed with good effect. 
Carbonic disulphide (10 — 20 per cent.) has sometimes been 
used as a solvent instead of light paraffin oil. 



PARAFFIN INDUSTRY. 3r> 

Another method of purification consists in pressing hot 
in upright or horizontal presses, whereupon soft paraffin 
oil, and brown colouring matter are removed ; bleaching 
is completed by agitating with animal charcoal for some 
time. Lastly, the paraffin cake is made to undergo liqua- 
tion on mats of cocoa-nut fibre, and finished as above 
described. [For a general account of liquation processes 
see Tervet, J". Soc. Cli. Incl, 1887, 355.] 

The loss on refining paraffin scale amounts to about 
16 per cent.; if the extracted oil be credited, 3 per 
cent. 

Tbe products wbich leave the retort after the solidifi- 
able paraffin, are thick or buttery. These are sold after 
*" treatment,"' for lubricating purposes, with or without 
addition of vegetable oil. Much of their colour can be 
removed by exact reaction with hydric peroxide, or (which 
is the same thing) exposure to light and moist air. 

The total working loss in this manufacture is usually 
about one-third of the weight of the crude oil. 

Solid paraffin is used chiefly for making candles, for 
which it is admu'ably fitted, by reason of the great lumi- 
nosity with which it burns : more or less stearate is in this 
case added. The softer kinds, when dissolved to saturation 
in naphtha, and mixed with about 5 per cent, of vegetable 
oil, are, as Stenhouse has shown, excellent waterproofers of 
wood, e.g., for matches and bari-els, cloth, paper, indiarubber 
Lose, leather, and other fabrics, to which they also impart 
greater tensile strength; and in this state they are in 
extensive use as lubricating " creams,'* when great 
durability is required. 

The imperfect hydrocarbides in the lighter liquid 
paraffin oils act somewhat energetically on lead and zinc, 
less upon brass and iron, very slightly on tin and copper. 

Vegetable oils, when mixed with even as littk' as 10 

c 2 



36 MAXUALETTE OF DESTRUCTIVE DISTILLATIOX. 

per cent, of lieavy paraffin oil, are far less liable to imdergo 
spontaneous combustion on " waste " tissue. 

Within recent times, considerable attention has been 
bestowed on the production of highly illuminating gas 
from the less valuable liquid products of the paraffin 
industry. Thus " Green " oil of sp. gr. '894, from the acid 
tar, has been found to yield 87 cubic feet per gallon of 
such gas. An oil of sp. gi*. '844 has, however, furnished 
88 cubic feet per gallon ; a gravity of '822 corresponds to 
90 cubic feet, with less tar, and that of a thinner quality. 
The produce of tar from the lighter oils is in general about 
one-half to one gallon of tar of sp. gr. 1-081 for every 
five gallons of oil ; from the heavier oils, about one-and-a- 
half gallons. It is, of course, neither acid nor alkaline. 
After passing through condensers and a washer, the gas 
traverses two purifiers, containing layers of chopped straw, 
sawdust, and lime. It is admkably adapted for compres- 
sion; the original compression being 30, the working pres- 
sure 6 — 10 atmospheres. Before such treatment it has the 
sp. gr. -700 ; during the process it deposits one gallon of 
light " gasoline " per 1,000 cubic feet — thereby losing 20 
per cent, of its illuminating power — the eventual illuminat- 
ing power being 25*9 candles, and the consumption (in a 
railway carriage lamp) -78 cubic foot per hour. 

According to Armstrong and Miller, the gas is practi- 
cally free from acetylene, but contains ethylene and 
crotonylene. The gasoline contains normal defines to 
C^; the acetylenes C^ and C., as well as benzene and 
toluene. The steam distillate from the tar yields members 
of the series C^, H2n_2, the three xylenes, mesitylene and 
pseudocumene, naphthalene, and some pseudolefines, with 
traces of paraffins. Greville Williams has analysed several 
samples of gasoline with the following results : — 



PAEAFFIX INDUSTRY. 



37 



Percentage of benzene 


Sp. gr. 




and toluene. 


•850 




65-6 


•835 




54-2 


•840 




52-0 


•830 




45-2 


•840 




44-4 


•800 




37-8 


•760 




24-G 



The retort employed in manufacturmg oil gas is 
essentially identical with that of Taylor. It consists of a 
cast-iron D-shaped chamber, having a capacity of ah out 
4;^ cubic feet, and acting as an upper retort ; the oil is led 
through this into a similar one placed below, and both are 
kept at a bright red heat. The pressure in the retort is 
equal to about 5 J inches of water, diminishing to IJ 
inches in the gas-holder. Two pau'S of retorts make about 
420 cubic feet of gas per hour. The cost ranges fi*om 
5s. 6d. to 16s. per 1,000 cubic feet. In another arrange- 
ment, the retort is one-chambered and constricted at the 
middle. The working temperature is 900° — 1,000°, and 
the oil is distilled at the rate of about 12J gallons per 
hour. 

The accompanying statistical table of annual working- 
comprises the returns made by twenty Scottish manufac- 
turers to the Rivers' Pollution Commission (1872). 



38 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



GO 



^ 

5 

^ 






O O o o o o o 

o o o o o o o 
o ^ . o .0000 



e S ra 
903 j= 



o o 



•8 



888 :888 :8 



o o 

CO i-l CO Tfl rH 



OCO . .OOCD .0 .OW5 
W3 . . CO CO CO • kO . ?0 00 
00 O) (KJ r^ lO 



O O 05 o 

O O r-l O 

o^ o^ o o^ 

0~ O" Oi" o" 

CO 1-1 Oi o 

CO 



o o 

. lO o 

. ^ o 
00" 



.000000 
. U3 o^ o^ o o o^ 

lo o' o'~ o" c<r 



C CO 

O -4 



«o o 

O 1-1 



CO o o 00 
o T o .00 

10 • O CO 



o o 
.0 o 

2 O O . 



• O O (M uO 

00 CO 10 CO 
r-i oq ?o 



00 000000 

00 000000 

.0^0^ . o^ o^ o^ o__ o_^ ^ 

• O^O" • OO^iO^O" O' OxS 

CDOO O'^OOOOO 

Tfi ,-i fM 0_^ uo !M 



O O O O O O rH O o o o o o 

.0 0000000000000 

^- O^ .0 O^ O^ 0_^ O^ C<l_ 00^ o o o o o^ 

^ <0 • O" O" O' 0"^ xo QO' ol io" o" o'~ o" o" 

^:o utiiOiO-ftcooo-^iooiOTiH 

■* OiCOOlM i>rHT-H3<IO^(M 



. O 

• o" 




s 


^'5^82 


.0000 

. CO rH (N 




11 


§00.. 

(N . . 


. ^ IC 

. CO r-H> ^ 


. .00 .OOiOOCDQO 



io o o 

O !M O r-t 



U5 '^ CO rH '^ 

CO Tt< CO rH 10 CO ■t-'^ Gi^ 



O J> O O Q 00 O 

o -H o o o .00 

O CO O 10 lO . 1> O 



.00000 
200000 

go^o 0^0 o^ 

H o" r-T o" co" <m' t> (m" i> 10" co" 00" i;d" cc" o' 

i> (M CO ^ -* -^ (M 




PARAFFIN INDUSTRY 



39 



Omitting tlie figures relating to cannel, we liave the follow- 
ing results, calculated (I) from the percentages given by 
corresponding returns, (II) from (I) and the total shale. 





I. 


11. 


Total shale 


100-00 tons 


663,587 tons 


Spent shale. . 








34-73 „ 


230,464 „ 


Coal 








34-87 „ 


231,393 „ 


Caustic soda 








•343 ton 


2,276 „ 


Oil of vitriol 








1-63 „ 


10,826 „ 


Steam 








•20 (H.P.) 


1,327 (H.P.) 


Crude paraffin 






• 


3 -20 tons 


21,235 tons 


Illuminating oil . 








•4424 ton 


2,936 „ 


Lubricating oil 








•880 „ 


5,842 „ 


Blue oil . . 








•19 „ 


1,261 „ 


Naphtha . . 








•37 „ 


2,455 „ 


Ammonic sulphate 






•32 „ 


2,123 „ 


(Equal to ammonia 






•08) „ 


535 „ 



The "horse power" does not probably include that 
which is required at the pits. The mean results above 
given are probably too low, and must be received with 
considerable reserve. 



Production of Shale in Scotland from 1873 to 1891. 


Year. 


East. 


West. 


Total. 


1873 

1874 

1875 

1876 

1877 

1878 

1879 

1880 

1881 

1882 

1883 

1884 

1885 

1886 

1887 

1888 

1889 

1890 

1891 




tons. 

439,615 

277,210 

377,108 

454,892 

581,351 

535,626 

«24,912 

730,777 

840,259 

898,754 

1,043,499 

1,365,157 

1,665,667 

1,655,427 


tons. 
84,480 
84,700 
46,314 
86,381 
102,767 
110,313 
87,516 
63,060 
71,912 
93,733 
87.230 
104,492 
76,083 
43,717 


tons. 

524,095 

361,910 

423,422 

541,273 

684,118 

645,939 

712,428 

793,837 

912,171 

994,487 

1,130729 

1,469,649 

1,741,750 

1,699,144 

1,390,320 

2,052,202 

1,986,990 

2,180,483 

2,337,932 



40 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

Other data are as follows : — 



Shale (tons) 

Crude oil (gals.) . . 

K^ aphtha and burning oil. . 

Lubricating oil .. ,, 

Paraffin scale (tons) 

Amnionic sulphate (tons) 



1885. 



1,609,920 

48,297,600 

brls. 495,050 

„ 30,665 

18,974 

12,950 



1886. 



1,699,144 

49,275,176 

492,751 

33,241 

21,118 

15,171 



1891.* 



2,337,932 
54,119,249 

498,848 

165,003 

24,518 

22,000 



There are at present 13 works, employing about 
11,000 men. 

The cost (1882) of production (including repairs) was 
0'50d.; of refining. 1*226?. ; of depreciation, •25<:/. ; tot^l, 
1-97 d. per gallon, excluding ammonia. According to 
another estimate, the total cost was 2-lOd, 

In an individual work, the returns were (1885) 38 per 
cent, burning oil, 24 per cent, lubricating oil, and 13 per 
cent, paraffin scale. The cost of refining the crude gallon 
was l'21d. Taken on the refined gallon, the cost was 
I'Q'dd. This has been reduced (1889) to 1 cwt. of coal per 
ton of shale in making ci'ude oil; and -lid. per gallon 
for refining. 

Tlie average price of ammonic sulphate per ton is 
given on the authority of Messrs. Bradbury and Hirsch, 
of Liverpool, in the following table : — 



Year. 

1868 
1869 
1870 
1871 
1872 
1873 
1874 
1875 
1876 
1877 
1878 
1879 



Price. 
£ s. 

14 10 

15 15 

16 
19 
21 
18 3 

17 2 

18 10 

18 12 

19 16 

20 5 
18 8 



Year. 

1880 
1881 
1882 
1883 
1884 
1885 
1886 
1887 
1888 
1889 
1890 



* The amount of naphtha was 2,429,056 gallons ; il 
gallons J and " gas oik" (-840— -865), 5,647,423. 



Price. 
£ s. d. 

19 

20 4 
20 8 
16 11 
14 9 
11 9 
11 3 
11 17 

11 18 

12 1 
11 9 



uminant, 18,522,533 



PARAFFIN INDUSTRY. 



41 



The total production in 338 works in the United King- 
dom during 1891, from all sources, they estimate at 143,500 
tons, viz. : — 



Gas works 
Iron „ 
Shale „ 



Coke and carbonising works 



Tons. 

107,000 

6,500 

27,000 

3,000 

143,500 



The production during the previous five years, adjusted 
from the report of the Chief Inspector under the Alkali 
Works Regulation Act, was : — 





1890. 


1889. 


1888. 


1887. 


1886. 


Gas works 
Iron 

Shale .. 
Coke and car- 
bonising works 


102,150 

5,050 

24,750 

2,300 


100,700 

6,150 

23,950 

2,800 


93,000 
5,300 

22,000 

2,500 


85,000 

5,000 

21,000 

2,700 


82,500 

4,000 

18,000 

2,000 


Total 


134,250 


133,600 


122,800 


113,700 


106,500 



About 80 per cent, is exported. 

The totals of the quantities of Scotch and American 
solid paraffin consumed were : — 

Tons. 

1887 35,042 



1888 
1889 
1890 
1891 



39,230 
43,804 
50,774 
52,340 



The following are some examples of individual varia- 
tions among oils from different Scottish shales : — 



42 



MAXUALETTE OF DESTRUCTIVE DISTILLATION. 

















^ 




















p^' 









































(M 




















<M 






I— J 












. 


1—1 






O 





10 








• 


10 










00 


r-i 


CQ 


eg 


CO 




*? 


W 


CO 




T-i 


CO 


lO 





CO 




00 


Tfl 


CO 
















,^^ 




















^ 









































(M 




















(M 




















rH 






^ 












* 












00 





? 


v^ 




IC 




■^ 


? 




I— 1 


^ 


r? 


lO 


-* 




1—1 
1— 1 


10 



















,_^ 




















f=i 









































oq 




















<M 




















1—1 






> 












* 








1— 1 


lO 


w 


10 


\rt 


Id 




^ 


? 


Oi 




t^ 


j> 


CO 




1—1 






CO 
























iH 


CO 


T? 





6 

rH 




10 


(M 


CO 
















/— N 




















P^ 









































lO 




















(M 




















1—1 


























hH 




















h- 1 


8 


? 


? 


? 


8 




? 


? 


8 




(M 




-<? 


lO 


I— 1 




^ 


(N 


§ 




O 

























M* 


9 


9 


10 


9 


Tf< 


, 


!>. 





9 


1— 1 












. 










(M 


10 

CO 


T? 


CO 


I— 1 





I— 1 


4f 


















^^ 




















pR 









































,—1 




















cq 




















I— 1 






M 






















O 


»o 


l-O 






















9 


x> 


1^ 


IP 


CM 


t- 


rH 


xa 


10 




(N 


i 


CO 


10 


1^ 

1—1 


I— 1 


CO 


r-i 


T— 1 




• 


• 












• 


; 










»o 


CO 


Oi 
















00 


00 


OO 












, 




■| 


'1 


1 


. 




, 




1 




.u 









. 





. 




1 




rj 


-* 


CO 


00 






r2 






^ 


=e 


CO 


00 


00 


m 











■3 


ti 


. 






g 


oc 









S3 






Sjd 

d. 
so 







1 




m 





PARAFFIN INDUSTRY. 



43 



The following are working results usually obtained 
from various Scottish shales : — 



Seam. Gals, crude oil per ton. 


"Fells" (thick) 


. 37 


„ (inferior) 


19-22 


Broxburn (Broxburn seam) . . 


. 31 


Young's (Uphall) Broxburn seam 


. 31i 


Young's Newliston (Dunnet seam) 


. 27 


Dalmeny (Broxburn seam) 


. 32 


Pumpherston 


. 18 


W. Lothian (Dunnet) . . 


. 19 


Caledonian (Tarbrax) 


. 26 


,, (Cobbinshaw) 


. 30 


Stanrigg . . 


. 40 


Burntisland 


. 30 



At the works of Young's Paraffin Light and Mineral 
Oil Company, the following has been an average yield of 
the various products from the crude oil : — 

Per cent. 

Gasoline 0-25 

Naphtha— sp. gr. -TOO— -760 5-75 

Burning oils — 

No. 1, sp. gr. -802— -804, F.P. 110° (Abel test) >| 
No. 2, sp. gr. •810--812, F.P. 110° (Abel test) j 
Crystal (No. 1 chemically treated) . . . . ;>38.00 

Lighthouse oil, sp. gr. '810 -'820 F.P. 140° | 

(Abel test) J 

Lubricating oils of various specific gravities . . 14.50 

Paraffin (solid) ll'OO 

Loss 30-50 



100-00 



The percentages given are only approximate, and are 



44 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



often purposely varied by alterations of the processes to 
suit the requirements of the markets. The loss is no doubt 
frequently considerably smaller than the proportion 
stated. 

At the Broxburn works an average yield has been as 
follows : — 

Per cent. 



Naphtha — sp. gr. -730 


500 


Burning oils — 




Petroline— sp. gr. •800/-802 


-| 


No. 1 oil— sp. gr. -SOS/'SIO 


> 37-28 


Lighthouse oil — sp. gr. -810 


- 


Lubricating oils 


. . 17-40 


Solid paraffin . . 


.. 12-52 


Loss . . 


.. 27-80 




100.00 


e Broxburn shale furnishes : — 






Per cent 


Crude oil 


.. 12-5 


Water 


8-5 


Gas 


3-0 


Ash 


. . 67-0 


Carbon in spent shale . . 


V)-0 



100.0 

The Burntisland Company produce 30 gallons of crude 
oil, sp. gr. '865 and 8 lbs. of sulphate per ton. The oil 
yields : — 



Illuminant 
Lubricant 
Scale . . 

[Loss . . 



Per cent. 

37-50 
18-75 
16-75 
27-00] 

100.00 



PARAFFIN INDUSTRY. 



45 



The following conspectus of operations and quantities 
(variable with the oil and the state of the markets) will 
render the whole process of refining more intelhgible : — 

Operations and Quantities. 





Crude oil. 
1 








1 

Distilled. 

1 








. 1 
Washed with acid tars. 

1 






1 
Washed with soda 
1 


tars. 






1 
Distilled. 






Light oil. 






Heavy oil (''Green "). 

1 


1 
Washed with 1| per cent, acid, 


170^ T. 




Cooled to 2° C. 


Washed with 1 per cent, soda, 


72^ T. 


a 


1 
Filtered and pressed. 


Distilled. 
1 


1 1 
reen oil. Hard seal 
1 (49^ C). 



Ill I 

N'aphtha, 3rd run light oil, Intermediate, Washed with 2 per cent, acid, 
"750." "806." "860-865." 170° T. 



Washed with 2 per cent, acid, 
170° T. 



Washed with 2 per cent, soda, 4° T. 



Burninc oil. " 805." 



Washed with 1^ per cent. soda. 
72° T. 



Distilled with 1 per cent. soda. 

I 



850" oil. 



[Distilled]. Washed with 2i per cent, acid, 170° T. 
Washed with 3 per cent, soda, 7° T. 



" Blue oil." 
I 
Cooled to 8° C. 

Filtered and pressed. 



Scaled blue oil. 

I 
Washed with 3 per cent, acid, 170° T. 

Washed with 4 per cent, soda, 7° T. 



Soft Scale (38° C). 



Lubricant, "888.' 



46 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

Paraffin is a mixture of neutral, non-oxygenated bodies, 
and contains about 85 per cent, of carbon to 15 per cent, 
of hydrogen. Its constituents are the " fatty hydrides" of 
which mention has aheady been made. This point was first 
conchisively proved by Gill and Meusel, who found that 
when excess of paraffin is heated with bromine in sunlight 
for some time, half the bromine is converted into hydric 
bromide. 

aH,„+, + Br, = C.H,.H. ,Br + HBr. 

This reaction is characteristic of hydrides. The same 
chemists found paraffin to yield cerotate (C27H5^02) when 
oxidised with chromic mixture. Their sample, then, which 
melted at 5Q°, consisted chiefly of cerotylic hydride C27H5f.. 
The softer and more fusible paraffins — melting at 9°, 16°, 
and upwards — are doubtless mainly composed of lower 
hydrides. Galletly isolated a shale paraffin melting at 80°. 
He has found the solubihty of paraffins to be inversely as 
their melting-point, and the specific gravity to be directly 
as their melting-point.) 

Crude paraffin has been recently placed under investiga- 
tion by F. Krafft {Deut. Ch. G, xxi., 2,256). He submitted 
samples of crude paraffin melting at 30° to 35° to a series 
of fractional distillations in a vacuum (H = 15 mm.), and 
succeeded in isolating saturated hydrocarbons, ranging 
between Cj^ and C23. Alcohol was employed as the 
medium of crystallisation. 

Krafft also obtained the principal physical constants 
for these bodies; they are shown in the following 
table : — 



PARAFFIN INDUSTRY. 



47 



— 


— 


Melting 
point. 


Boiling-point. 
H = 15 mm. 


Density at 
the melting- 
point. 


Heptadecane 


CirHgg 


22-5 


170 


0-7767 


Octodecane 


^isHss 


28-0 


181-5 


-7768 


Nonadecane 


C19S40 


32-0 


193-0 


0-7774 


Eicosane . . 


^20^42 


36-7 


205 -0 


-7779 


Heneicosane 


C21IT44 


40-4 


215 


-7783 


Docosane . . 


C22H46 


44-4 


224-5 


-7782 


Tricosane . . 


C24H48 


47-7 


234-0 


-7785 



Paraffin and similar oils may be converted into jellies 
or faii'ly hard solids by mixing with them 5 — 10 per cent, 
of fatty acid and 1 — 2 per cent, of caustic alkali. Accord- 
ing to Messrs. Chenall, 650 parts of petroleum, 250 parts of 
soda, and 90 parts of rosin, furnish, with the aid of heat, 
a design that can be moulded. (Patent 4,446, 1891.) 

In one of the large Scottish refineries, a yield of over a 
million pounds of paraffin wax was distributed as follows 
with respect to meltmg-point : — 



Percentage. 

10.17 
18-02 
42-33 

29-48 

100-00 



M.P. (F.) 

110° 
115° 
120° 
125° 



According to Thorpe and Young, solid paraffin is 
gradually changed into liquid kinds and defines by re- 
peated distillation, 

^ntl2n+2 ~ ^n-p^2(n-p)+2 "I" ^P ^2p' 

Paraffin. Paraffin. define. 



little or no gas being evolved. This operation, which, 



48 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

when carried out by one continuous heating in a single 
stiJl, is termed " cracking," is frequently applied to heavy 
petroleum oils, with or without the aid of superheated 
steam. 

On the other hand, it is quite possible for defines to 
yield paraffins : — 

Olefine. Carbon. Paraffin. 

This reaction probably occurs in the manufacture of 
oil-gas from paraffin oils. 

D. T. Day has, in fact, shown that pure ethylene 
(which at 344° undergoes no change) slowly suffers con- 
traction at 350° — 355°, with formation of a condensation 
product ; but at 400° — 408° it contracts to half its volume, 
and contains about 40 per cent, ethane, with nearly as 
much methane ; and at 450° a little carbon is deposited, 
while the gas contains about 70 per cent, ethane, and less 
than 1 per cent, methane. In neither case is hydrogen 
formed. The reactions are, perhaps : 

Condensed olefine. Paraffin. Paraffin. 

when n = 1, 2, &c., the right-hand term is CH^, C^H^q, &c. 

[Riebech has applied the cracking process, under pres- 
sure, to the production of light oils. The best results are 
obtained with brown coal-tar at 3-6 atmospheres, with 
petroleum and its " residues " at 2-4 atmospheres, and with 
oil-gas tar at 4-6 atmospheres.] 

For the following very valuable tables (I and II) the 
author has to express his indebtedness to the manager of 
one of the leading Scottish paraffin oil companies : — 



PARAFFIN INDUSTRY. 



49 







2 S 


8 










1 


i g 


8 


i 


"• ^I^? 






1 


^^^ s? g ^ 


i 

CO 


8 CO O CD rH 




i 


^ 


cot.^ : : ^ :o 


-"g 


co" 










J (jq 








o o 


o 








a 


oi 


. . T' ^ 


o 


X '"' 


q-J 




o 


■IS 




O -« CD 
O CO o 


8 


-5 

i 


6 xo c<i ri 
^ CO ^ i2 






w 


O CO l> O Tfi 


iCi o o 




rH 


a «^ 








M rH Tf( 1 




1—1 


" 




. 


CO O 


8^ 




Cf^ 






1 


00 A- 


O 


tn 








»o ^ 


o 


-Q 


d 05 O CO 






a 


CO CO Oi O lO i '~' 


^ 


Q Tfl 00 (N p 




-i 

o 

o 


1 


00 (M ^ 


rH (N 1 


"^ 


§ ^^^'^ 




1 






(7q 
















0} 




00 (M 


o 








1 


1 


CO CO 
.H 00 
CD CO 


9 


I— 1 


et-I 

^ O t- rH •- q 








(M CO iO X O' ^ CD lO 




_ 


2 :* ^„ ^„ - 2i : : : : 






§ 


CO T}( CD r-l X O O lO 




CD 


S ^ rH-O^c^*- , 






n 


IXNOOO OSOOi 




. 00 


VO «^ 








CO (>1 (N 




I— 1 






1 


V CO CO 


8 
8 


5q 








Tft J> »0 


tH CO 




^ 


9 : ::::•••-• 




ai 


1 


lO Tfi CD 


00 \fi 




O TTi -"T I— 1 

l>^ -^ iH rH 




^ 
^ 


^ 


(N CO t^ I ! 


o ! c<i 




CD 


I— 1 






rH 1 ^ -CD 1 


r-( 00 










00 






•O 




lO lO 1 O 




S+H ^ 




§ 


2 


.H 00 1 O 
M 1^ O 


r— 1 

1 




w 


CO CD O 




^ ?^ t^.Hi«00 








lOOTjtCiiMlCOiO-'T' *"* 


i 


*r ,:, °° 2° ^ : : : : 






§ 


cptrOOOiOO riOCO 


g ?? ^^ s'^ 






S 


COCOiHOC<J Tf(r-I(>^ 


•"^ 


CD*^ to 
CO 








; ; ; ; ; ; ; ; 


: : 


^ s o ■ S £ 












cq.2^ S g 












V c ^ Q, .S 












C 3 g " O . . . . g 








• • • 


• ' 


S^^a^l =5 








: : : : : : : : 


. . 






















■^ O ^ ^ f U 


® 8 








: O t. 3 ^ ^ 3 • 


as O 




















is 


^'>- 










o r 










"c3 ® 




•g 03 ^ •'-'^ cr 3 2 03 ^ c3 o 
|0m kWfiOO J» O PLH 








1 " 








k 


O 






OccPm 





60 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



II. Analytical Results from Good Average Shale, 



Specific gravity 
Moisture at 104' 
Volatile matter 
Fixed carbon. . 
Ash . . 



•.: }»-{,. 



Composition of A sJi. 




99-96 



Soluble in water 


8-27* 


Silica . . 


55-60 


Ferric oxide . 


12-23 


Alumina 


. 22-14 


Lime . . 


1-55 


Magnesia 


. . Trace 


Sulphur 


0-94 




100-73 


Total sulphur in shale 


1-80 


ash 


1-31 



Composition of Organic Constituents. 



Carbon 




25-27 


Hydrogen 




3-67 


Oxygen 




5-65 


Nitrogen 




1-14 


Sulphur 




0-49 



36-22 



* Coiitiiins -92 sul] huric oxide (SO3). 



PARAFFIN INDUSTRY. 51 



Composition of Organic Constituents, exclusive of Sulphur, 
Nitrogen, and Ash. 

Carbon 73-05 

Hydrogen , . . . . . . . 10-62 

Oxygen 16-33 



100-00 



The subjoined comparison shows that this organic 
portion corresponds to a definite chemical relation : — 



Carbon . , 
Hydrogen 
Oxygen ., 



Found 


CgHioO 


73-05 


73-47 


10-62 


10-20 


16-33 


16-33 



100-00 100-00 

The decomposition which this organic matter under- 
goes at a low heat has been found by the author to be in 
the proportion 

7Cefl,„0 = 0,,H,„Oj = 18C + C^fie,'^, + 4H,0 

Fixed Gas and Water. 

V carbon. oil. 

which agrees with the experimental ratio on page 49 : — 

Fixed carbon 
Gas and oil. . 
Organic water 

100-0 100-0 



P 2 



Found 


Calc. 


31-2 


31-5 


58-3 


58-0 


10-5 


10-5 



52 



MANUALETTE OF DESTEUCTIVE DISTILLATION. 



Similarly, at a high heat, 
70,H.„0 = C,,H,„0, = 60 + C,,-H,fi, + 4H,0 





Fixed 


Gas and Oil. 


Water 




carbon. 










Found. 


Cale. 


Fixed carbon 


. . . 


12-8 


10-5 


Gas and oil 


. 


7(3-0 


79-0 


Organic water 


• • • 


11-2 


10-5 



100-0 



100-0 



The results for Boghead coal are as follows : At a low 



temperature — 



(Calc.) 100 
(Found) ~ 



Fixed carbon. 

. . 33-3 
.. 33-3 



Gas and oiL 

63-3 
64-1 



+ 



Organic water. 

3-3 

2-6 



At a high temperature — 

3C„H,„0 = 60 + C3„H,,0, 

Fixed carbon. Gas and tar. 

(Calc.) 100 .. 13-3 . 83-3 

(Found) — .. 12-8 .. 84-6 



+ 



H,0 

Organic water. 

3-3 

2-6 



Cellulose, from which the organic matter in question 
must at one time have been derived, has also an nC^ 
formula, and the same characteristic feature reappears in 
many of the constituents, both of natural and artificial 
petroleum. Hence it follows that any theory of destruc- 
tive distillation, as here, considered, must deal mainly with 
the migrations of an nC^ group. [See COAL Tar.] 

The organic matter of shales, so far as hitherto analysed, 
corresponds to a mixture of bodies lying between the fourth 
and fifth cumulates of cellulose (CgHgO — Cg) with more or 
less H in excess. 



PAKAFFIN INDUSTRY. 53 

It is Avortliy of remark that the "aromatic" hydrides 
CnH2n-6) occur oiily in very minute quantities in any one of 
the low-temperature industries. 

The following special table contains the melting-points 
and boiling-points of the normal primary paraffins over an 
adequate technical range. The numbers have been cal- 
culated by the author (^Philosophical Magazine, March, 1884) 
from equations in which all the results of observation have 
been combined. Where experimental values (marked with 
an asterisk) are known, they in nearly every case lie close 
to the calculated ones, which may be regarded as cor- 
rected determinations. The symbol n is the coefficient 
of C in the general formula CJl^n+i for paraffins; and the 
symbol x indicates a melting-point or boiling-point which 
cannot possibly be exceeded in the odd or even series 
respectively of n. 





Normal Para 


ffins. 




N. 


Melting Point. 




Boiling Point. 


4 


— 




+ 2-35* 


5 


11_ 




39-13* 


6 


— 




70-68* 


7 


— 




98-66* 


8 


— 




124-00* 


i) 


-52-35* . 




145-81 


10 


31-24* 




166-76 


11 


25-79* 




184-09* 


12 


11-38* 




201-80* 


13 


5-85* 




215-79 


14 


+ 4-37* 




231-06 


15 


9-67* 




242-47 


16 


n-16* 




255-84 


17 


22-09* 




• 265-22 


18 


27-75* 




277-11 



54 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



N. 


Melting-Point. 


Boiling-Point 


19 


32-26* 


284-87 


20 


36-67* 


295-57 


21 


40-73* 


302-01 


22 


44-28* 


311-70 


2a 


47-91* 


317-08 


24 


50-86* 


325-99 


2^ 


54-06 


330-43 


26 


57-24 


338-68 


27 


59-39* 


342-36 


2S 


.62-40 


350-04 


29 


64-06 


353-08 


30 


66-99 


360-27 


ai 


68-18* 


362-75 


32 


71-09 


369-54 


33 


71-84 


371-52 


34 


74-78 


377-96 


35 


7542* 


379-53 


oc (odd) 


134-18 


552-58 


oc (eveD 


) 140-56 


555-67 




COAL TAIi 


I. 



Coal-tar is formed by a destructive distillation of coal 
at a high temperature, usually a bright red-heat, or beyond. 
Although it contains fatty hydrides, they are chiefly liquid 
ones, and not paraffin. Among its constituents are 
aromatic hydrides (of which traces only are found in 
natural or artificial petroleums), their alcohols (occurring 
in very small quantities in petroleums), and naphthalin 
(absent from petroleums). Chrysene occurs both in the 
low and high-temperature oils. 



COAL TAR. 



55 



If the general formulae of fatty be compared with those 
of aromatic compounds, as in the following examples — 



— 


Fatty. 


Aromatic. 


Hydrides 

Alcohola ,. 

defines 


CnH2n+2 
CnH2n+20 

C„H2„ 


CnH2n-6 
CaH2n-60 
C.H2n-8 



we observe that aromatic bodies contain Hg less than the 
corresponding fatty bodies. Thus is the high-temperature 
industry, to the extent that it is specially characterised by 
arornatic compounds, a dehydrogenising process. 

Coal, moreover, is less hydro genised than cannel and 
similar shales ordinarily worked for oil. Thus the average 
composition of British coal used for gas-making may be 
taken (exclusive of ash) as — carbon, 86; hydrogen, 6; 
oxygen, 5J; sulphur, 1; nitrogen, 1-^ per cent.; ash, 2^; 
pit water, 3J per cent. Cannel contains — carbon, 85 ; 
hydrogen, 7 J ; oxygen, 5| ; sulphur, 1 ; nitrogen, 1| per 
cent. ; ash, large, very variable ; pit water 2-3 per cent. 

Tidy has given percentages of nitrogen in coal, ranging 
from -91 to 1*44 per ceut. ; E. Ronalds, 1-2 to 1*69 percent.; 
Beilby, from 1-45 to 2*2 per cent. 

Small percentages of resinoid extract can be obtained 
from coal by treatment with alcohol, or chloroform. The 
former has approximately the composition CgH qO ; the 
latter O^^^^o^ (Siepmann). The caking power is not, 
however, due to these bodies. 

The organic matter of coal has a composition inter- 
mediate between CgH20 and Cg — i.e., the fourth and fifth 
cumulates of cellulose. 

It was formerly the custom to prepare coal-tar in 



56 MANUALETTE OF DESTEUCTIVE DISTILLATION. 

horizontal iron retorts, at 940°. This method admitted of a 
comparatively small consumption of fuel under the retorts, 
which, however, wore out very rapidly — on the average, in 
about ten months. Hence horizontal clay retorts are now 
almost universally employed. These, on the other hand, 
require an increased amount of fuel to heat themT— and are 
always worked hotter than iron retorts ; moreover, they 
produce an undesirably large amount of naphthalin, and 
consequently a diminished quantity of benzol.'" Never- 
theless, it is said that a gas-work exists in which, despite 
the clay retorts, no appreciable amount of naphthalin is 
formed. If this be correct, we must attribute the gene- 
ration of naphthalin not so much to temperature as to 
impurities (perhaps organic sulphur and oxygen) present 
in the coal distilled. 

A clay retort is semicircular in section, having a 
diameter of 18 inches, a length of 9 feet, and a thickness 
of 2^ inches. It is flanged in front, so as to receive an 
iron door, which is tightened with wet clay, and pressed 
on by a screw (or, more frequently, pressed on by a lever, 
and spontaneously luted by pitch). Five of such retorts 
can be conveniently heated together ; the best working 
temperature being about 1,150°. The charge is sufficient 
to fill them to about three-fourths of their capacity. 
[Kunath has pointed out that a diminished gas space in 
the retort must necessarily lead to the formation of a 
thinner tar.] The residual coke is drawn and quenched 
every three hours (a minimum) to eight hours. By means 
of an exhausting apparatus, the distillation is kept in pro- 
cess at an average internal pressure of about half-an- 
inch of water. Some graphitic carbon is always formed, 
and remains strongly adhering to the inside of the 
retort. ? 

The products of destructive distillation leave the retort 



COAL TAR. 



57 



at about 480°, and after travelling rather more than 20 
feet, cool down to about 100°. 

Heniy's and Wright's experiments show that, as the 
distillation proceeds, carbonic dioxide, marsh gas, and other 
hydrocarbides are evolved in diminishing quantity ; hydro- 
gen, and perhaps carbonic oxide, in increasing quantity. 
Schulze considers that phenols and phenoids precede 
aromatic hydrocarbides, and perhaps give rise to them. 
Cyanogen compounds occur, under the influence of the 
highest temperature, towards the close of the distillation. 

L. T. Wright distilled 2 cwt. of a Yorkshire-Derby- 
shire coal in clay retorts at guch (high) temperatures as to 
require variable times for complete generation of gas. 
The results as regards tar and fixed carbon were as 
follows : — 



Duration 
of heat. 


Gas per foot super 
of Eetort. 


Specific gravity. 
Tar. 


Percentage fixed 
Carbon in tar. 


8 


Cubic feet. 
50 


1-084 


8-69 


7 


62 


1-103 


11-92 


6 


91 


1-149 


15-53 


5 


133 


1-204 


24-67 



Tars, obtained similarly, were analysed with the sub- 
joined results, including also the yield of gas in c. ft. per 
ton: — 



Specific gravity. . 


1-086 


1-102 


1-140 


1-154 


l-20( 


Liquor . . 


1-20 


1-03 


1-04 


1 05 


•38 


Crude Naphtha. . 


9-17 


9-05 


3-73 


3-45 


100 


Light Oil 


10-50 


7-46 


4-47 


2-59 


-57 


Kreasote 


26-45 


25-83 


27-29 


27-33 


19-44 


Anthracine Oil. . 


20-32 


15-57 


18-13 


13-77 


12-28 


Pitch . . 


28-89 


36-80 


41-80 


47-67 


64 08 



Gas 



6.600 



7,200 



8,900 10,Gl: 



11,700 



58 MAXUALETTE OF DESTEUCTIVE DISTILLATION. 

Naphthalin made its appearance prominently in the 
1*154 tar: most anthracene was found in the 1-140 tar. 
Increased temperature was found to destroy preferably 
the light oils between crude naphtha and kreasote. Thus, 
a tar of sp. gr. 1-23 yielded — 



Liquor 


, . 4-39 


Crude naphtha 


.. 4-11 


Light oil , . 


absent 


Kreasote 


.. 18-99 


Anthracene oil 


.. 12-14 


Pitch 


.. 59-14 



98-77 

Sometimes the retorts are heated by "producer" gas, 
for making which the red-hot coke, even when of very 
poor quality, is extremeiy handy. When the coke is of 
fair quality, one part of it, converted into producer gas, is 
sufficient to carbonise 10 parts of coal, provided a regene- 
rative arrangement be used. 

All the products of distillation, after leaving the retort, 
pass into a " hydraulic main " ; here the liquid products are 
deposited, and thereby separated from the gaseous ones. 
The bent pipe from the retort dips slightly under the hquid 
in the main, into which no air consequently passes when 
the retort is open. 

The illuminating property is due, probably, chiefly 
to acetylene and other degraded hydrocarbides formed at 
the moment of combustion. Obviously, also, all the 
constituents of tar which have any sensible vapour-tension 
at the ordinary temperature must to some extent be 
present ; and many of them have, in fact, been traced by 
Davis. 

When coal-gas is passed through a scmbber containing 



COAL TAR. 59 

natural or artificial oils of high boiling-point, it gives np 
(as in the low-temperature industry) a notable quantity of 
light oils, containing paraffins and benzol. This process 
was patented by Caro, Clemms, and Engelhorn in 1869. 
Davis (1882) aids the absorption by refrigerating the 
gases, and thus obtains a total of 1 j — 3| gallons of 90 
per cent, benzol per ton of coal. According to another 
estimate, 17-candle gas should yield about 1^ gallons of 
90 per cent, benzol. The scrubbed gas is a very valuable 
fuel. 

In the case of " 17-candle " gas, Wright estimates 
that l-J gallons, on the average, of 90 per cent, benzol 
could be extracted from the gas from a ton of coal by 
scrubbing with oils. 

Davis states the amount in one case (TliornclifFe coal) 
as 4'4 gallons, the temperature of the scrubber being kept 
very low (4-4° C). 

According to Deville, Paris coal-gas contains constantly 
1 per cent, by volume of pure benzene. 

The yield of tar in very large English works is about 
5*3 per cent. ; ammoniacal liquor, 14*1 per cent. ; sulphate, 
•87 per cent.; gas (10,198 cubic feet), 16*6 per cent. 
Specific gravity of gas, -48 ; illuminating power, 17 candles. 

The treatment which the crude tar undergoes is re- 
markably similar to that to which crude paraffin oil is 
submitted. The liquor is separated from it and treated 
for ammonia exactly as in the low-temperature industry ; 
its specific gravity being about 1*02 (4° Tw.), and the 
percentage of ammonia about 2. It is observed that an 
increase of heat in the retorts leads to an increased 
amount of cyanide and sulphocyamde in the liquor. 

Coal yields from 6 — 15 per cent, of liquor, from 3 — 6 
per cent, of tar (cannel sometimes as much as 9 per cent.), 
and about 50 — 70 per cent, of coke (containing 2^ per 



60 MANUALETTE OF DESTEUCTIVE DISTILLATION. 

cent, of ash) ; the remainder represents the yield of gas, 
and the working loss (about 10 per cent.). It is usual to 
distil coal, or such a mixture of coals, as shall yield about 
10,000 cubic feet of gas (sp. gr. 0-5—0-6) per ton, or about 
20 per cent. 

In a given product of coal-gas the middle portions 
contain most, the latest portions least ammonia. 
Foster found the nitrogen (1-73 per cent.) in a 
Durham gas-coal to be distributed as follows during 
distillation : — 



Evolved as ammonia 
„ as cyanogen . . 
„ uncombined . . 

Remaining in coke 


. . 14-50 

1-56 

.. 35-26 

. . 48-68 



100-00 

Here the ammonic, uncombined, and residual nitrogen 
are in the ratio N2 : N^ : N^. The distribution seems to 
depend somewhat on the proportion of ash, such coals as 
contain little ash giving but little ammonia in the distil- 
late. This relation is intelligible when we remember that 
coal-ash is an alkaline substance. 

It was observed by Knoblauch that 2^ per cent, of 
lime added to the coal increased the yield of gas 5 per 
cent., and diminished the illuminating power 5 per cent. 
There was some increase in the ammonia. 

Leyboid found about -2 per cent, (by volume) hydric 
cyanide in the gas of the hydraulic main, and about -02 
per cent, in the gas of the holders. The impurity is now 
under extraction. 

L. T. Wright found the grains (G), of sulphur per 100 
cubic feet other than hydric sulphide to depend on the gam 
made per ton : — 







COAL TAR. 


■ ». " 


Cubic feet per 


ton. 




a 


11,620 






.. 44-17 


10,772 






. . 36-93 


9,431 






. . 26-75 


8,370 






.. 19-16 


6,896 






. . 13-91 



61 



The above results refer to bituminous coal ; but similar 
ones were obtained with cannel. 

As regards the distribution in the tar, Watson Smith 
obtained the following numbers with a tar containing 1-67 
per cent, of nitrogen : — 

Coke. Nitrogen per cent. 

Crude benzene . . . . . . 2*33 

Light oil 2-19 

Kreasote oil . . . . . . 2*01 

Ked oil filtered from crude anthra- 
cene 2-19 

Pitch 1-60 

And, according to the same authority, the residual nitrogen 
per cent, is found to be, in the cokes indicated — 

Coke. Nitrogen per cent. 

Gas retort (Lancashii-e ?) ., 1*38 

Beehive oven .. .. .. 0*51 

Simon-Carves oven . . . . 0-38 

or inversely proportional to the temperature. 

Modern tar is heavier than the liquor ; this must neces- 
sarily be the case where naphthalin and phenols are pro- 
duced in quantity. The sp. gr. of Enghsh tars is about 
1-1 to 1*15 ; of Scotch tars, which are derived from cannel 
coal, about 1-1. Cannel tars are poorer in useful aromatic 
compounds than are bituminous tars. 

Tar is treated with steam (or distilled with one-fifth of 
its volume of water, or distilled by the heat of a steam- 



62 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

coil) to remove light naphtha, or crude " benzol." The 
stills hold from 500 to 4,000 gallons, and are horizontal 
cylinders. The steam brings over about 5 — 10 per cent, 
at most of hght naphtha (sp. gr. 0*78 — 0*88*) — according as 
the coal is bituminous or cannel — and some ammoniacal 
water, which is treated like the other "liquor." The 
residue of the distillation is heated by fire to about 200°, 
when most of the heavy oil comes over, and afterwards 
to over 300°. The residual pitch, which amounts to 30 — 
50 — 70 per cent, of the tar, is after several hours' cooling 
(either in the still or a separate tank), run off into moulds. 
It is generally utilised for '' asphalt," by mixture with 
about four times its weight of sand, chalk, or other inert 
material; or for "patent fuel," by moulding with four 
parts of coal dust or similar material. 

The hght naphtha is run off the " liquor " beneath it, 
and churned with 5—12 per cent, of oil of vitriol, and 
afterwards with about 2 per cent, of caustic soda (in 
aqueous solution, of sp. gr. 1*4). Lime may be ads^anta- 
geously used instead of soda, if great care be taken to 
avoid excess. The percentage of loss is about the same 
as that of the added vitriol. Sometimes the naphtha is 
distilled between the acid and alkaline treatment ; on the 
other hand, the lime and acid treatment may be performed, 
if desired, in the same tank. Mixtures of lime and caustic 
soda are also used ; and this is probably the preferable 
course. It is also undoubtedly advisable to re-distil the 
crude naphtha before submitting it to this chemical treat- 
ment. The residues of this second distillation, when 
mixed with lime {see RosiN Oil), yield a lubricating 
" grease," as is the case with several genera of unsaturated 
hydrocarbides. Finally, the purified naphtha is distilled 
by steam. About half of it consists of " 50 per cent. 

* Formerly this distillate was allowed to reacli the sp. gr. -95. 



COAL TAR. 63 

benzol" (to 140° C.) and the remainder (to 170° C.) con- 
stitutes " solvent " benzol, the later fractions yielding 
some " burning naphtha." " 90 per cent, benzol " boils at 
and below 100°. Various fractions can be obtained of a 
character intermediate to these. 

The heavy or " dead " oil may be used, as such, for 
preserving or "kreasoting" timber; for which purpose 
portions boiling above 310° are better adapted than the 
more volatile phenols. Kreasoted timber owes its preser- 
vation, according to WilHams, chiefly to pyridine and 
quinoline bases, which it retains even after a lapse of 
thirty years ; in a less degree to naphthalin and phenols, 
neither of which is found in old kreasoted timber. Some 
part of its durability may also be due to acridine. The oil 
is more commonly distilled. The earlier portions of the 
distillate (150°— 200°) contain impure phenol; the follow- 
ing portions (200°— 212°) are rich in naphthalin ; the next 
fi-action (212° — 270°) contains kreasols; and the last (to 
360°) yields crystals of anthracene on cooling. Naphthalin 
is not at present utilised on the large scale ; but anthracene 
is the source of artificial alizarin. Tar yields less than 
1 per cent, of crude anthracene. The mother-liquid of 
the anthracene, after further concentration by distillation, 
and a second deposition of crystals, is chiefly valuable for 
illuminating, and more especially for lubricating purposes. 
The treatment of the phenol fraction is the object of a 
special industry, that of carbolic acid. 

Instead of passing steam through the retort in the first 
distillation of coal-tar, direct heat alone is very frequently 
apphed (as in the crude paraffin oil still), the water naturally 
suspended in the tar providing for some time the necessary 
steam. In this method the gases at first extricated are 
sometimes passed through a purifier, and afterwards 
burned. The " first runnings " from the still are very 



64 



MANUALETTE OF DESTRUCTIVE DISTILLATIOX. 



light oils, almost free from phenols, and accompanied olP 
course by ammoniacal water. As soon as the latter has 
completely passed over, a considerable access of heat is 
necessarily required to volatilise, unaided, any further 
portion of the tar ; so that this period of the distillation is 
usually very well marked. Light oils of the naphtha class 
are distilled up to 170° at least; impure phenol (carbolic 
acid) and naphthalin to a point exceeding 220^ ; kreasols to 
270°; and anthracene oil to 360°. The residue is pitch. 
As in the case of paraffin stills, the worm must be kept hot 
at the end of the distillation. Not unfrequently, super- 
heated steam at various temperatures is employed in the 
last, or last two, stages. Stills of the largest size are re- 
charged about every two days. 

Cannel coal-tars yield little, if any, " 90 per cent, 
benzol," but a large proportion of xylol. Of phenols, 
cannel-tar yields the largest total bulk, but least phenol 
proper ; Newcastle tar containing least " total phenols," 
furnishes the largest proportion of phenol proper. Lanca- 
shire gas-tar yields about 5 per cent, of crude phenols, 
containing 65 per cent, of crystalKsable phenol (W. Smith.) 
The following percentages, taken from Crace-Calvert, may 
still (the author is assured by a distinguished practical 
authority) be taken as fairly correct, viz. : — 



— 


Light 
Oils. 


Phenols. 


Heavy 
Oils. 


Naphthalin. 


Wigan cannel 


9 


14 


40 


15 


Newcastle . . 


2 


5 


12 


23 


Staffordshire 


5 


9 


35 


29 



It is difficult to reconcile the numerous confficting 
statements made on the subject of coal-tar distillation, but 



COAL TAR. 



65 



the following may be taken as an average of recent 
results : — 



First runnings 

Light oils 

Kreasote oils, naphthalin and phenol 

Anthracene oil 

Pitch 



2-5 

5-0 

27-5 

10-0 

55-0 

100-0 



7-5 



The relation of pitch to tar is thus about the same as 
that of coke to coal ; and the kreasote oils, &c., generally 
weigh half as much as the pitch. Sometimes as much as 
75 per cent, is taken as pitch, the quality of which is then, 
of course, soft. Good hard pitch of sp. gr. 1*28 melts at 
about 200°, and has been found to have the composition 
CeHsO. 

The following data have been given by Schultz on the 
authority of Riitgers — 



Composition of Londo 

Benzol of 50 per cent. 
Solvent naphtha 
Burning naphtha 
Kreasote oil . . 
30 per cent, anthracene 

Pitch 

Loss 



Berlin Gas- Tar. 

Benzol and toluol for anilines 
Bright (solvent) oil . , 
Crvstalhsed carbolic acid 



Gas- Tar. 



1-1 

1-0 

1-4 
33.2 

1-0 
58-6 

3-7 

100-0 



0-8 
0-6 
0-2 



6^ 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



Kreasol (disinfectiug quality) 


0-3 


Naphthalin 


3-7 


Anthracene (pure) 


0-2 


Heavy oil (for pickling timber) 


. 24-0 


Pitch 


55-0 


Water and loss 


15-2 



( V. supra^ pp. 57, 58.) 



100-0 



According also to the same authority the yield of 
anthracene very seldom exceeds 0*5 per cent., and the 
maximum of crude naphthalin is 8 per cent. ; the tar at 
Berlin constitutes 4-8 per cent, of the coal. 

Anthracene from cannel tar generally contains paraffin, 
a troublesome impurity, best removed by w^ashing with 
carbonic disulphide. 

The portion of coal-tar and pitch which is insoluble in 
ordinary solvents, is known by the name of " free carbon," 
an expression obviously very erroneous. 

Schulze states that the neutral tar-oils boiling at 170°— 
210° consist of about 50 per cent, resinifiable matter, 15 
per cent, trimethylbenzenes, 15 — 20 per cent. tetrame*:hyl- 
benzenes, and 15 — 20 per cent, of naphthalin. The three 
kreasols occur in about the proportion metakreasol 40, 
orthokreasol 35, and parakreasol 25. 

There can be little doubt that the future economical 
treatment of dead oil, and in general of crude oils of high 
boihng-point, will in the main turn upon some method of 
distillation in vacuo. 

The following complete analyses of London and 
average cannel gas-tar (Scotch) have been made in the 
author's laboratory : — 



( 


:OAL TAR. 


( 




London. 


Scotch Cannel 


*Carbon 


.. 77-53 


85-33 


^Hydrogen 


6-33 


7-33 


^Nitrogen 


1-03 


-85 


Sulphur 


•61 


-43 


Oxygen 


. . 14-50 


6-06 



100-00 



67 



100-00 



If we deduct nitrogen and sulphur, we shall obtain the 
following results : — 





London. 


C21H02O3. 


Scotch. 


C18H20O 


Carbon 


78-82 


78-26 


86-44 


85-71 


Hydrogen . . 


6-44 


6-83 


7-42 


7-94 


Oxygen , . 


14-71 


14-91 


6-14 


6-35 



100-00 100-00 100-00 100-00 

The ubiquitous C3 unit again appears in the mean com- 
position of the tars ; it must, therefore, be common to both 
kinds of gas. 

A conspectus of operations and quantities in the ti eat- 
ment of coal-tar is given on the next page. 



* Mean of two determinations. 



QS 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



< 
D 

Q 

o 
< 

O 



a; o 



aH 




v 




o a~ 




n 




— lO 








,c "^ 










,sl 


II 


1 


O CO 

;:: to 


— -o q 


-s-?- 


-w 




t/2x: 


g J2 


o 


1 


Ph 


fil 





^ ft 



- = — S o'"'^ I ~ J .h" ~ 1 ■ 
2 -cis -a^ iS S 

& != ^ 



— O 2 
M 

— s §9 . 
1 ^og* 






COAL TAR. 



69 



Annexed is a table of the products of destructive dis- 
tillation of coal. The formula, boiling-points, and 
melting-points are added, so far as known. 



Destructive Distillation of Coal. 



Name. 


Eormula. 


B.P. 


M.P. 


Hydrogen 


Ha 








Metliylic hydride 


CH4 








Hexvlic 


CeHn 


68° 






Octylic „ 


CsHis 


119 






Deeylic 


C10H22 


171 






Paraffin . . 




C„H2„ + 2 








Ethylene 




C2H4 


-102-5 






Tritylene 




CaHe 








Tetryleue 




C4H8 


-5 






Pentylene 




C5H10 


31 






Hexylene 




CeHjs 


71 






Heptylene 




C7H14 


97 






Acetylene 




C2H2 








Crotonylene 




C4H6 


25 






Terene . . 




C5H8 








Hexoylene 




CeHio 


80 






Styrolene 




CsHg 


145 






Indene . . 




C9H8 








Thiophene 




C4H4S 


84 






Thiotoluene 




CsHeS 


113 






Thioxene 




CfiHsS 


137 






Benzene . . 




CfiHe 


80 


5* 


ir 


Parabenzene* . 




CeHe 


97 






Toluene . . 




C^Hg 


111 






Orthoxylene 




CsHio 


143 






Paraxylene 




CsHio 


137 






Metaxylene 




Cgiiio 


137 






Cumene . . 




C9H12 


1G6 






Ethylbenzene . 




CsHio 


133 






Pseudocumene . 




C9H12 


165 






Hemellithene . 




C9H12 


175 






Mesitylene 




C9H,2 


163 






Cymene . . 




C10H14 


166 






Durene . . 




C10H14 


196 


80 


•5 


Terpene . . 




C10H16 


171 




, 


Naphthalin 




C,oH8 


218 


80 


Methylnaphthalin 


CiiHio 


242 


-x8 


Naphthalin liydride . . 


CioHio 




210 


Naphtols, — o & 


CioHsO 


279, 288 


94, 33 


Phenyl 


CiJI,o 


254 


70 


Acenaphthene . . 


CioUio 


285 


100 



* ? Dipropargyl. 



70 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

Destructive Distillation of Coal — (continued). 



Name. 


Formula. 


P.P. 


M.P. 


riuorene 


C13H10 


295 


113 


Phenanthracene 




CuHie 


340 


99 


Anthracene 




C14H10 


360 


213 


riuoranthrene . . 




C'lsHio 




109 


Pyrene 




CieHio 




148 


Anthracene hydride . 




C14H12 


305 


106 


Methy lanthracene 




^15Hl2 


, . 


200 


Chrysene 




CisHis 


, . 


249" 


Retene 




CrsHis 


350° 


99 


Picene . . 




C22H14 


519 


338 


Water .. 




H2O 


100 





Hydric sulphide 




H2S 




-85 


„ cyacide . . 




HCN 


26 


-18 


„ sulphocyanide . 




HCNS 






Carbonic oxide . . 




CO 


-193 


, , 


„ dioxide 




CO2 


--78 


. , 


„ disulphide . 




CS2 


47 


-110 


Sulphuric dioxide 




SO2 


-10 




Hydric acetate . . 




C2H4O0 


120 


15 


Acetonitril 




C2H3N" 


77 




Ethylic alcohol (?) 




CsHgO 


78 


-130-5 


Phenol 




CgHfiO 


182 


42 


Hydric benzoate 




C7H6O2 


250 


120 


Kreasols, — o, m p. 




C^HgO 


118, 201, 199 


31, (?),36 


Pyrokreasols, — a, )8, 7 . 




C28 1^2602 




104,124,195 


Phlorol 




CsH^oO 


219 


, , 


Cumarone 




CgHeO 


170 




Ammonia 




NH3 


-33 


-70(?) 


Butylamine 




C^HnN 


75-5 




Aniline . . 




CgH^N 


182 


-8 


Cespitine 




C5H13N 


96 




Pyridine.. 




C6H5N 


115 




')-Pieoline 




CgH.N 


144 




a-a-Lutidine 




C7H9N 


142 




j8-Lutidine 




C7H9N 






a y-Lutidine 




C7H9N 


157 




Collidine 




CsHiiN 


170 




Parvoline 




C9H13N 


188 




Coridine . . 




C10H15N 


211 




Rubidine 




CnHi;N 


230 




Viridine 




C12H19N 


251 




Acridine . . 




C13H9N 


360 


107 


Carbazol 




C10H9N 


355 


238 


P aeny Inaphtylcarbazol 




Cj.HhN 


.. 


330 


Leucoline 




Cgd^N 


220, 238 




Lepidine. . 




C10H9N 


254, 268 




Iridoline. . 










Cryptidine 




CnH„lV 


272 




Tetracoline 




C12H13N 


292 





COAL TAR. 71 

Destructive Distillation of Coal — (continued). 



iXame. 



Peiitacoline 

Hexacoline 

Heptacoline 

Octacoline 

Pyrrhol . . 

Carbon (hydrogenated) 

Sulphur . . 

Nitrogen. . 



Formula. 



Ci3Hi,N 


312 


ChHi7N 


327 


C15H19N 


347 


CieHoiN 


362 


C4H5N 


133 


Cn 


.« 


S2 


400 


N2 


-193 



P.P. 



M.P. 



115 

213 (?) 



The following are the specific gravities of some of the 
more important of the coal-tar compounds : — 



Compound. 


Sp. gr. 


AtO^ 


At 15° 


At 18°. 


Benzene .. 

Toluene .. _ 

Xylene (mixed isomers) . . 

Naphthalin 

Carbonic disulphide 

Phenol 

Aniline , . 


•8991 

•8841 
•877 

1-036 


•8846 
•8702 

1 -272 


I'-iss 

1-065 



Action of Heat on the Organic Matter in Coal. 

Professor W. Foster {Proc. Inst C.E., April, 1884) has 
completely analysed, and distilled at a high temperature, 
two samples of Yorkshire and one of Durham coal. His 
mean results, apart from sulphur, nitrogen, pit- water, and 
ash, correspond to the following relations : — 

33C + 



2C,,H,30 = 

Organic matter 
in coal. 



(Calc.) 100 
(Found) — 



Fixed carbon. 

Gl-5 ., 
Gl-5 . 



C,5H3.0 



Gas and tar. 

35-7 . 



H^O 



Organic water. 

2'^ 



38-5 



12 MAXUALETTE OF DESTRUCTIVE DISTILLATIOX. 

Foster has also similarly examined a Scotch cannel. 
His data may in Hke manner be reduced as follows : — 

2C12H12O = 12c + Cj^H^^O + H2O 
(Calc.) — .. 41-9 .. 52-9 .. 5*2 
(Found) — . . 41-3 . . 58-7 

The Heywood cannel gas-coal, which may be taken as 
representing an average Scotch cannel, has (page 49) been 
analysed and distilled. The reactions are — at a low 
temperature — 



^Q^YL^^O = 270 + C^'R.e^s 


+ H2O 


Fixed carbon. Gas and tar. 


Organic water. 


(Calc.) 100 .. 59-6 .. 37-1 


3-3 


(Found) — .„ 584 .. 38*3 


.. 3-6 


and at a high temperature — 




4CgH„0 = 24C + C„H,e03 


+ H^O 


Fixed carbon. Gas and tar. 


Organic water. 


(Calc.) 100 .. 52-9 .. 43-8 


.. 3-3 


(Found) — .. 52*5 .. 43-9 


.. 3-9 



Mills and McMillan {Journ. Soc. Chem. Tnd., 1891) 
distilled a Scotch bituminous coal w^ith the following 
results : — 

At a low temperature — 
28Cj3H,,0 = C\,,H„3 + C3„H,,09 + C3„H,„,03 4 16H,0 

Coke. Tar. Gas. 

At a high temperature — 
30C.,H„O = C,,„H,, + (J3oH,„0, + 2C3„H,3„03 + 16H,0 

Coke. Tar. Gas. 

It is evident that the high temperature volatilises in 
gas twice as much carbon as the low temperature does. 



COAL TAR. 



73 



The following results are known as regards the com- 
position of the organic matter in coal : — 



Yorkshire and Durham . 
Balquhatstone 
Boghead . . 
Average cannel 
Heywood gas cannel 
Good average Scotch sha 






. . C12H12O 

.. C,H,20 

It may now be regarded as proved that this organic 
matter breaks up when heated in multiples of C3. 



Average Composition of Coal- Gas. 

P. Frankland {Journ. Soc. Chem. Ind., iii,273) has given 
the composition of fifteen samples of purified coal-gas pre- 
sumably bituminous). The mean percentage and variations 
are as follows : — 



Ethylene and its 
equivalents. 


Hydrogen. 


Carbonic Oxide. 


Marsh Gras. 


6-69 

1-45 

Variation. 


47-39 
3-47 
Variation. 


4-05 

0,;69 

Variation. 


38-83 
1-57 
Variation. 



These ratios correspond to 

3C2H4 : 24H2 : 2C0 : 20CH, : 200^ 

( = 102 vols.; the last being added to fulfil the condition 
of unpuritied gas). Summing the above formulae, we have 
the collocation CgoHj^gOg, which may otherwise be ex- 
pressed as 30CH^ : HH^O : 4H2. Having regard to variation, 
we shall be correct in regarding average unpurified coal- 
gas as consisting of redistributed marsh-gas and Avater. 
Here also the C3 unit recurs. 



74 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



The same author (loc. cit.) gives the composition of 
three samples of gas from Scotch cannels. His figures 
show that this gas tends to consist of redistributed methyl 
and water ; but the data are too few, and their variation 
too great, to allow of any very exact inference. 

The output of the United Kingdom in each twelve 
months since 1857 is given below : — 



1858 
1859 
1860 
1861 
1862 
1863 
1864 
1865 
1866 
1867 
1868 
1869 
1870 
1871 
1872 
1873 
1874 



Tons. 

66,109,603 

71,979,765 

84,042,698 

86,407,941 

81,638,338 

86,292,215 

92,787,873 

98,150,587 

101,754,294 

104,500,380 

103,141,057 

107,427,457 

110,431,192 

117,352,028 

123,497,316 

127,016,747 

125,067,916 



1875 
1876 

1877 
1878 
1879 
1880 
1881 
1882 
1883 
1884 
1885 
1886 
1887 
1888 
1889 
1890 
1891 



Tons. 
131,867,105 
133,344,766 
134,610,763 
132,607,866 
134,008,228 
146,818,522 
154,184,300 
156,499,977 
163,737,327 
160,757,781 
159,351,418 
157,518,482 
162,119,812 
169,935,219 
176,916,724 
181,614,288 
185,479,126 



(Average present price, 8s. per ton at the pithead.) 



The American (U.S.) bituminous coal of all kinds raised 
in 1888 was 91,106,998 tons of 2,240 lbs., having a value 
of 122,497,341 dollars. 

Mr. L. T. Wright has compiled the following very 
interesting table showing the percentage value of each 
product to the total revenue of the Companies indicated : — 



Company. 


Gas. 


Coke. 


Tar. 


Ammonia. 


Sundries. 


Nottingham, 1881 and 1882,, 
S. Metropolitan, 1883 
G-ashght and Coke Cos., 1883 
Cie. Parisienae, 1881 


75-06 
72-05 

78-47 
70-70 


8-29 
15-18 
11-43 
18-00 


8-21 
5-34 
2-98 
3-48 


3-27 

7 '04 
6-86 
1-91 


5-17 
•39 

•26 
6-00 



Id 1889 there were 578 gas undertakings in the United 



COAL TAR. 



75 



Kingdom, with an authorised capital of 76,593,724/. The 
amount of coal carbonised was 9,633,011 tons: and the 
amount of gas produced 98,081,319 cubic feet. 

In 1889 the Paris Gas Company sent out 11,013 milKons 
cubic feet. 

There are 971 gas companies in the United States, and 
47 in Canada. 592 companies in the United States manu- 
facture their gas from coal, and 296 under various patents 
and processes. In Canada 24 companies manufacture 
from coal and 16 from other processes. One company 
manufacturing gas from coal with an output of 11,000,000 
cubic feet received 75c. per 1,000 feet, 26 companies, 
with an output of 1,879,900,000 cubic feet of coal-manu- 
factured gas, received 1-50 dols. ; 6 companies manufactur- 
ing by other processes, with an output of 900,000,000 
cubic feet, receive 1*50 dols., and 45 companies, manu- 
facturing from coal, with an output of 468,000,000 cubic 
feet, receive 2*25 dols. per 1,000 feet. The output of 
495 coal-gas companies is 17,502,305,000 cubic feet, the 
income from which is 30,452,710 dols.; 188 companies 
manufacturing by other processes have an income of 
10,291,000 dols. from an output of 5,554,000,000 cubic feet. 
The average price of coal-gas is 1-73^^0 ^ols. ; of gas 
manufactured by other processes, 1*81 -^^ dols. In the 
matter of pubhc lamps, 1,056 receive gas at a cost of Ic. 
per hour, 100 at IJc, 142 at Ij'-^c, and 100 at l^c. ; 6,000 
lamps range from Ic. to 4-7c. per hour ; 104,000 lamps 
realise 3,319,287 dols., an average of 30*17 dols. per lamp. 
The output of gas by 517 companies manufacturing from 
coal requires 1,908,611 tons of coal. The output of 206 
companies using water and other processes require 178,563 
tons of anthracite coal. The capital required for all 
the gas interests amounts to 261,000,000 dols., the income 
from which is about 50,000,000 dols. [1890.] 



76 :maxualette of desteuctive distillation. 

Appendix to Coal-Tar. 

In the maimfacture of iron by the blast farnace method, 
tar and ammonia are naturally among the products when 
coal is employed. Both of thepe products admit of collec- 
tion. [For drawings of various kinds of condensing and 
scrubbing plant for this purpose, see Journ. Soc. Chem. Ind., 
1885, p. 217.] The volume of the gases from which they 
are separated is about 130,000 cubic feet per ton. The 
percentage composition by volume of these gases is, 
according to W. Jones, carbonic oxide, 25 — 30 ; carbonic 
dioxide, 3 — 8 ; hydrogen, 5 — 7 ; marsh gas, 2 — 4; nitrogen, 
b2 — 60. The yield of ammonic sulphate is probably about 
16 pounds per ton; of tar, or, more correctly, tar-emul- 
sion, 20 gallons. The tar, Avhich is intermediate in its 
nature between shale and ordinary tar, contains a great 
amount of gas bubbles in suspension, and intumesces 
very much when heated : it is of rather " dry " quality. 
It contains no considerable amount of true phenol, benzol, 
or anthracene. The following results were obtained in 
the author's laboratory : — 

Sp. gr. of tar 1*00005^ 

After steaming (100"^) . . . . I'OOOloj 

Volatile in steam (100^) . ., 7-34 per cent. 

Sp. gr. of portion volatile in 

steam -90800 



COAL TAE. 



77 



Examination of Portion Volatile in 


Steam. 


Percentage. 


Bciling-Poiut. 


Sp. gr. 


Per cent, of phenols 

and phenoids in 

fraction. 


1-70 

9 12 

12-53 

32-80 
43-85 


100 
152 
175 

200 
Above 200 


•86936 
-87014 
•88546 
•90631 
•92241 


6*25 

9-38 

17-50 



Watson Smith examined another sample of sp. gr. -954, 
and obtained the following (volume) percentage results :— 

Water (ammoniacal) . . 
Naphtha and oil to 230° 

Oil to 300° 

300° to sohd distillate . . 
Solidifying distillate . . 



30-6 
2-9 
7-0 

13-0 

16-8 



The coke amounted to 21-5 per cent, by weight; loss 
5-5 per cent. Hard paraffin was esthnated at -54 per cent. 
The amount of coke is extremely large. 

Blast furnace tar contains 17-5 per cent, by volume of 
phenols. Amongst these W. Smith has found meta- 
kreasol, metaxylenol, pseudo-cumenol, and naphtols. Allen 
found in Gartsherrie tar (1887), carbon, 83*64 ; hydrogen, 
10-59, and sulphur, -09 per cent. 

A specimen of average Scotch cannel gas-tar gave the 
subjoined numbers ; — 

Sp. gr. of tar 

After steaming . . 

Yolatile in steam 

Sp. gr. of portion volatile in 

steam . . . . . . • • '93334 



1-09430^ 
M2830) 

10''33 per cent. 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



Examination of Portion Volatile in Bteam. 



Percentage. 


Boiling-Point. 


Sp. gr. 


Per cent, of phenols 
in fraction. 


9-85 
18-19 
26-00 
22-85 
23-11 


o 

100 
155 
175 

200 
Above 200 


•86926 
-88255 
•91426 
•94763 


5-00 
10-00 
14-38 



Products from Cohe Ovens. 

Mr. Jamieson, of Newcastle, has (1882) proposed the 
following simple process for collecting products from 
ordinary coke ovens. The oven is lighted at the top ; 
and the products of combustion, drawn downwards by 
means of an exhauster, cause destructive distillation of 
the coal beneath. Paraffiniferous tar and combustible gas 
reach the base of the oven, whence they are carried 
through perforated iron pipes to a main. The exhauster 
produces an inward pressure of 1 inch (water), and effects 
the combustion of 2 cwt. of coke per ton of coal. There 
is a yield of from 5' 6 to 8 gallons of crude (low-tempera- 
ture) oil, and 3 — 10 pounds of amnionic sulphate per ton. 
Sp. gr. of the oil about -97. The gas amounts to 200 
•cubic feet per hour per ton. 



Analysis 


of the Oil 




Lubricant 


• • . • 


. . 39-5 


Illuminant 


. . 


.. 37-7 


Scale . . 


. . 


. . 13-5 


Tar and loss, Siii. 


.. 


9^3 



100-0 



COAL TAR. 79 



Average Analysis of the Gas. 



Carbonic dioxide 


. . 4-22 


„ oxide 


. . 23-88 


Hydrogen 


. . 26-67 


Oxygen 


. . 3-29 


Nitrogen 


.. 41-93 



100-00 

Hydrocarbides do not seem to have been determined 
in the gas. The tar contains no benzol, but very small 
quantities of toluol and rather more xylol; the greater 
part of it boils at 250° — 350°, the distillates up to the 
latter temperatui'e yielding no deposit on cooling. Above 
350°, paraffin melting at 58° passes over. There is only a 
trace of phenol, and rather more kreasol: these are fol- 
lowed, on fractionating, by obscure resinous phenoids. 
Phenols and phenoids together amount to about 5 per 
cent. Anthracene is not present. The whole distillate is 
remarkable for the entire absence of fluorescence. 

It should be borne in mind that the composition of 
this tar depends very much on that of the coal from which 
it has been obtained. Thus Watson Smith found from 
5^ to 9 per cent, of scale in samples of different origin. 
Pitch or coke on rectification is, of course, low in this tar. 

Watson Smith has examined a sample of tar from the 
Simon-Carves coke ovens. These are worked at an ex- 
tremely high temperature, and the tar consequently 
contrasts strongly with that from the Jamieson process. 
Sp. gr. 1-106.. The (volume) percentages on distillation 
Avere as follows : — 



80 



MAN U ALETTE OF DESTRUCTIVE DISTILLATION, 





Water . . 


6-2 


Naphtha 


to 120° 


1-6 


Below 


210° 


2-9 


^^ 


220° 


1-3 


j> 


230° 


0-5 




300° 


186 


Above 


300° 


34-2 


Half-coked pitch 


30-4 


Loss (by 


diff.) 


4-3 



V Mostly Naphthalin. 

Naphthalin and anthracene. 
Mostly anthracene. 



100-0 



Very little " red " or " anthracene " oil was present. 
Available anthracene, -73 per cent. 

*' Gas-Producer'^ Tar. 

The tar from a Sutherland gas-producer has been 
fractionated by Watson Smith. In general character it 
occupies a position between the Jamieson and Simon- 
Carves tars, but near the former. Sp. gr. 1-08. The 
(volume) percentages are — 

Below 230° (excluding water) . . 5*4 

230°— 300° 10-0 

300° to solidification of distillate . . 14*5 

Oils, solidifying . . . . . . 10*4 

Coke, 30 per cent, by weight ; loss and water, 32 per 
cent. Naphthalin and anthracene could not be detected ; 
paraffin amounted to 6*7 per cent, on the weight of the 
tar. The enormous residue of coke is very noteworthy. 



Hydrocldoric Tar. 

An important modification in the conditions of formation 
of coal-tar has been studied by E. Heusser (Ger. Pat. 24758, 
1883). When a mixtnre of chlorine with hydric chloride 
is passed through an ordinary charged gas retort, it acts 
as a hydrogenating or dissociating agent, producing a tar 



WOOD TAR. 81 

very rich in benzol, and having the following average 
composition : — 

Water 10 

Benzol 18 Boihng at 60^—180° 

Chloro-compounds, heavy 

hydro carbides, naphtha- 

lin, anthracene. , . . . 20 

Pitch 52 

100 

18 per cent, of the crude benzol was reduced to 10 per 
cent, by purification and distilhng to 150°. 

On the other hand, zinc chloride, in presence of hydric 
chloride, greatly increases the yield of heavy hydro- 
carbides from coal, and can even convert some of the 
lighter constituents of tar, when distilled theremth, into 
heavy ones. 



WOOD TAR. 

Wood consists essentially of cellulose (nC^H^fi.) and 
13 per cent, of an isomeric gum, together with 20 — 25 per 
cent, of water, and a little mineral matter. When heat is 
applied to it in closed vessels, it decomposes, giving ofi*, 
among other products, a quantity of steam;* at firsts there- 
fore, the process is necessarily under *' low-temperature " 
conditions. As cumula ive resolution continues, less water 
relatively is given off, and the heat can exert its full effect; 
the second stage of the distillation is, therefore, under 
" high-temperature " conditions. 

* Furfurol can be obtained at about 200^, or even lower. 

F 



82 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

Cellulose is stable at 150°. The first effect of lieat is 
at first to dehydrate it. By interpolation among Violette's 
well-known results on the heating of wood (Ann. Ch. Phys. 
[3], xxxii. 304), it appears that nQfi^O^ corresponds to a 
temperature of about 185°, and nQ^fi^ to about 220°, in 
the absence of pressure ; in presence of pressure, the latter 
temperature corresponds to nQ^fi^. At a point some- 
what below 430°, and without pressure, the residue has 
the composition, nCgHgO. The final stage TzCg is probably 
not attained under ordinary experimental conditions. 

Wood thus yields both aromatic and fatty bodies ; and 
these are specially characterised by being to a great extent 
oxy-compounds, as is natural in a series of cellulose deriva- 
tives. It is very interesting to note, as a further consequence 
of the mixed conditions of this distillation, that naphthalin 
and parafiin are both present among the products. \_See 
Cellulose.] 

The heat is allowed to reach bright redness ; charcoal 
is left in the retort, illuminating gas is evolved, and the 
tar is separated and condensed in a very wide copper 
worm. Sulphur-compounds and ammonia are not given 
off. AVood may yield approximately — 

Charcoal . . . . 20 — 30 per cent. 

Acid water . . . 28 — 50 „ 

Oily (light or heavy) tar 7 — 10 „ 

Gas and loss . . . . 20 — 37 „ 

Morgan has found the following results (1885) with 
coppice oak: — 

Liquid distillate (tar, acid, 

&c.) . . . . . . 50 — 60 per cent. 

Glacial acid . . . , 3*44 „ 

Naphtha (-8263) . . . 1-03 

Charcoal , , . . . . 31*25 „ 





WOOD 


TAR. 


Tims, dry 


wood is not unfi 


•eqiiently split up in the p 


rtion — 






CeH.oO, 


= 30 + 


4PI^0 -^ C3H,0 


Wood. 


Carbon. 


Water. Gas and tar. 


100 


22-2 


44-5 33-3. 



83 



though this equation must not be taken as indicating the 
mode of decomposition (page 7). The general met hylic 
character of the products is strongly marked ; and in the 
case of different woods, at the same temperature, the 
total methyl in the distillate is — if Stolze's observations be 
correct — a constant quantity. 

The retort is nearly always made of thick boiler-plate, 
and either horizontal or vertical ; the former position is the 
better of the two. [Pierce uses a brick still, capable of 
holding 56 cords (100 tons) of wood; he distils during six 
days and cools during six days. The products are — char- 
coal, 30 per cent. ; 5 gals, pyroligneous acid and 175 cubic 
feet gases per 100 lbs.] When the object of the distiller is 
to obtain the maximum quantity of acid, the retort should- 
not be heated beyond 350°— 400°. He, then, probably 
derives his products, and their collaterals, from the residues 
/iC^HgOj — wC^HjO of cellulose. When wood is heated for 
the purpose of making gas, the retort is followed by a 
heated empty chamber or " generator," in which takes 
place what is virtually a second destructive distillation. 

According to Jakowlew — 







Acetic 


acid. 


100 parts wood } 


ield— 


I. 


II. 


Linden 




10-24 


10-17 


Birch 




9.52 


0.29 


Aspen 




8-0«) 


8-37 


Oak.. 




7-92 


8.24 


Pine. . 




b'^b 


6-12 



8i MANUALETTE OF DESTRUCTIVE DISTILLATION-. 





Aceti 


c Acid. 


100 parts wood yield — 

Fir 


I. 

5-24 


II. 

5-09 


Birch bark . . 


2-20 


2-38 


Cellulose from bircli 


6-21 


• • 


Cellulose from pine 


5-07 





The wood should, in any case, be dry. When worked 
for gas, the charge is about 50 — 60 kilos., yielding about 
16 cubic metres of gas in 1*5 hours. When worked for 
tar, the charge amounts to one or two hundredweight or 
more, which are distilled in 12—14 houi-s, the initial heat 
being low ; in this case the gas is burned under the retort. 
Much decomposition ensues under 150° C. ; but the more 
carbonaceous products pass over abov^e that temperature. 
As is usual in destructive distillation, the tar becomes 
thicker and darker as the process advances, and the rapid 
application of a high temperature leads to loss of valuable 
products with increase of gas. The writer has seen in use 
round cast-iron retorts 1^ inch thick, 7 feet long, and 3^ 
feet in diameter ; when worn underneath, these could be 
re-set bottom upwards, and had been known to last from 
three to ten years. Charge, about six hundredweight. 
When the gas is utilised, a ton of wood requires about 
7 — lOJ hundredweight of coal for its distillation, the latter 
being demanded by oak wood. 

In the South United States the destructive distillation 
of wood is carried on (according to Clark) in cast or 
wrought iron or steel retorts, the two latter being especially 
used for large retorts, and the former for small ones. They 
are generally cyhndrical; 3 — 9 feet in diameter, and 5 — 30 
feet long. The furnace gases are first brought under a 
protecting brick arch below the retort, and afterwards 
reversed above it. The most resinous pines, preferably 
with a deep red section, are selected, the old tapped 



WOOD TAE. 85 

trees giving the most abundant yield. The fuel is mainly 
the gas given off by the distillation itself The tempera- 
ture for the first 12 hours is 290°, afterwards increasing 
to 450°. The following are average results from 3.6 
charges: — Wood, 4,573 lbs.; light oil, -875 — -95 sp. gr., 
13-8 gals.; pine oil, -950 — 1*040 sp. gr, 73*5 gals.; pyro- 
ligneous acid, 1-02 sp. gr., 185 gals.; charcoal of poor 
quality, 1*511 lbs. The distillates are allowed to settle 
when the oil floats on the acid. It is distilled down to 
four-fifths, and used for kreasoting purposes. 

Retoi-ts in which the wood is urged forward by a chain, 
or leaves armed with scrapers, are in use for the distillation 
of wood. 

Crude wood-gas contains about 40 per cent, of carbonic 
oxide, 26 per cent, of dioxide, and 11 per cent, of marsh- 
gas. The earlier portions contain a good deal of carbonic 
dioxide with hydrogen and marsh-gas: next follow 
imperfect hydrocarbides and carbonic oxide. The last 
portions are very rich in this oxide. The purified gas 
contains about 3 vols, of hydrogen, -25 vol. marsh-gas, 
•08 vol. hydrocarbides, and -3 voL carbonic oxide. It is 
1*2 times heavier than coal-gas, which it considerably 
exceeds in illuminating power, and requires very open 
burners for its proper combustion. 

The watery portion of the distillate from a ton of wood 
amounts to about 100 — 130 gallons, containing 4 — 8 per 
cent, of the weight of the wood in " glacial acetic acid " 
(hydric acetate), and having the sp. gr. 1-03 — 1*04. This 
is termed "pyrohgneous acid." It is allowed to rest 24 
hours, and then drawn ofi" from below the tar proper 
(wliich, however, is frequently beneath it), and may be 
used at once for making iron mordant, which is a solution 
of scrap iron in aqueous hydric acetate, and contains 
ferrous, ^vith some ferric acetate. It is also treated witli 



«b MANUALETTE OF DESTEUCTIYE DISTILLATION. 

litharge, in order to prepare plumbic acetate (" sugar of 
lead"). A better product is, however, obtained by re- 
distilling the crude pyroligneous acid, an operation which 
is conducted in copper stills, heated by hot gases or an 
internal steam coil (at 25 lbs. pressure). Cast-iron stills 
can be used, but are less satisfactory. Tar deposited here 
must be drawn off hot. The first portion, or 20 per cent, 
of the distillate, consists of dilute crude ivood spirit or 
methylic alcohol (CH^O) ; this is used in preparing 
"methylated spirit" or "finish," a mixture of impure 
methylic with ordinary alcohol. As the methylic alcohol 
leaves the still, a quantity of tar which it held in solution 
separates out. The subsequent acetic distillate has a 
brownish-yellow colour. It is purified by conversion into 
sodic or calcic acetate, by saturation with the correspond- 
ing carbonate. The resulting solution is evaporated to 
dryness and roasted to a point just short of decomposition 
(240° in the case of sodic acetate) ; this treatment destroys 
all tarry matter. The residue can now be distilled with 
hydiic sulphate or chloride, either with or without a 
previous crystallisation from water; the operation is 
performed in horizontal retorts of cast-iron. If sodic 
acetate be the salt chosen for treatment with hydric 
sulphate, the residue in the retort is sodic sulphate, which 
can be sold to the soda manufacturer. The amount of 
hydiic sulphate or chloride used must depend on the 
amount of acetate present ; but this latter is always kept 
slightly in excess when hydric chloride is used, so as to 
avoid the presence of chlorine in the distillate. Calcic 
acetate requires rather less than an equal weight of 
aqueous hydi^ic chloride of sp. gr. 1-16. When hydric 
sulphate is employed, it is difficult to avoid contaminating 
tlie product with sulphurous oxide, more especially when 
imperfectly roasted acetate is used ; in this case, there 



WOOD TAR. 87 

must be fresh rectification over some oxidiser, potassic 
dichromate for instance. 

Many distillers rectify their crude " naphtha " (with or 
without the acetic distillate added) with hme. This keeps 
back tarry matters, and converts methylic acetate into 
alcohol. The high specific gravity of the acetate renders 
this operation important. Cofiey's stills are in use for the 
further rectification of the naphtha. 

Naphtha can be made " miscible " with water by diluting 
till perfect precipitation ensues, agitating warm with 
melted parafiin, cooling with sustained agitation until 
the paraffin sets, filtering and redistilling. The paraffin 
can be steamed and used again several times. 

Hydric acetate, even in the glacial condition, can also 
be prepared by a process contrived by Melsens. This 
consists in half-saturating the aqueous solution with 
potassic carbonate, evaporating to dryness, and heating 
to incipient fusion. The residue, which consists of hydi'O- 
potassic acetate [KH. (0211302)2], is transferred to a retort, 
and distilled below 300°. The distillate is at first 
somewhat aqueous, but soon increases in strength, and 
then solidifies on cooling. The residue in the retort is 
neutral acetate, which can be evaporated again and 
distilled with a fresh portion of hydric acetate. 

In preparing acetic distillates, the spouts of the retorts 
and worms must be made of copper. Worms have also 
been constructed of tin, and even silver ; earthenware is 
not so advantageous. 

Little, if any, glacial acetate is now made in this 
country. 

Among the constituents of crude wood spirit, the fol- 
lowing have been traced : acetone (at least 3*4 per cent.) 
and higher ketones; aldehyde, dimethylacetal, and allyl 
alcohol, propyl aldehyde, and dimethylfurfuran ; methylic 



88 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

formate and acetate, formic, crotonic, and angelic acids ; 
pyroxanthin, CjgHjgOg ; traces of ammonia and methyl- 
amines. 

The tar proper is seldom utilised, at any rate, in Great 
Britain; and mnch of the Russian wood-tar is adulterated 
with brown British naphtha. [Genuine Russian tar, from 
the roots of conifers, has the sp. gr. 1*06.] On distillation, 
it yields (at 70°— 250°) a hght oil of sp. gr. -841— -877. 
This contains, successively, oxy-products, including syl- 
vane, CgHgO, and benzol to 100° ; chiefly aromatic hydrides 
to 150° ; more aromatic hydrides and phenol, kreasol, &c., 
together with o^z/-phenol {G^fi^, a characteristic product) 
to 200°; then naphthalin and paraffin. The paraffin 
contains lignocerate, ^24)^Afi2^ ^^^ retene. Some pitch 
remains behind. The 150° — 200° fraction is known as 
" wood kreasote ;" it contains kreasol and phlorol. The 
acid tar (180° — 300°) holds phenol, parakreasol, a-metaxy> 
leuol, guiacol, kreasol, casrulignol, and the dimethylic 
ethers of pyrogallol, methylpyrogallol, dimethylpropyl- 
pyrogallol (" picamar "), and propylpyrogallol. The inter- 
mediate fatty hydrides seem to he absent ; but they are 
represented, certainly as far as Cjq, by the corresponding 
fatty ketates (acids), ethylic aldehyde, and methylic 
alcohol. Valerolactone {C^B.^q02) has also been found in 
crude pyroligneous acid. 

The more volatile portion of Swedish pine-wood tar 
yields, after treatment with potash, two terpenes — 
australene, boiling at 158°, and (-I-) sylvestrene, boiling 
at 175°, the two together constituting about 80 per cent, 
of the oil. According to Hager, pure beech kreasote is 
not soluble in twice its bulk of anhydrous glycerin, as is 
the case with other kreasotes. 

Most woods are available for acetate making; those 
being (according to Payen} the best which are " hard," or 



WOOD TAR. 89 

whose cells contain most " matiere incrustante " (oxy- 
cellulose?). Hence tlie trunks are better than the 
branches. Pine-wood yields most tar (14 per cent, from 
dried stems, 18 per cent, from roots) ; beech most liquor 
(45 per cent.) Sawdust can also be used ; bat it requires 
to be forced through the retort by means of an endless 
screw. Peat yields similar products. In Russia the outer 
bark of the birch, after stacking, is made to furnish a 
gi'een tar or " dagget," exceptionally rich^ in pyrocatechin ; 
this is used in the treatment of leather, to which it imparts 
a peculiar smell. 

The kreasoting of wood with wood-tar was known to 
Glauber (1648) ; and the preparation of pyroligneous acid 
is at least as ancient. 

Apple Tar. 

In certain cyder districts, presumably French, the marc 
of apples is destructively distilled. It yields very luminous 
gas and a yellow tar ; the latter turns black on exposure 
to the air, and is thick, but becomes fluid at 80^. The 
product from 100 parts of tar are — 





"Water 


. . 


30-5 




"Benzol" .. 


. . 


15-0 


61-5-< 


Phenol 


. * 


8-0 




Kreasote . . 




3-0 




^Undetermined 


carbides, &c. 


5-0 


f Paraffin oil. . 




4-5 


! Paraffin . . 
^ Carbon 




11-0 
21-0 




Loss 




2-0 



90 MA NU ALETTE OF DESTRUCTIVE DISTILLATION. 



Cork Tar. 

Cork furnislies illuminating gas and a liquid distillate. 
The latter consists of a lighter aqueous and a lower tarry 
portion. The aqueous layer contains hydric acetate and 
higher homologues, ammonia, some methylamine, hydric 
cyanide, and methylic alcohol. 

The tar, which is very fluid, yields 27 per cent, boiling 
below 210° (naphthahn, benzene, 4 per cent, of the tar ; 
toluene, 3 per cent, of the tar). The oil boiling above or 
below this contains very little of a phenolic nature. Much 
anthracene occurs in the portions of highest boiling-point. 

Jute. 

The analyses hitherto made of jute by Cross and Bevan 
point to a mean composition Cj2HjgOg = 2CgHjQ05 — HgO. 
It has been found by the present writer to break up on 
destructive distillation in a different manner from wood, 
viz. : — 



C'lsHlsOg 


= 5C + 


SH^G 


+ C^HgO, 




Fixed carbon. 


Water. 


G-as and tar. 


Calc. 100 . . 


19-6 .. 


29-4 


51-0 


Found — .. 


17-0 . . 


3M 


51-9 



The results are calculated to dry original substance, 
the substance distilled having contained 9*3 per cent, of 
moisture. The "water" in the above statement con- 
tained hydric acetate equal to 3*0 per cent, on the dry 
substance. 

The following experiment on the destructive distil- 
lation of jute was performed in the author's laboratory, 
as in the case of cellulose. 

The sample contained 10'65 per cent, of water, and 



EOSIN OIL. 91 

yielded 1*29 per cent, of ash. The results, reduced as 
before, are iu accordance with the relation : — 



C„H„0, = 70 + 


C^H^O, 


+ SH^O 


Fixed carbon. 


Gas and tar. 


Organic water. 


Calc. 100 .. 27-5 .. 


43-1 


. . 29-4 


Found — .. 27-5 .. 


41-3 


31-2 



The formula for jute is calculated from the analysis of 
Cross and Bevan {Trans. Chem, Soc. 1882, 100—101), 
Avho regard it as having the constitution of an aromatic 
cellulide. This may account for the unusual relations 
between the co-efficients of C on the right-hand side of 
the equation. Jute furnishes 3*0 per cent, of acetate 
when distilled as above described. The amount of tar 
from 100 grammes exceeded Ice. (a little having been 
lost). The gas may have been 38-8 per cent. 

Jute is somewhat " aromatic " in character. This may 
be the reason for its behaving, when distilled, in a different 
manner from wood. 



ROSIN OIL. 

Ordinary pine resin or rosin — a French or South 
American product— is essentially a mixture of hydric pinate 
with sylvate, both of which bodies have the formula 
^20-^30^2' ^^^^ ^^ ^^ probable that the corresponding 
anhydrides are often present. These bodies are perhaps 
oxidation-products of turpentine or turpentines: — 

40,„H„ + 3i), = 2C,„H3„0, + 211,0 
Rosin is stable at 150°. AVhen distilled with about 



92 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

ten parts of zinc dust, it yields toluene (meta)etliym ethyl- 
benzene, naphthalln, and some metliylnaphthalin. 

In the now obsolete manufacture of rosin gas, 100 
pounds of rosin furnished 1,300 cubic feet of illuminating 
gas of high quality, containing about 8 per cent, of 
carbonic dioxide, 8 — 9 per cent, of olefines, and having 
the sp. gr. -58. The tar, in this case, vv^as very fluid, and 
contained benzol, toluol, xylol, cuniol, cymol. 

The destructive distillation of rosin much resembles 
that of wood; but it is wholly a low-temperature industry, 
and can be carried out below 350°, though this tempera- 
ture is often exceeded. 

The retort consists of a vertical cylinder, about two 
diameters high, and having a spherical top and bottom, 
or it may be less preferably pan-shaped. Ordinarily the 
helm is short, but in some cases attains a heiglit of 5 — 8 
feet. It is charged to within a few inches of the top with 
rosin ; an ordinary charge consisting of about 70 barrels, 
holding about 25 gallons (solid after melting) each.* 
Direct heat is applied to the bottom of the still ; and the 
entire operation lasts about 16 hours. Water passes over 
throughout the entire operation. 

The products are — 

60—70 gallons "spirit." 

1,600 „ " oil," for grease-making (if fired 

slow). 
6 — 7 cwt. coke. 
40 — 50 gallons weakly acetic water. 

These numbers may be restated in average per- 
centages : — 



The sp. gr. of solid rosin is about 1'075. 





EOSIX OIL. 




Spirit 




3-1 


Oil 


, . 


85-1 


Coke 


. . 


3-9 


Water . . 




2-5 


Gas and loss 


. . 


5-4 



93 



100-0 

There is very little gas ; but it is heavy, and power- 
fully anaesthetic, containining carbonic oxides, ethylene, 
butylene, and pentine. The layer of coke, containing a 
good deal of gravel and other mineral impurity from the 
rosin, is about 6 inches thick ; sometimes, however, it is 
preferred to work for pitch. 

It is probable that chemically pure rosin would leave 
no fixed carbon on distillation. 

Furck applies direct heat to the bottom of the retort, 
drives superheated steam through an upper central coil 
therein, in order to maintain the temperature, and passes 
steam through the whole mass of rosin. The following 
are the products : — 



Acetic water . . 


. . under 165° 


Spirit (15 per cent.*) . . 


?» 


Oil {25 per cent.) 


„ 290° 


„ (25 per cent.) 


„ 315° 


„ (12^ per cent.) 


„ 350° 



The residue in the still is liquid, and is run off through 
a cock, as pitch. 

Distillation without steam is ordinarily preferred. Oil 
is, moreover, difficult to separate from the water of 
steam distillates. The finest products are produced 
from pale rosins, distilled at the lowest available tern- 



Keckoned on the volume of the rosin. 



94 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

peratures. For particulars of an examination of the 
entire course of a distillation, see page 14. 

The nature of the distillate is partially known. 
Benzol and toluol have been found in minute propor- 
tions in the products of the steam process ; but the 
characteristic feature is a series of C^^^ bodies, directly 
related to turpentine and to the original rosin, just as the 
hexyUc hydride (CgH^^) of petroleum is related to its 
present cellulose (nCgH^QO^). 

Rapidly distilled oil may contain as much as 10 per 
cent, unaltered rosin. Even good quahties have been 
alleged to contain as much as 4 per cent. 

The "bloom" or fluorescence can be more or less 
removed by sun-bleaching, or addition of hydric peroxide, 
nitro-benzol, dinitro-benzol, nitro-toluol, liquid dinitro- 
toluol, dinitro-naphthalin, carbonic disulphide, or by 
heating with sulphur. It is probable also that the bloom 
may be removed by all these reagents from parafiin oils. 

Kosin oil turns the plane of polarisation of light 
30° — 33° to the right — a property which enables it to 
be easily detected and determined. It can be fraction- 
ally dissolved in aqueous potash, and wholly in glacial 
acetic acid. Sp. gr. about '99. 

At the request of the late Prof. Anderson, a partial 
investigation of rosin oil was made by the author. A 
fraction from the "spirit," boihng pretty constantly at 
154o_156°, had the sp. gr. -853 at 14*4°, and almost 
exactly the composition of turpinol {Q-^^R^^^fi. The 
turpinol of Wiggers and List is said to have the sp. gr. 
•852, and to boil at 168°. Their product gives a crystal- 
line hydrochloride CjQlIjg2HCl, but rosin turpinol does not 
appear to do so, and is certainly not identical with ordi- 
nary turpinol. When rosin turpinol is treated with strong 
oil of vitrei, it yields a liquid having the odour of 



EOSIN OIL. 



95 



terebene. When treated with bromine, it famishes an 
oily product, containing from 81 — 43 per cent, of the 
reagent ; chlorine is similarly taken up to the extent of 
50 per cent.; hydric chloride, to the extent of 18 — 19 
per cent. Another fraction, boihng at 188^ — 193°, and 
dried over sodium, agreed in composition very closely 
with turpentine, but it could not be made to yield a 
solid hydrochloride. From these experiments it would 
appear that the order of this destructive distillation is 
(1) acetate, (2) turpinol, (3) terpenes. The spirit, how- 
ever, contained a remarkable fraction of constant low 
boiling-point, consisting of a highly hydrogenised com- 
pound ; when this is distilled with aqueous hydric 
iodide, it produces a polymerised turpentine, and another 
compound not yet examined. 

The following Table, chiefly due to Renard, contains 
a list of the known constituents of rosin oil : — 



Hydrocarhide!^. 



Name. 


Formula. 


Boiling-Point. 


Amylene 


QHio 


35°-40° C. 


Hexylene 


^&S.\2 


67-70 


Pentane . . 


C5H,2 


35-38 


Hexane . . 


CeHii 


64-66 


Toluene hexahydride . . 


C7H14 


95-98 


„ tetrahydride . . 


C7H12 


103-105 


Toluene 


CjHs 


111 


Xylene hexahydride 


CgHig 


120-123 


„ tetrahydride . . 


C8H14 


128-130 


Xylene . . 


CgHio 


136 


Cumene hexahydride . . 


C^gHis 


147-150 


„ tetrahydride . . 


C9H16 


155 (?) 


Cumene . . 


C9H12 


151 


Terebenthene (1) . . 


CioHie 


154-157 


(2) 


C10H16 


171-173 


Cymene hexahydride . . 


C'loHjo 


171-173 


Metiso-cymene . . 


C10H14 


175-178 


Metapropylethyl benzene 


C11H16 


193-195 


Dioctene . . 


^16-^28 


260 


Diterebentyl 


C20H30 


343-346 


Diterebentylene . . 


C2oH,8 


— 


Didecene. . 


C20H36 


332° 



96 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



Aldehydes, 



Formate . . 








CH„0.2 


A cetate . . 








an^Os 


Propionate 








CsHgO^ 


Butyrate 
Isobutvrate 








C4HSO2 
C4HSO2 


Valerate . . 








C5H10O2 


Metliylpropylacetate . 








CfiHioO^ 


Oenantliylate 








C7H14O2 


Nonylate. . 








C9S18O2 


Undecylate 








C11H22O; 



Name. 


Formula. 


Boiling-Point. 


Isolutyl aldehyde 
Valeraldehyde . . 


C4H8O 
C5H10O 


60-62 
96-98 


Ketates. 



101 

118 

146 

164 
153-155 
173-175 



Alcoliols, 



Metliylic alcohol 
AllyHc 



CH4O 
CsHeO 



67 
103 



Kenard considers that about 80 per cent, of rosin oil 
consists of diterebentyl, 10 per cent, of diterebentylene, 
and 10 per cent, of didecene. 

The hexahydrides are isomeric with the define series, 
and boil at about the same temperature as the defines. 
When treated with hjdric nitrate or sulphate, they do not 
form nitro-compounds or sulphonates ; strong nitrate, in 
fact, converts them into oxalate. The terebenthenes are 
IcEvorotatory. The methyhc alcohol amounts to '03 per 
cent, on the rosin ; it is found in the aqueous distillate. 

The long white crystals which separate from undried 
rosin oil, especially the fraction 100° — 105°, on long 
standing, have received various formulae. Recent evi- 



EOSIN OIL. 97 

dence is in favour of the expression CyHj4 02.H2 0. 
According, however, to later researches by Renard, the 
formula is C^H-^^-^H^O, corresponding to a derivative ot 
toluene tetrahydride. 

Rosin ^' spirit " has been used as a substitute for 
turpentine in painting, varnish-making, and currying. 

Both rosin " spirit " and " oil " have the property of 
combining with alkaline and other hydrates to form 
peculiar greasy bodies ; which again can hold together, 
in the form of a buttery mass, an enormous excess of 
hydro carbide. This phenomenon is mainly owing to the 
" unsaturated ^' character of the turpentines, one of their 
oldest recognised chemical properties. Synthetical ex- 
periments carried out in the author's laboratory show that 
the following turpentme mixtures — 

C10H16 + 2CaH202 
C10H16 + NaHO 
C,oH,, + KHO 

furnish what are probably real chemical compounds of 
these. The first solidifies in a few minutes ; the second 
in a few days; the third after a longer period. The 
minimum ratio in the "rosin grease" of commerce is 
about 13(CiQHjg) : CaH202; so that the original calcic 
compound is capable of converting at least eighteen 
times its weight of liquid hydrocarbide into " grease." 

The various rosin greases are all, when destructively 
distilled, decomposed into rosin oil and hydrate. 

In the actual preparation of rosin grease, a small 
portion is rapidly stirred with about three-fourths of its 
weight of slaked hme made to a cream with water. The 
oil and hydrate quickly unite, extruding the superfluous 
water, which is at once run off; the solid compound is 
then diluted with more oil, and the solution stirred into a 

G 



y» MAXUALETTE OF DESTRUCTIVE DISTILLATION. 

further final quantity, nntil the total dilution already 
mentioned is attained. The whole operation takes about 
half-an-hour. 

Rosin grease is used as a lubricant for iron bearings, 
and especially for the axles of pit waggons, which are 
much exposed to moisture. On account of the rapidity 
with which it acetifies under the influence of heat and 
friction, it is not adapted to brass bearings. As ordinarily 
sold, it nearly always contains a kindred grease, made 
from the unsaturated coal-tar hydrocarbides which are 
left when crude benzol is rectified ; baric sulphate, china 
clay, and plumbago are also frequently added. 

A siccatiye rosin oil is prepared by passing an air 
current through a mixture of rosin oil with litharge or 
red lead. The preparation dries in twenty-four hours. 

The purification of rosin oil can be to a great extent 
eff'ected by treatment with hme-water to remove acetate, 
and re-distillation with or without a ciu-rent of steam. 
Open steaming removes almost every trace of odorous 
matter, and the fluorescence of the heavier oil is some- 
times concealed by adding nitro-benzol. It has been 
proposed to lighten the colour and remove the odour by 
stirring with 1 per cent, of water, 8 per cent, of hydro- 
chloric acid (to be diluted Avith 1^ times its weight of 
water), 1 per cent, of red lead, and a further 5 per cent, 
of the dilute hydrochloric acid. After some days the oil 
is removed, washed free from acid, and exposed to sun- 
light. Great care is requisite with processes of this 
kind, inasmuch as oils, if chlorinated, are unsuitable for 
lubricants. Good results would be obtained by steaming 
at ordinary pressures, followed by distillation over an 
alkali {e.g., 3 per cent, of caustic soda), an alkahne reducing 
agent, or zinc dust. 

Rosin oil, more or less refined, is used as a lubricant 



EObIN OIL. 99 

for batching jute, and for the adulteration offish, colza, 
and other oils. It can only be made into a grease Avith 
great difficulty. It should be kept in tin vessels. 

The exports of rosin from New York amounted, in 1881, 
to 920,943 barrels; in 1882, to 906,882 barrels; in 1883, 
to 960,870 barrels. 

Appendix to Rosin Oil. 

Dyagoiis Blood. — When this resin is distilled with zinc 
dust to complete decomposition, a light-coloured oil is pro- 
duced, which is completely volatile in high pressure steam. 
The fraction 100° — 150° of this oil contains toluene, ethyl- 
benzene, and styrolene (which is of course partly con- 
verted into metastyrolene, and constitutes Q>^ per cent, of 
the total distillate). The 200°— 300° fraction consists in 
part of a phenolic oil O^^^^o^^, boiling at 236° — 240°; 
and of two oils not soluble in alkali, whose formula? are 
CnHjgO (fragrant, boiling at 214°— 215°) and C,^Yl.,^fi 
(less fragrant, boihng at 256°— 260°). 

Guaiacum. — The chief product of distillation over zinc 
dust is kreasol (about 50 per cent.), which is accompanied 
by toluene, xylene, and paraxylene (about 30 per cent.), 
small quantities of pseudocumene, and a solid hydrocarbido 
guaiene, 0^^^^. 

Elemi. — In a similar manner, elemi yields toluol, meta- 
and para-methylethylbenzene, and ethylnapthalin. 

A^nmoniacum. — This resin furnishes, with zinc dust, a 
characteristic hydrocarbide C13H20, belonging to the ben- 
zene series. 

Amber. — A fossil pine-resin. Its constituents are an 
organic sulphur compound, pyrites, a fragrant oil, a 
bitumen Cj^H^gO, hydric succinate, 3 — 8 per cent., 10 — 20 
per cent, of two resins soluble in potash or alcohol, and 
70 — 80 per cent, (not taken up by these solvents) havhig 

g2 



100 MANUALETTE OF DESTRUCTIVE DISTILLATIOX. 

the formula C20H30O2. When distilled it melts at 
350° — 400°, swells up, gives off carbonic dioxide and 
inflammable gas, succinate, acetate, an oiJy body, and 
chrjsene. The sulphur, which may amount on the whole 
to '48 per cent., is from one-half to three-fourths in 
organic combination. Ash, -08 — '12 per cent. 

Caoutchouc. — When caoutchouc O^OjQHjg) is submitted 
to a temperature of about 316° in a close vessel, it yields 
a very light volatile distillate, and a residual mass which 
furnishes a good varnish when dissolved in oil. The dis- 
tillate consists of isoprene or pentine (CgHg), together with 
caoutchin (C^oH^g), and other polymers of the terpene 
group : rectification is performed with the aid of steam. 
It soon turns brown in contact with air, especially if 
water be present. It is said to have the peculiar property 
of dissolving copal without the aid of heat, and readily 
takes up many resins and oils. 



PETROLEUM. 



Petroleum is a natural mixture, chiefly of fatty 
hydrides, and proceeds from an unknown source. Petro- 
leum springs generally occur near the base of mountain 
chains. 

The main points to be considered in respect to the 
geological conditions under which petroleum and gas 
occur in quantity seem to be as follows : — 

1. They occur in rocks 'of all geological ages, from 
Silurian upwards. The most productive areas are palasozoic 
in North America, miocene in the Caucasus. 

2. There is no necessary relation to volcanic action. 



PETEOLF.U:\r. 



101 



3. The most productive areas for oil in great quantity 
are where the strata are comparatively mi disturb eel. Oil, 
but in less abundance, frequently occurs when the strata 
are highly disturbed and contorted, but gas is rarely so 
found. 

4. The main requisites for a productive oil or gas field 
are a porous reservoir (sandstone or limestone) and an 
impervious cover. 

5. Both in comparatively undisturbed and in highly 
disturbed areas, an anticlinal structure often favours the 
accumulation of oil and gas in the domes of the arches. 

6. Brine is an almost universal accompaniment of oil 
and gas. 

According to McGee : "Every richly-productive gas 
field, at least in the Eastern States and Canada, is a 
dome or inverted trough formed by flexure of the rocky 
strata ; and in every such dome or inverted trough there 
is a porous stratum (sandstone in Pennsylvania, and 
coarse-grained magnesian sandstone in Ohio and Indiana) 
overlain by impervious shales. These domes or arches 
vary in dimensions, from a few square miles in some of 
the Pennsylvanian areas, to 2,600 square miles in the 
great Indiana field. Within each gas-charged dome there 
are found three or more substances arranged in the order 
of their weight ; gas at the top, naphtha (if it exists in 
the field) and petroleum below, and finally w^ater, which 
is generally salt, and sometimes a strong and peculiar 
bitter. This order is invariable throughout each field, 
w^hatever its area, although in Indiana, at least, the oils 
are found most abundantly about the springing of each 
arch, while towards its crown gas immediately overlies 
brine ; and the absolute altitude of the summit-level ot 
each substance is generally uniform whatever the depth 



102 MAXU ALETTE OF DESTRUCTIVE DISTILL ATIOX. 

beneath the surface. Since the vohmie of gas or oil 
accnmulated in any fiekl evidently depends on the area 
and height of the dome in which it is confined, and upon 
the porosity and thickness of rock in which it is contained, 
the productiveness of a given find may be definitely pre- 
dicted after the structure and texture of the rocks have 
been ascertained. 

" In all productive bitumen fields the gas and oil are 
confined under greater or less pressure. When a gas well 
is closed, it is commonly found that the pressure at the 
well-head gradually increases, through a period varying 
from a few seconds in the largest wells to several minutes, 
or even hours, in wells of feeble flow ; and that afterwards 
the pressure-guage becomes stationary. This is the ' con- 
fined pressure,' 'closed pressure,' or 'rock pressure' of 
the prospector; or, more properly, the 'static pressure.' 
When a well is open, and the gas escapes freely into the 
air, it is found that if the stem of a mercurial or steam 
gauge is introduced, a certain constant pressure is indi- 
cated. This is the ' open pressure ' or ' flow pressure ' of 
the gas expert, and the capacity of the well may be 
determined from it. The static pressure varies in diff'erent 
fields. In Indiana it ranges from 300 to 350 pounds per 
square inch, in the Findlay field it is from 450 to 500 
pounds, and in the Pennsylvania field it varies from 500 
to 1)00 pounds. 

" The cause of this enormous pressure is readily seen 
in Indiana. The Cincinnati arch (in which the gas of the 
great Indiana field is accumulated) is substantially a dome, 
about fifty miles across, rising in the centre of a strati- 
graphic basin fully 500 miles in average diameter. 
Tliroughout this immense basin the waters fafling on the 
surface are in part absorbed into the rocks, and conveyed 
towards its centre, where a strong artesian flow of water 



PETROLEUM. 103 

would prevail were the difference in altitude greater ; and 
the hght hydrocarbons floating upon the surface of this 
ground water are driven into the dome, and there sub- 
jected to hydrostatic pressure, equal to the weight of a 
colamn of water whose height is the difference in altitude 
between the water surface within the dome and the land 
surface of the catchment area about the rim of the 
enclosing basin. Accordingly, the static pressure is 
independent of the absolute altitude of the gas rock and 
of its depth beneath the surface, except in so far as these 
are involved in the relative altitudes of the gas rock and 
a catchment area perhaps scores or even hundreds of miles 
distant. Gas pressure and oil pressure may, therefore, be 
estimated in any given case as readily and reliably as 
artesian water pressure ; bnt while the water pressm^e is 
measured approximately by the difference in altitude 
between catchment area and well-head, that of gas is 
measured approximately by the difference in altitude 
between catchment area and gas rock, and tliat of oil 
is measured by the same difference, minus the weight of 
a column of oil equal to the depth of the well. It follows 
that the static pressure of gas (as indicated at the surface) 
is always greater than that of oil, particularly in deep 
wells. It follows also that the pressure, whether of gas 
or oil, is not only constant throughout each field, but 
diminishes but slightly, if at all, on the tapping of the 
reservoir, until the supply is exhausted ; and hence that 
pressure is no indication of either abundance or per- 
manence of supply." 

The comparatively simple structure of the petroleum 
region here described does not obtain all over the world. 
Often the strata in which oil occurs dip at high angles, or 
they may have been sharply folded and broken, the 
denuded edges of the petroleum-bearing bed being 



104 MANUALETTE OF DESTEUCTIYE DISTILLATION. 

exposed at the surface. In such cases the yield of wells 
is comparatively small, there being httle or no artesian 
pressure to force up the oil. Such regions rarely now 
contain much gas. 

Although there is much variety of geological structure 
in petroleum- bearing regions, there is frequently an anti- 
chnal arrangement of the strata, the oil coming up along 
the arch. 

There is no uniformity in the geological ages of the 
strata which yield petroleum. Even in North America the 
age ranges from lower silurian to tertiary; both gas 
and oil also occur in the drifts. Rocks of secondary age, 
however, with the exception of the cretaceous, are not 
oil-bearing in North America. In Europe, only small 
quantities occur in palasozoic rocks. In Hanover it ranges 
from trias to cretaceous. In Eastern Europe it is mainly 
tertiary, and wholly so in the Caucasus. 

In other parts of the world the petroleum-bearing 
beds are, so far as is known, rarely of older date than 
upper secondary. Volcanic rocks occasionally contain 
petroleum, but there is good reason to believe that these 
cases are generally the result of impregnations into porous 
reservoirs of volcanic rocks from neighbouring sedimentary 
strata. 

The oil and gas fields of Pennsylvania and New York 
have a very simple geological structure. The rocks he 
comparatively undisturbed, being only gently folded into 
a series of anticlinals and synclinals parallel with, and 
along the north-west side of the main axes of the 
Alleghanies. These folds have themselves a gentle 
inchnation towards the south-west. In the Alleghanies, 
and to the south-east of the range, where the rocks are 
greatly distru'bed, neither oil nor gas is found. Some of 
the larger gas wells are on or near the summits of anti- 



PETROLEUM. 105 

clinals, but many are not so placed. In the Trenton 
limestone fields of Oliio and Indiana, the productive 
areas are mainly over anticlinals, gas occurring at the 
crown of the arch, oil on the slopes. 

The essential conditions for a largely productive field 
of gas or oil are — a porous reservoir (generally sandstone 
or limestone) in which the hydrocarbons can be stored, 
and an impervious cover of shale retaining them in 
the reservoir. But over large areas the limestone has 
been dolomitized, and so transformed into a cavernous 
and porous rock in which gas and oil are stored. The 
enormous quantities of gas and oil given out from beds of 
limestone and sandstone can be fully accounted for when 
their porous nature, thickness, and extent are taken into 
consideration. Some of these rocks can contain from 
one-tenth to one-eighth of their bulk of oil. 

The high pressure under which gas and oil flow 
from deep borings is in most cases of an artesian 
character. 

In Kansas, gas occurs mainly in the lower coal 
measures. In Kentucky and Tennessee, oil is found in the 
Ohio shales (Upper Devonian), in Colorado in shales of 
cretaceous age. In California it is found in tertiary 
strata, mostly much disturbed. 

In Mexico, the West Indies, and parts of South 
America, tertiary strata seem to be the chief source of 
oil. The age of the petroleum-bearing unfossiliferous 
sands, &c., of the Argentine Republic (province of Jujuy) 
is not certainly known; they have been referred by 
diff"erent writers to various ages from silurian to tertiary ; 
they are probably sub-cretaceous. In Europe and Asia 
the petroleum-bearing beds are of secondary or tertiary 
age, the paleozoic rocks yielding only an insignificant 
supply. 



106 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

In North-West Germany we find petrolenm in the 
Kenper beds, and more or less in other strata up to and 
including the Gault. As we pass to the south and south- 
east from this district we find, as a general rule, that oil 
occurs in newer strata. The various productive horizons 
of different districts are as follows : — 

North-West Germany . . Keuper to Gault. 

Rhone Vallev 1 t 

•^ L . . Jurassic. 

Savoy J 

^•^ . I ., .. Neocomian and Cretaceous. 

Sj)ain J 



la-aryJ 



Oligocene. 

Lower Tertiary (Flysch). 

Eocene. 

Neocomian to Miocene. 



Elsass . . 

Bavaria. . 

Italy . . 

Galicia 

North-East Hu 

Poland -^ 

Koumania r . . . . Miocene. 

Caucasus J 

The important districts of Baku occur on plains over 
anticlinals of miocene beds. 

The petroleum-bearing sands are interstratified with 
impervious clays, separating the strata into distinct pro- 
ductive horizons. 

In Algeria oil occurs in lower tertiary beds. Tlie 
Egyptian petroleum comes from miocene strata. 

Petroleum seems to be unknown in peninsular India ; 
but it occurs in many places along the flanks of the 
Himalayan range, and also in Lower Burma, generally in 
lower tertiary strata. In Upper Burma and Japan, the 
oil-bearing rocks are probably newer tertiary. In all 
these areas the beds are greatly disturbed, and the same 
is the case with the great Carpathian field; but it fre- 



PETE OLEUM. 107 

quently happens that the most productive regions are 
along antichnal hnes. 

In New Zealand, oil occurs in cretaceous and tertiary 
strata. 

Gas occurs in the jet-rock of the upper lias in East 
Yorkshire, along with some heavy hquid bitumen. The 
gas sometimes finds its way down into the ironstone 
mines worked in the middle lias. Mr. G. Barrow states 
that one blower burnt for over twenty years in the 
Crag Hall ironstone mine, a few miles south-east of Salt- 
burn. The jet rock of the upper lias in Yorkshire often 
has hquid bitumen in the beds and inside the fossils, 
especially in the ammonites. 

Bitumen, in various forms, and in small quantities, is 
not uncommon in the fossiliferous palseozoic rocks of 
England. Petroleum occurred in the Deep Main Pit at 
Biddings Colhery, Alfreton, Derbyshire; and in larger 
quanticies in Southgate Colliery, near Chesterfield, from 
the roof of the "top hard" coal. Petroleum, in small 
quantities, has frequently been found in the Derbyshire 
lead mines, which are worked in the carboniferous lime- 
stone; gas also occurs in these mines, which has some- 
times caused explosions. The Mineral Statistics of the 
United Kingdom give the following as the production of 
petroleum in Derbyshire :— 1886, 43 tons; 1887, 66 tons; 
1888, 35 tons; 188i», 30 tons; 181)0, 35 tons; the whole 
of this being from the Southgate Colliery. Petroleum is 
found in the sandstone beds in the coal measures of 
Shropshire: some of it was sold years ago under the 
name, " Betton's British Oil." 

From the very frequent occurrence of sahne water in 
most petroleum-bearing beds, we might occasionally 
expect to find that petroleum or gas occurs with rock 
salt ; but this seems to be seldom the case. Marsh gas 



108 MAXUALETTE OF DESTRUCTIVE DISTILLATION. 

has been noticed, although rarely, in rock-salt mines at 
Northwich (where petroleum also occurs), and Winsford, 
but only in small quantities. In North- West Germany, 
and also in Roumania, rock salt and petroleum occur in 
closely associated strata, but not together. 

Gas was found in the early borings for salt at Middles- 
brough ; and at the Seaton Carew boring some oil Avas 
obtained. In both cases the source probably was the 
upper beds of magnesian limestone. 



United States. 

The earliest notice dates from 1(52 7, where some oil 
springs near Lake Erie were \asited by Daillon, a French 
missionary. In 1789 it is recorded that the Indians sold 
the oil to the white people at four guineas a quart. 

There is good reason to believe the petroleum of 
Pennsylvania w^as knoAvn to races who preceded the 
Indians, as here and there shallow wells or holes 
abound, evidently made for petroleum, the history and 
uses of which were unknown to the Indians. Some of 
these ancient pits still remain in the wilder parts of 
Warren Co., but elsewhere they have disappeared. The 
early petroleum Avells were very shallow, only a few feet 
deep, in which water and petroleum collected, and the 
latter, floating on the top, Avas taken up by blankets. 

Petroleum and gas in deep wells and borings seem to 
have been discovered accidentally in 1814, in Ohio, Avhen 
boring for salt and brine. In 1829, a rather remarkable 
event occurred near Burkesville, Cumberland Co., in 
Kentucky. In boring for salt-water, oil Avas struck, Avhich 
discharged many barrels at interA^als of from two to five 
minutes. After spouting in this Avay for three or four 



PETROLEUM. 109 

weeks, the flow became constant at several thousand 
gallons per day. The oil flowed into the Cumberland 
river, and when set on fire it burned on the surface of the 
water for more than forty miles below the well. 

Although the impoi-tance of boring for oil should have 
been apparent from the success of the accidental trial in 
Kentucky, and from others in Alleghany, no systematic 
attempt to drill for oil was made till 1859, when Mr. 
Drake, the superintendent of the Seneca Oil Company, 
put down the famous " Drake Well " at Titusville. This 
was bored only 69-| feet to an oil-bearing bed; the 
oil rose to within 10 feet of the surface. The well pro- 
duced, at first, 25 barrels a day by pumping ; but after- 
wards the yield fell to 15 barrels. Numerous wells were 
drilled in the following year (1860), and in 1681 the 
first " flowing well " was obtained on Oil Creek. At once 
many other wells were bored, some flowing at the rate 
of from 2,000 to 2,500 barrels per day. Wells were 
quickly bored in other areas, and the oil industry rapidly 
developed. The first pipe for the transport of oil was 
laid in 1865. 

In accounts of the earlier explorations for petroleum, 
we read little of natural gas; the gas had probably 
escaped into the air, and it was only met with in quantity 
and under pressure where deep borings were carried out. 
As far back, however, as 1821, natural gas was used in a 
small Avay for lighting houses at Fredonia, Chatuaqua 
Co., New York. In 1845 it was observed near Utah. No 
further development of this industry seems to have taken 
place till 1870, when gas engines were run by natural gas 
at Pine Grove, in Venango Co. In 1872 gas was dis- 
covered at Newton, and was laid on in pipes to consumers 
for fuel and light. Gas was used in iron-making at 
Leechburg in 1874. 



110 MAXUALETTE OF DESTRUCriYE DISTILLATIOX. 

Pennsylvania^ New York, Ohio, and Indiana. — The 
quotatiou given on p. 101 sufficiently illustrates the 
general character of this important region. Its amazing 
productivity is well known, and statistics of the various 
districts are readily available. To emphasise some 
points of chief geological interest is all that can here be 
attempted. 

The geological position of the gas and oil-bearing 
rocks range from lov/er silurian (Trenton limestone) to 
lower carboniferous. Until the gi'eat stores of the Trenton 
limestone were discovered, the Devonian and lower car- 
boniferous strata were the most important sources. 

The oil-sands of Venango Co., Pennsylvania, are often 
in lenticular beds, the longer axes of the beds ranging 
from north-east to south-west. In thickness they range 
from a thin band up to 100 feet. Their width may be 
only one or two miles, their length sometimes 20 miles. 
Some of the strata die out before reaching the outcrop, 
and consequently are known only by borings. 

AVhen two or more such beds occur in vertical succes- 
sion, the lowest usually contains most oil or gas. The 
lenticular nature of the sand may explain how in some 
cases neighbouring wells affect each other, whilst else- 
where they may not do so. 

The early borings were mainly along valleys. When 
explorations were carried on over high ground, the beds 
discovered were called " mountain sands." These he some 
hundreds of feet above the true Venango sands; they 
occasionally contain some oil and gas. Beneath the 
Venango group, other gas or oil-bearing sands were 
subsequently discovered, the most important of which are 
the Warren sands of Warren Co., and the Bradford sands 
of McKean Co. The Berea grit is the most important 
source of oil in Eastern Ohio. 



PFTKOLEUM. Ill 

Tn all cases these productive sands are underlain and 
overlain by shales. The underlying shale is the source of 
the petroleum or gas ; the sand is the porous reservoir in 
which they are stored ; the overlying shale is an imper- 
vious cover Avhich retains them in the reservoir. 

When gas and oil are found stored in limestone, they 
may sometimes have been produced in the limestone 
itself, but the impervious cover of shale is still required to 
retain them. The Trenton limestone, the chief source of 
gas and oil -in Indiana, and an important source now in 
Western Ohio, is the upper member of a series of lime- 
stones which have been proved to a depth of 1,'S()0 feet. 
The true Trenton limestone itself is several hundred feet 
thick. All this thickness of limestone may have produced 
the hydrocarbons, although they are stored mainly in the 
upper part of the Trenton. But not always so : it is only 
when the Trenton limestone occurs in the cavernous con- 
dition that it is highly productive. This condition is due 
to some of the lime having been removed, its place being 
taken by magnesia. 

The storage capacity of the porous sandstone and lime- 
stone is very great, and sufficiently accounts for the great 
yield of the wells. The Waterlime bed, at 500 feet in 
thickness, and ^vith a capacity of only 0*1 per cent., would 
contain 2,500,000 barrels of oil per square mile. One 
hundred square miles of such rock would yield the entire 
production of New York and Pennsylvania up to January, 
1883. But the capacity for storage is often much more 
than the figures taken here. Carll has shown that some 
rocks can contain from one-tenth to one-eighth of their 
bulk in oil. 

As already described, the most productive areas of the 
Trenton limestone are mainly over anticlinal lines, in the 
arches of which the gas and oil are stored. Sometimes 



112 



MANUALETTE OF DESTKUCTIYE DISTILLATION. 



these anticlinal areas are closed at one or both ends, by 
the compactness and impermeability of the rock. 






Kvipufj 



pmo^o 




5 



B'^ 



limestone, 
shale, 
limestone. 
Eiver sha 
shale, 
harle. 


1 

CO 

cy 


iagara 
iagara 
[in ton 
udson 
edina 
tica S 


3 



;z; ;z; O W ^ h:> H 



o 
w 
o 

o 



o 

o 

X 
H 

O 

H 
O 
K 
02 



t- O kO 



The anticlinal structure seems to be of more import- 
ance with gas than with oil, the gas collecting in the 



PETROLEUM. 113 

crest of the arch. But complete anticlinals are not always 
formed ; often there is merely a lessening of the dip, the 
gas colleoting on the terrace. In Eastern Ohio man;y of 
the gas and oil-fields have this terrace-hke structm-e. 

The village of Murraysville (Co. Westmoreland), north- 
east of Pittsburg, is the centre of the principal gas area, 
which is about half-a-mile wide by 6 miles long. It con- 
tained (1884) nine wells, one of which is 1,320 feet deep. 
Tarentum. Washington (Penn.), and Canonsburgh are 
other centres. 

The (computed) value of natural gas used in the 
United States was 475,000 dollars in 1883, and 1,460,000 
dollars in 1881. 

The depth of the petroleum wells in the United States 
increased from 436 feet in 1861, to 1,606 feet or more in 
1878. There has been a further increase in depth since 
the latter year, especially in certain localities. Thus the 
comparatively recently drilled Gordon well in Washington 
Co. has a depth of 2,400 feet. The cost of this well is 
stated to have been 7,500 — 8,000 dollars. 

The surface diameter generally averages about 10 
inches, and the bottom diameter 5f inches. 

The distribution of petroleum from the oil districts, 
and the mode of conveyance, are certainly among the 
most striking features of the industry. Pumping-stations 
convey the oil from something like 21,000 isolated oil 
wells of Northern Pennsylvania, and carry it to Philadel- 
phia, New York, Baltimore, &c. It is pumped from 
valleys over the hills, the highest elevation being in any 
one place above 1,500 feet. The pumping-stations are 
distant from 20 to 25 miles, and the oil is pumped in from 
the 20-mile station in advance into enormous reservoirs of 
100 feet in diameter, and 40 feet to 50 feet in height ; it 

H 



lU 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



is again pumped out for another 25 miles, and so on 
to Baltmiore and Philadelphia. 

Petroleum is apparently produced by the long-con- 
tinued application of a gentle heat to some derived form 
of cellulose ; for if the temperature were a high one gas 
must be evolved from the soil in more places, and in far 
greater volume than is ever found to be the case. 

An exceptional well (the " Delameter '') in Butler Co. 
is said to evolve 1,000,000 cubic feet per hour (about 300 
tons per day), at a pressure of iOO lbs. per square inch. 
This gas has an illuminating power of T-J candles, and 
contains about 82 per cent, marsh gas, 10 ethylene, and 
7^ hydrogen. 

Ford has given the following analyses of gases from 
the " gas wells " of Pennsylvania : — 



Carbonic dioxide . 


. 0-00 


•61 


•81 


„ oxide 


•40 


•61 


•81 


Oxygen 


. 2-60 


•40 


•61 


Ethylene 


•80 


•61 


•81 


Hydrogen . . 


3-51 


29-75 


2^94 


Marsh gas . . 


. 88 -40 


68 01 


94 02 


Nitrogen 


. 4-29 


0-00 


0-00 



100^00 100-00 100-00 100 



00 


•67 


40 


3-12 


61 


2-90 


61 


2-45 


67 


31 ^52 


72 


39-97 


00 


19-35 


00 


100 -00 



A good well yields about 15,000,000 cubic feet m 24 
hours, at a pressure of under 200 lbs. per square inch. 
Carnegie's results (Pittsburg, 1884) are as foUows : — 



Carbonic dioxide 


•8 


•6 


.. 


•4 


.. 


•3 


„ oxide .. 


1^0 


•8 


•58 


•4 


1-0 


•6 


Oxygen .. 


1^1 


•8 


•78 


•8 


2-10 


1-2 


Ethylene . . 


•7 


•8 


•98 


-6 


•80 


•6 


Etbylic hydride . . 


3-6 


5-5 


7-92 


12-30 


5-20 


4-8 


Marsh gas 


72-18 


65^25 


60^70 


49-58 


57-85 


75-16 


Hydrogen 


20-02 


26^16 


29-03 


35 -92 


9-64 


14-45 


Nitrogen . . 




•• 


-• 


•• 


23-41 


2-89 



100-00 100-00 100-00 100-00 100 00 100-00 



PETROLEUM. 115 

Petroleum contains in solution both hydrogen and tlie 
fatty hydrides C — C^, which are gases or vapours nnder 
ordinary conditions; these latter were detected by Ronalds 
and Fouque. The Hquid terms C^ — C^^ were isolated by 
Pelouze and Cahonrs, and by Schorlenimer : solid paraffins 
C25 — C3Q are also present, in amonnt increasing with the 
density. The last chemist found traces of benzol and its 
homologues (aromatic hydi'ides). In the portion of Penn- 
sylvanian petroleum boihng at 170° — 190° Engler found 
•2 per cent of pseudocumene and mesitylene. (Baku oil 
contains about '1 per cent., and small quantities occur in 
the oils of Alsace, Galicia and Italy.) Warren has detected 
the olefines C^^ — C^g ; gaseous defines also occur. Of the 
above constituents, hexylic hydride, CgH^^, a substance 
closely related to cellulose, nCQH.^QO^, is the most charac- 
teristic; this was also found by Greville Williams in 
boghead cannel oil. The highest known hydi-ocarbide in 
American petroleum is unsaturated, melts at 260°, shows 
a strong blue fluorescence, and has the formula (CqE.^)?i, 
n being probably 4. The oil of high boiling-point also 
contains anthracene, chrysene, pyrene, fluoranthrene 
(C.H,) n, &c. 

Native petroleum is always more or less coloured, and 
requires refining with caustic soda and vitriol, just as is 
the case with artificial petroleum. Sp. gr. -73 — -97, the 
lighter gravities predominating : sp. gr. of Peunsylvanian 
oil, '79 — '83. American petroleum is distilled prior to 
export, in order to remove the dissolved gaseous hydro- 
carbides, which, if allowed to escape into the air, would 
furnish a readily inflammable and explosive mixture. 
Such distiUation may be performed under reduced 
pressure at first, and the evolved vapours liquefied by 
compression. The processes of purification present no 
peculiar features. 

h2 



116 MAXUALETTE OF DESTRUCTIVE DISTILLATION. 

The distillates from average petroleum of sp. gr. -79 
have been stated as follows: — 







Per cent. 


Sp. gr 


Gasohne 




. . 1—1-5 


'Q6 


"C Naphtha" 




10 


•70 


"B Naphtha" 




2-5 


•72 


"A Naphtha" 




. . 2—2-5 


•74 




16-5 




lUuminant . . 




. „ 50—54 


•81 


Lubricant 


. . 


17-5 




Wax 




2 




Loss .. 


•• 


10 





100-0 

After the illuminating oil has been removed, the stills 
are sometimes fired more slowly, thus causing their con- 
tents to undergo partial destructive distillation. The 
heavy oil is thus " cracked " into marsh gas and hydrogen, 
naphthas, illuminant, and a thick " residuum '* (lubricant). 

Ohio petroleum of sp. gr. -791 has furnished: — 

16 per cent. Naphtha, 70° Baume. 
68 „ Burning oil. 
6 „ Paraffin oil. 
10 „ Residuum. 

Maybery and Smith found a sample of it (sp. gr. '925) 
to contain 11'97 per cent, of sulphur. 

In the census year 1879-80, the total amount of crude 
petroleum treated was 731,533,127 gallons, at the follow- 
ing cost (Peckham) : — 



PETROLEUM. 



117 



Fuel 

Acid 

Alkali 

Bone-black 

Packages . . 

Bmigs, paint lioops, 



;lue, &c. 



Dollars. 

1,319,008 

1,206,200 

105,770 

62,815 

15,319,215 

645,412 



The value of the crude oil is estimated at 16,340,581 
dollars. 

The 12 refineries at Pittsburg employ (1886) 9(^0 
hands, whose wages amount to say 490,000 dollars. The 
capacity of these refineries is 77,008 barrels crade a week. 
The yield of refined oil is about 75 per cent, of the crude, 
which, if the refineries were all running to their capacity, 
is equal to about 3,500,000 barrels refined oil a year. 

Petroleum and its waste products are themselves de- 
structively distilled in the United States for gas. 

Petroleums vary very much. The best and safes 
guide to their composition and usefulness is a knowledg 
of their specific gravity and the percentage of bromin 
they absorb in dry solutions. 

The follo^ving table shows the amount of petroleur 
raised in the United States, and exported : — 



Years. 


Barrels. 


Production. 


Export. 


1859 

1860 

1861 

1862 

1863 .. 

1864 

1865 

1866 

1867 


5,000 
520,000 
2,113,600 
3,056,000 
2,610,000 
2,130,000 
2,721,000 
3,732,600 
3,583,000 


26,000 
259,000 
672,OCO 
759,000 
709,000 
1,605,000 
1,596,000 



118 



MANUALETTE OF DESTRUCTIVE DISTILLATION". 



1868 
1869 
1870 
1871 
1872 
1873 
1874 
1875 
1876 
1877 
1878 
1879 
1880 
1881 
1882 
1883 
1884 
1885 
1886 
1887 
1888 
1889 
1890 
1891 



Years. 



Barrels. 



Production. 



3,716,000 

4,351,000 

5,371,000 

5,531,000 

6,357.000 

9,932,000 

10,883,000 

8,801,000 

9,015,000 

13,043,000 

15,367,000 

19,827,000 

26,048,000 

29.638,000 

30,460,000 

24,000,000 

24,089,758 

21,600,651 

26,803,400 

28,249,597 

27,615,929 

35,163,513 

45,000,000 

50,150,000 



Export. 



2,313,000 
2,446,000 
3,316,000 
3,800,000 
3,722,000 
5,800,000 
5,492,000 
5,533,000 
6,080,000 
8,315,000 
7,914,000 
9,944,000 
9,961,000 
14,804,000 
14,574,000 
15,628,000 

15,892,259 
16,431,300 
29,051,067 
27,336,254 
33,809,573 
34,452,131 
33,119,256 



The subjoined table shows the fluctuations in the price 
■V barrel of petroleum in America : — 





Per Barrel. 




Per Barrel 


Year. 


Dollars. 


Year. 


Dollars. 


1859 


. 19-77 


1875 


1-33 


1860 


9-77 


1876 


2-61 


1861 


0-52 


1877 


2-37 


1862 


1-00 


1878 


] 17 


1863 


3 11 


1879 


0-88 


1864 


7-85 


1880 


94 


1865 


6-65 


1881 


0-85 


1866 


3-76 


1882 


0-76 


1867 


2-40 


1883 


0-74 


1868 


3-57 


1884 


0-85 


1869 


5 -64 


1885 


0-88 


1870 


3-86 


1886 . ; 


0-81 


1871 


4 -42 


1887 


0-67 


1872 


3-68 


1888 


0-90 


1873 


1-84 


1889 


0-77 


1874 


117 


1890 


0-77 



PETROLEUM. 119 

Kentucky and Tennessee, — As petroleum fields, these are 
not of great importance. But there are some other 
peculiarities which render Kentucky interesting and 
instructive, as a source of gas, which here occurs in the 
Ohio shale. Elsewhere the incursion of salt water into a 
gas well is the sure precursor of failure, showing that the 
reservoir is becoming exhausted ; but here salt water and 
high-pressure gas occur together. Some of the wells here, 
also, have been long productive; one, at Moreman, has 
been producing gas and brine since 1863. Salt has been 
manufactured here from brine since 1872. Professor Orton 
estimates that the gas from this well has had a total value 
of 200,000 dollars. 

Colorado. — Professor Newbery describes the oil here 
as occurring in the middle cretaceous beds— the Colorado 
shales. Borings have been made to a considerable depth 
at Florence, near Canon city; the deepest (in 1888) was 
3,047 feet. The wells give a steady stream of oil, of 
from 20 — 100 barrels per day, the average being about 
50 barrels. Some of the wells are said to increase in 
flow. There are oil spiings in Western Colorado, but 
these have not yet been developed. The production in 
1887 was 76,295 barrels, and in 1888 was 297,612. 

The total yield of the district in 1890 was about 
1,200 barrels per day, but the wells could yield 2,000 
barrels per day of 31° Baume oil. Out of 300,000 barrels 
of crude oil, 100,000 barrels of illuminating and 5,000 
barrels of lubricating oil have been manufactured. 

Wyoming. — Petroleum has long been known to occur 
here, but it has not been largely worked. The best 
known district is in Carbon Co., where wells to a depth of 
800 feet were put down. Oil came at first under con- 
siderable pressure, but soon fell to a steady flow of from 
600 — 1,000 barrels per day. The oil is of low quality, the 



120 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

luminant averaging only about 25 per cent. It is said 
that oil of a better quality, in some cases yielding 61 per 
cent., exists further to the north-east. 

California, — Petroleum is chiefly found in the southern 
counties. It occurs mainly in sandstone of tertiary age. 
The beds are generally inclined from 30° — 85°, and, con- 
sequently, with outcropping edges. High-pressure wells 
are naturally rare, and the oil is obtained by pumping. 
An exception occurred at Adam's caiion, Ventura Co., 
where a boring 720 feet deep met with oil, which rose 75 
feet into the au% and flowed at the rate of 800 baiTels per 
day. The yield is comparatively small, but the wells give 
a steady production for a longer time than most gushing 
wells. Some wells are now 1,000 feet deep ; one is 2,330 
feet ; but most are less than 1,000. 

There is not much natural gas in California ; it occurs 
near Los Angeles, flowing at a low pressure. The cost of 
wells is stated in the official reports to be about three 
times what it is in Pennsylvania, partly on account of the 
steep inclination of the beds. (The Los Angeles wells 
yield about 160,000 barrels of heaA'y quahty per annum.) 

The statistics of the production of oil in California for 
the past eight years are reported as follows : — 1879, 
568,606 gallons; 1880, 1,763,215; 1881, 4,194,102; 1882, 
5,402,671; 1883, 6,000,000; 1884, 6,000,000; 1885, 
8,760,000; 1886,10,950,000; 1887, 28,500,000. Through- 
out the southern portion of the State there has been a 
great development in the production, and several com- 
panies have been foniied to work it. 

Russian Petroleum. 

Petroleum is found in abundance on the shores of the 
Caspian Sea, more especially in the neighbourhood of 



PETROLEUM. 121 

Apsclieron and Baku ; and tliere are also solid deposits of 
naphthagil or neft-gil, which resembles bitumen, and has 
been worked for hght oil and paraffin. Neft-gil yields 
about 15 per cent, of crude paraffin, and 40 per cent, of 
illuminating oil ; but the yield sometimes amounts to 
40 per cent of paraffin. 

The naphtha region of the Apsclieron peninsula has an 
area of 4*3 square miles, and may be divided into two parts 
— Balakhany, which has yielded naphtha since the earliest 
times, and Sabountchi, which was explored in 1872-3. The 
district (as Abich long ago pointed out) lies over the crown 
of a low anticlinal, which is probably the easterly con- 
tinuation of the great Caucasus anticlinal. 

Another, and an increasingly important, productive 
area is on the shores of the Caspian at Bibi-Eibat, south of 
Baku, and about ten miles from Balakhany. 

The surface is occupied by loose sand, the rocks below 
being of late tertiary date ; beneath these probably he the 
cretaceous and Jurassic strata, which form the main mass 
of the Caucasus, but it is doubtful if any borings have 
touched these rocks. 

The most important area of the Caucasus, after Baku, 
in some respects, is that of Kouban. This lies at the 
north-western end of the range. The wells here are 
usually of smaller depth, and are less productive than at 
Baku, although one well — as far back as 1879 — is said to 
have been bored to a depth of 1,020 feet ; and, in 1860, 
several thousand barrels of oil per day were given by one 
well for a considerable time. Here, as at Baku, tlie 
heaviest oil sometimes comes from the highest beds. 

The third productive area is near Kertch, in the Crimea. 
The wells here are not deep, and, compared with the two 
other districts, are not highly productive. One well, 
however, has been carried to a depth of 940 feet, and 



122 MAXUALETTE OF DESTRUCTIVE DISTILLATIOX. 

produced about 30 barrels per day for a time, its total 
production being about 3,500 barrels. 

Around the Caucasus there are several other petroleum 
fields, which will rise in value when the highly productive 
district of Baku declines. Attempts have recently been 
made to work those near Batoum. 

The construction of the new line of railway from 
Vladikavkas to Petrovsk, which is now being commenced, 
will open up a new and hitherto almost unknown 
petroleum field, situated in Terskoioblasti, near the town 
of Groznii. 

There are comparatively few petroleum areas in the 
interior of Russia ; but oil has been noticed in the govern- 
ments of Samara, Simbirsk, Kazan, and elsewhere ; it is 
also recorded from Petchora, in Archangel. 

Since 1876 above 300 wells have been added, and the 
yearly production of crude oil has increased from 6,000,000 
to 115,000,000 poods, or from 30,000,000 to 575,000,000 
gallons ; and this remarkable increase has been effected on 
the same old territories that were known centuries ago — 
viz., Bibi-Eibat, Balakhany, and Sabountchi, and Surak- 
hane, at a distance respectively of from three to nine 
miles from Baku, and of a total area not exceeding 1,200 
acres. 

The average cost of a well, including labour, derrick, 
boring tools, pipes for casing, boiler, engine, &c., is 
reckoned to amount to 20,000 roubles, or about 2,000/. 

There are 136 refineries, of which the twelve largest 
are furnished with 216 stills, of a capacity of 750,000 
gallons, and producing yearly 125,000,000 gallons of 
kerosene ; and the 124 small refineries, having 325 stills, 
of a capacity of 475,000 gallons, produce yearly about 
15,000,000 gallons of kerosene. Owing to low prices, forty 
of the above-mentioned small refineries have entirely 



PETROLEUM. 123 

stopped operations, and at many others, not except- 
ing large ones, work has now for the same reason been 
partly suspended. It is estimated that by using the actual 
working capacity, taking 300 working days, the twelve 
large refineries are prepared to turn out yearly 200,000,000 
gallons, and the 124 small refineries 125,000,000 gallons 
of kerosene. 

The number of labourers employed on the different 
works has greatly diminished during the last few years, 
owing to a variety of mechanical improvements econo- 
mising mechanical labour, but partly owing also to 
temporary suspension of operations on account of bad 
business. Wages have not much altered, and are as low 
as Is. per day for unskilled, and from 2s. to 4s. for sldlled 
labourers. 

With regard to the future prospects of the actually- 
worked territory near Baku, the level of the subterranean 
petroleum deposits of that territory is steadily lowering at 
the rate of about 50 feet for every 500,000,000 gallons of 
crude oil extracted. The average depth of productive 
wells some ten years ago was 200 feet ; it is now about 
500 feet. 

The number of Avells in working has now increased to 
335 at Balakhano-Sabountchi, to 13 at Romany, and at 
Bibi-Eibat they have remained unchanged at 14. 

The average depth of the bored wells in working is 
96 sagenes (sagene = 7 feet) at Balakhano-Sabountchi, 
120 at Bibi-Eibat, and 103 at Romany. As regards the 
average production of naphtha every 24 hours, only 
including the ordinary bored wells and not the springs, 
it reaches 2,803 poods at Balakhano-Sabountchi, 4,007 
poods at Romany, and 5,616 poods at Bibi-Eibat. 

The highest price of crude oil at the wells is at present 
1 copeck per pood, or less than a farthing for five gallons, 



124 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

and it is estimated that even at such a low figure the cost 
of production is, in the average, safely covered. The 
cost of producing refined oil is more amenable to cal- 
culation. The production of 1 pood of kerosene requires, 
in the average, 3^ poods of crude oil, at 2 copecks per 
pood, dehvered at the refinery, G J copecks ; sulphuric acid, 
IJ copecks ; caustic soda, ^ copeck ; labour, 4 copecks ; 
total, 12 i copecks. The above quantity of crude oil, upon 
having been refined, leaves 1^ poods of residue, which, as 
liquid fuel, may be realising at 2 copecks per pood, giving 
fully 3 copecks, which have to be deducted from 12^ 
copecks. The cost of producing 1 pood of kerosene is 
thus made out to amount only to 9^ copecks, or of 5 
gallons to about 2d. and a very small fraction. The cost 
of heating is not taken into account, as the given quantity 
of 3J poods of crude oil still leaves J-pood partly used up 
for heating, partly destroyed by the very process of 
refining. For storing petroleum in tanks for a period of 
from three to twelve months respectively, from 1 to 3 
copecks per pood, or from about \d. to |d per 5 gallons, 
is charged. For conveying crude oil from the wells to 
the refineries by pipe on a distance of about 8 miles, the 
rate is \d. per 5 gallons, and it was formerly |d The 
freight on the same quantity from Baku to Tsaritsin has 
been reduced from 20 to 13 copecks, or from about bd. to 
'6ld. The railway rate from Baku to Batoum has been 
reduced to 16 copecks per pood, or M. per 5 gallons. 
Through transports to the different markets of Russia and 
Europe at fixed rates are available, but to a very limited 
number of traders. The costs of transports from Baku to 
the more distant markets are as follows : — To St. Peters- 
burg, per 5 gallons, Is.; Warsaw, ditto, lOtZ. ; Odessa, 
ditto, Id. ; Vienna, ditto. Is. M. ; Berlin, ditto, Is. M. ; 
Constantinople, ditto, Id.-, Marseilles, ditto, 8i<i. ; Ant- 



petroleu:m. 



12: 



werp, ditto, S^d. ; Hamburg, ditto, ^\d. ; London, ditto, 

Upon the annexation of Bakn by Russia, in 1801, the 
monopoly of the production of petroleum was granted to 
a refiner named MeerzoefF. This arrangement continued 
until 1872, when an excise duty upon all petroleum raised 
was imposed. 

The duty was abolished in 1877. Mr. Marvin states 
that, from 1821 to 1825, MeerzoefF paid the Government 
131,000 roubles revenue, and afterwards, up to 1839, from 
76,000 to 97,000 roubles a year, or, at the high rate of the 
the silver rouble then prevailing (ranging between six 
and seven roubles to the pound sterling), on an average 
about 10,000/. to 12,000/. sterling. During this period the 
production of crude petroleum rose steadily to more than 
1,000,000 gallons. Afterwards the output was as under : — 



Years. 


Tons. 


Eevenue in 
Eoubles. 


1840. . 
1841. . 
1842. . 
1843. . 
1844. . 




• 




3,565 
3.421 
3,470 
3,434 
3,443 
3,432 
3,480 
3,490 
4,351 
3,340 


105,000 
117,000 
124,000 
119,000 
125,000 
100,000 
93,000 
94,000 
108,000 
100,178 


1845. . 
1846. . 
1847. . 
1848.. 
1849. . 




. 





In 1849 there were about 130 pit wells in operation. 
Between 1850 and 1863 petroleum yielded a total revenue 
of 1,195,000 roubles. From then to 1867 the average 
revenue yearly was 162,000 roubles, and afterwards, until 
the abolition of tlie monopoly, and substitution of an excise 
duty, in 1872, 136,000 roubles. The production in the 
meantime was as follows : — 



126 



MANUALETTE OF DESTRUCTIA-E DISTILLATION. 



STears. 


Tons. 


Years. 


Tons. 


1863 . . 


5,484 


1868 


11,900 


1864 . . 


8,700 


1869 


27,180 


1865 . . 


8.900 


1870 


27,500 


1866 . . 


11,100 


1871 


22,200 


1867 . . 


16,100 


1872 


24,800 



In 1872 the number of pit wells had increased to 415, 
and two wells had been drilled. 

After the abolition of the monopoly, Meerzoeflf for a 
time maintained his supremacy in the trade, but, in 1873, 
the Khalify Company struck a flowing well, and thus 
obtained the largest supply of the crude material, and a 
year later the Transcaspian Trading Company — afterwards 
called the Baku Petroleum Company — took the lead in the 
business. In 1875, Messrs. Robert and Ludwig Nobel 
inaugurated a new era in the Russian petroleum industry, 
introducing improved appliances for producing, trans- 
porting, and refining the oil, and gradually building up 
the great organisation which, under the name of the Nobel 
Company, now conducts so large a proportion of the 
Russian petroleum business. 



Years. 


Tons. 


Years. 


Tons. 


1873 


64,000 


1876 . . 


194,000 


1874 


78,000 


1877 . . 


242,000 


1875 


94,000 







In 1877 the number of di'illed wells had increased 
to 130. 

From 1877 the production of the crude oil has been 
as follows : — 



Years. 


Tons. 


Years. 


Tons. 


1878 


320,000 


1885 . . 


. . 1,370,967 


1879 


270,000 


1886 . . 


. . 2,419,354 


1880 


420,000 


1887 . . 


2,338,709 


1881 


490.000 


1888 . . 


.. 2,821,935 


1882 


680,000 


1889 . . 


. . 3,314,516 


1883 


800,000 


1890 . . 


. . 3,841,071 


1884 


1,130,000 







The sp. gr. of the crude oil ranges from 'S2 — '89 ; more 



PETROLEUM. 127 

usually from '875 — -888. Sabomitchi oil is rather lighter 
than that of Balakhany. 

From 35 to 40 per cent, of the oil may be regarded as 
of illuminating quality. It has furnished 27 per cent, of 
refined product of sp. gr. -821 and flash-point 32°; or 22 
per cent, of sp. gr. -823 and flash-point 50° ; 33 per cent, 
of sp. gr. -820 and flash-point 25° ; 38 per cent, of sp. gr. 
•8215 and flash-point 22=^. 

The sp. gr. of Russian kerosene is -810 — -820. 

Baku petroleum is refined — at first, by continuous 
distillation in 25 intercommunicating stills, each holding 
about 4,000 gallons — into " benzene " of sp. gi*. '754, 
"gasolene" of sp. gr. '787, and "kerosene" of sp. gr. 
•820 — ^822, or even •SGO. The kerosene is pumped into 
u'on tanks lined with lead, each having a capacity of 
57,000 gallons. Here it is churned by an air-blast with 
1^ per cent, of strong sulphuric acid. After subsidence 
it is washed with a solution of caustic soda, and theuAvith 
sea-water. The time required for treatment after distilling 
is 15 — 16 hours. 

Gas and tar are also made from the naphtha residues 
(sp. gr. '903). These are run, at the rate of 100 kilos, in 
24 hours, through two pipes alternately, 13 — 15 cm. wade 
and 2^25 metres long. The pipes are placed in a furnace 
and charged with pumice. 1,000 kilos, of residues yield 
500 cubic metres of gas, and 300 kilos, tar (of " coal " 
quality) ; the tar contains •G per cent, of (30 per cent.) 
anthracene, and 17 per cent, crude "benzol" (boiling at 
120°, and containing 4 — 5 per cent, only of real benzol and 
toluol). The benzol is much contaminated with foreign 
light hydrocarbides, and requires freezing out. About 
300,000 gallons of it are exported yearly (sp. gr. -73 — '16), 
Sometimes, after distilling oif the benzol, the remainder of 
the tar is again destructively distilled. Ordinarily, these 



128 



MA^UALETTE OF DESTRUCTIVE DISTILLATION^ 



residues (" astatki," sp. gr. -880 — 903) are used as a fuel, 
the efficiency of which is about 1-J- times that of coal 
(j). 129). For the preparation of lubricants, see Journ. 
Soc. C/i. Ind.,lSS5,^. 111. 

As regards comparative viscosity, the following table, 
due to Redwood, will prove of interest : — 

Viscosities of Russian and American Oils. 



1. Refined rape oil. 

2. American mineral oil, sp. gr. '885 

3. „ „ „ -913 

5. Russian , „ -909 

6. „ „ „ -915 

7. „ » „ -884 



Temperature. 
Fahr. 


1 


2 


3 


4 


5 


6 


7 


Degrees. 
















50 


7121 1 


45 


425 


1030 


2040 


2520 


.. 


60 


540 1 


05 


29 5i 


680 


1235 


1980 




70 


405 


90 


225 


485 


820 


1320 


., 


80 


326 


73 


171 


375 


580 


900 




90 


260 


63i 


136 


262 


426 


640 




100 


213i 


54 


111 


200 


315 


440 


101*5 


110 


169 


50 


891 


153 


226 


335 


739^ 


120 


147 


i7 


78 


126 


174 


245 


531 


130 


123i 


i4f 


63i 


101 


135i 


185 


3981 


140 


105t 


il 


58 


82 


116 


145 


317^ 


loO 


95i 


37i 


52 


70i 


95 


115 


250 


160 


85 




46 


63i 


83^ 


93i 


200 


170 


76 


. 






58 


10\ 


77i 


161 


180 


69 








52i 


6U 


67i 


134i 


190 


64i 








47 


56i 


61 


1151 


200 


58^ 


. 






42 


481 


54 


99i 


210 


54 


. 






40 








85 


220 


50 


. 






38 










77 


230 


47i 








. , 






. 




70^ 


240 


45i 




















641 


250 


43i 


. 


















59i 


260 




, 














\ 




54 


270 




. 


















48i 


2S0 




. 


















46i 


290 




. 


















44i 


300 


•• 


• 


















42f 



PETROLEUM. 



129 



The following table was given by M. Gonlishambaroff. 
in an article '' Sur les proprietes Physiques et le Pouvoir 
Calorifique des Petroles et des Hniles Minerales" (Comptes 
Eendus, Ixix, 442—453) :— 



Crude Petroleum Oil 





Pennsyl- 
vania. 


EUSSIAN. 






1 


it 


Carbon 

Hydrogen . . 
Oxygen 


per cent. 

84-9 

13-7 

1-4 


per cent. 

86-3 

13-6 

0-1 


per cent. 

86 -6 

123 

1-1 


per cent. 

87-1 

11-7 

1-2 




100-0 


100-0 


100-0 


100-0 


Sp. gr. at 0° C. . . . . 

Heating power, British 
thermal units 

Theoretical evaporation at 
8 atin. pressure, in lbs. of 
water per lb. of fuel 


•866 
19,210 

16-2 


•884 
22,628 

17-4 


•938 
19,440 

16-4 


•928 
19,260 

16-2 



Allen (1887) found astatki to contain carbon 84*94, and 
hydrogen 13*96 per cent. 

The Baku petroleum is, according to Mendeleyeff, 
strongly characterised by the presence of defines ; some 
acetylenes also are present. Its specific gravity for a 
given boiling-point is greater than that of American or 
Scotch oil ; and its viscosity— exceptionally large at first- 
is sooner degraded by heat. It contains at most i per 
cent, of solid paraffins. [The Tcheleken oil, however, 
yields about 6 per cent.] Markownikoff and Oglobine 



130 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

have found a series of liyclrocarbides OJiin (isomeric with 
the ordinaiy defines and hexhydrobenzenes), boiling at 
101°— 247°, having the sp. gT. -7714— -8294, and n = l -15, 
They tenn these substances " naphthenes." 

The still coke is steel-grey, hard and gHstening, and 
difficultly combustible. Sp. gr. 1*829. It contains — water, 
0-24; hydrogen, 0*65; carbon, 94-27; ash, 4*52 per cent. 
The ash contains 15*07 sand, calcic oxide, 5*48, and 76'71 
ferric oxide per cent. ; this last constituent being derived 
from the coiTosion of the retorts. 

Other Caucasian petroleum differs from that of Baku 
by containing far fewer aromatic hydrocarbides. That 
from the springs of Zarskije Kolodzy, in Tiflis, yields a 
portion of lower boiling-point, containing C4HJQ — C^H^q, 
with a little benzene and toluene. The fraction 
180° — 200° contains principally isomers of cymene, meta- 
methylpropylbenzene, with a little of the hydrocarbide 
Cj^Hjg, and defines. In the 240° — 250° fraction occur 
(1) a modification of propylnaphthalene, (2) Cj^Hj^ and 
Cjc^Hj^, and lastly C^gHj^. The investigation of this 
petroleum is attended with much difficulty, by reason of 
a decomposition into defines, &c., which occurs with 
increasing intensity as the temperature rises dming 
distillation. 

Near Wosdinschinski in Northern Caucasia, naphtha 
springs in several places from the soil, and there are large 
deposits of sulphur. 

The Caucasian oil stratum reappears at Krasnovodsk, 
on the eastern side of the Caspian ; and the same stratum 
has been traced for 300 miles across Turkestan to the foot 
of the Himalayas. 

The water in the Caucasian petroleum wells is remark- 
ably rich in sodic bromide and iodide, the wells being 
about 600 — 900 feet deep, and worked by hand. 



PETROLEUM. 131 



Canadian Petroleum. 



The greater part of the Canadian petroleum hitherto 
produced is found in Lambton Co., Ontario. It occurs 
along an anticlinal Hue, the wells being confined to a 
narrow belt of from one to four miles wide and about 
twenty miles long, running from north-east to south-west. 
The oil is here found in Devonian rocks. 

Oil was first pumped here about 1839. Up to 1862 
there are no statistics : in that year the production was 
11,775 barrels. The yield gradually rose to 575,000 
barrels in 1879, it dechned to 250,000 in 1883—1886, and 
then suddenly rose to 868,345 in 1887; in 1888 it again 
declined to 772,392 barrels. The average depth to the 
oil rock is nearly five hundred feet. Several wells have 
been bored in Essex Co. One well in Comber Co. obtains 
a small quantity of oil from the Trenton hmestone. Few 
of these wells produce as much as twenty-five barrels per 
day; the great majority pump only about one barrel- In 
the early days of the Ontario oil industry the wells seem 
to have been much more productive. 

Gas and oil now found in cretaceous strata of the 
prairies and Athabasca may have been derived from 
underlying Devonian rocks ; but in the Rocky Mountains, 
at Crow's Nest Pass, oil is probably native to the cretaceous 
beds. 

Oil in a white sand has been found in Ontario by a 
Natural Gas and Fuel Company. This is said to be the 
first white sand oil secured in Canada. The oil is dark- 
green in colour, 45 gravity, and possesses all tLe cliiirac- 
teristic features of Pennsylvania oil. It is the first and 
only oil found in Canada which is free from the peculiar 
taint and maJ odours of oil produced from limestone rocks. 

] 2 



132 MANUALETTE OF DESTEUCTIVE DISTILLATION". 

Oil is found in the Medina at a depth of 750 feet; 
on the top, and for a considerable distance through it, the 
rock is a reddish hue, changing to grey towards the 
bottom ; the oil was found in the grey sand. 

In Nova Scotia oil is known to occur, it being fre- 
quently seen to rise through the waters of Lake AinsHe, 
and swamps in the district are often found to be covered, 
and many springs impregnated with petroleum. Several 
companies have been formed to test this district, but 
beyond '' indications," nothing has been found. Desultory 
boring has been done in New Brunswick also, on similar 
indications and with identical results. At several points 
in the Province of Quebec, notably in the Gaspe Peninsula, 
oil is known to exist, and much exploratory work has 
been done. In the region lying to the north of the 
territories of Alberta and Saskatchewan, and drained by 
the Peace and Athabasca rivers, lies an immense oil 
region, the exploration of which, slight as it has been, 
has been sufficient to show that it is of great value in this 
respect, and may be expected at a future time to contri- 
bute largely to the output of Canadian petroleum. 

As has been observed, however, the production is at 
present confined to Lambton Co., Ontario, where the oil 
occurs in two distinct " pools," known as the Oil Sprmgs 
and the Petrolia fields, the former comprising an area of 
about two square miles, and the latter of about twenty-six 
square miles (which furnishes nine-tenths of the entire 
yield). 

In 1881, the ratio of cmde to refined oil Avas as 
190-50; in 1887 it was as 100—38. It is now about 
100-^42. In 1882 there were almost 1 600 wells, yielding 
collectively 2,400 barrels per day. The wells are about 
470 feet deep. 

It is ^estimated that some 3,500 wells are now being 



PETROLEUM. 133 

pumped, 2,500 of which are in the Petroha field, and the 
remainder on the Oil Springs field. About 400 new wells 
are annually drilled, to take the place of about the same 
number that are annually abandoned. The oil from these 
is run oiF by pipe hues into the tanks of the various 
tanking companies, the total capacity of which is about 
1,000,000 barrels, certificates being issued to the owners 
therefor. 

Thirteen refineries are in operation, nine of which are 
located in Petrolia, two in London, one in Sarnia, and one 
in Hamilton, These employ about 260 men in and about 
the works, and throughout the oil-producing territory 
there are about 2,000 men employed directly or indirectly, 
in the production of crude and refined oil. 

Muspratt examined Canadian petroleum with the fol- 
lowing results : — 



Light coloured naphtha (sp. gr. -794) . . 


20 


Heavy yellow naphtha (sp. gr. -837) . . 


50 


Lubricating oil rich in paraffin . . 


U 


Tar 


5 


Charcoal . . 


1 


Loss 


2 



100 

The paraffin amounts to about 3 per cent. 

Canadian oil is more difficult to purify than the 
American kind. Even a treatment with litharge and soda 
frequently fails to remove its organic sulphur. It is also 
richer in aromatic compounds, and poorer in gaseous 
paraffins. 

In 1887, Canada produced 594,411 ban-els (of 35 imp. 
gals, each) of crude petroleum. In 1891, 755,298 barrels, 
valued at 200,909/. 



134 manualette of destructive distillation. 

Galician Petroleum. 

The Carpathian!^. — The most important petroleum fields 
skirt the Carpathians, especially along their southern, 
eastern, and northern flanks. In Ronriiania, petroleum lies 
in clays and sandstones of the " Paludin beds " (miocene). 
The oil occurs in four horizons, the lowest being the 
richest in gas and oil. Argillaceous beds, with thick 
deposits of salt, occur under the Paludin beds ; this salt is 
of great thickness, over 650 feet. Formerly the petroleum 
was extracted by shafts of more than 600 feet in depth ; 
about 400 such shafts have been sunk in the neighbour- 
hood of Sarata. When drilling was introduced, the beds 
were pierced to a depth of 1,300 feet. 

Campina, about forty-five miles west of Sarata, is 
another important petroleum district. Wells have been 
drilled to a depth of 1,200 feet. 

Petroleum and salt are worked in Bukowina. 

In Galicia petroleum occurs in the lower eocene beds, 
but sometimes, perhaps, in the upper cretaceous. The 
strata are for the most part highly inclined, generally 
dipping away to the north from the Carpathian highlands, 
but the beds are often contorted. Paul's sections of this 
district show that petroleum frequently occurs in anti- 
clinals of the folded strata. 

Petroleum has long been known to occur in Galicia, but 
it has not been much sought for till recent years. Borings 
now go down to over 1,000 feet ; oil, sometimes with much 
gas, being chiefly found in beds of sandstone. 

The district round Sloboda was formerly the most im- 
portant petroleum field. The development has progressed 
to the west along the line of the petroleum belt, and in 
the district of Ustrzyki a very important area has been 
opened up. The wells do not }aeld large quantities of oil ; 
but they last for a comparatively long time. 



PETROLEUM. 



135 



Galician oil first became an article of commerce in 1854, 
wlien it was sold in Vienna. The first important well 
was completed at Bobrka, in 1861, and the entire develop- 
ment of the Sloboda-Rnngurska section of the Kclomea 
field commenced in 1881 — its present yield exceeding 
1,600 barrels per day. Here and at Wietzno very pro- 
ductive wells have been drilled ; but Ustrzyki is the most 
important locality. 

The oil belt is 220 miles long by 40 — 60 miles wide, 
with a direction mainly north-west to south-east. The oil 
is found chiefly in coarse and fine sandstone, but was 
probably formed in the overlying shale. The sandstones 
belong to the neocomian, cretaceous, and lower eocene 
formations. 

The results of the distillation by Nawratil (1882) of 
nineteen samples of Galician oil are condensed in the 
subjoined table, and show its variable character: — 



No. 


To 150°. 


150°-300°. 


Above 300°. 


Coke and 
Loss. 


1 


43-5 


33-5 


22-9 


•15 


2 


26-6 


42-0 


30-4 


1-0 


^a 


27-5 


34-2 


37-0 


1-3 


36 


11-4 


39-8 


46-5 


2-3 


4 


12-4 


43-6 


41-5 


2-5 


5 


13-5 


50-3 


34-3 


1-9 


6 


19 


29-2 


47-1 


4-8 


7 


22-0 


37-4 


30-1 


2-5 


8 


13-3 


32-8 


49-4 


4-0 


9 


10-9 


34 9 


50-9 


3-3 


10 


20-0 


31-2 


43-3 


5-5 


11 


9-8 


45-4 


40-6 


4-2 


12 


20-9 


30-3 


44-0 


4-8 


13 


11-3 


31-9 


52-3 


4-5 


14 


19-6 


33 1 


42 9 


4-4 


15 


3-4 


38-6 


54-5 


3-5 


16 


8-0 


32-6 


53-2 


6-2 


17 


6-7 


28-2 


58-2 


6-9 


18 


5-7 


29-1 


5G-7 


7-5 



Specific gravity, -799- -902. 



136 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



These figures may refer to ordinary wells. The oil 
from di'illed wells is generally more uniform, having, 
ordinarily, an average sp. gr. '85. 

Gintl obtained the following results with Galician 
rock-oil : — 





West GaHcia. 


East Galicia. 


Yery light oil . . 
Light oil. . 

Heavy oil 

Paraffin 

Hard pitch 

Loss 


20 

50 

(Sp. gr. -824) 

10 

ib 

10 


20 

50 

(Sp. gr. -864) 

"s 

8 
14 




100 


100 



The Sloboda-Rungui'ska oil furnishes about 10 per 
cent, petroleum spii'it, 36^ per cent, kerosene, and 41 per 
cent, intermediate and heavy oils. The Ustrzyki oil, 
which is rather heavier, }delds about 6 per cent, spirit, 
29 per cent, kerosene, and 51 per cent, intermediate and 
heavy oils. The former contains at most 6 per cent, of 
scale ; but the Boryslau oil contains 8 — 10 per cent., and 
that of Starmia 20 — 25 per cent. 

According to Lachowitz, the Boryslau (Galician) oil is 
free from defines, but contains benzene hydrocarbides as 
far as mesitylene, together mtli the usual paraffins. 
{AnnaUn., ccxx, 188.) 

Pawlewski found the Kleczany crude oil to contain 
2 per cent, of aromatic hydrocarbides, mainly consisting of 
benzene and paraxylene. 

The depth of the wells in the Ustrzyki district is 220 — 
250 metres ; the first indication of oil being met with at 30 
metres. In Slobo da-Run gurska the depth is greater, 
ranging to 400 metres. 



PETROLEUM. 



13^ 



In 1889-90 the total Galician production was 523,300 
barrels, having a value of about 234,181/. The official 
figures (probably understated) for Austria-Hungary, are 
as follows : — 

Barrels. 

16(5,500 
233,000 



1883 
1884 
1885 
1886 
1887 
1888 
1889 
1890 



333,000 
433,000 
532,000 
665,000 
746,000 
816,000 



The declared value of petroleum refined in the Austria- 
Hungarian Emphe was as stated below : — 



1886 
1887 
1888 
1889 



£ 
600,840 
655,320 

758,554 
785,816 



At the Peczenyzen refinery (Kolomea), the oil is dis- 
tilled in horizontal stills, containing each 200 barrels, and 
12 charges a month are worked off. Only the benzene 
and kerosene are collected, the rest being used for fuel. 
Pot stills are used elsewhere. The loss amounts to about 
10 per cent. 

Roumanian petroleum may possibly be connected with 
that of Gahcia. The oil-fields stretch along the South 
Carpathians, in the provinces of Prahova, Dimbovitza, 
and Bazen. Istrati, who examined the oils from eight 
districts, found them to yield 42 — 65 per cent, photogen, 
5 — 20 petroleum naphtha, and 11 — 2b solid paraffin. 



138 MANUALETTE OF DESTRUCTIVE DISTILLATION. 



MixoR Sources of Petroleum. 

Petroleum occurs in India, in Upper and Lower Burmah 
(including the Arakan Islands), in Assam, in the Punjab, 
and in Baluchistan. 

The petroleum of Burmah occurs in the upper tertiary 
strata, probably of the age of the Swalck formation in 
India. 

The oil occurs in soft sandy beds, covered by a stiff 
blue clay, chiefly on the top of an anticline, the beds on 
each side dipping north-east and south-west, at angles up 
to 35°. 

The petroleum fields are those of Beme and Twin- 
goung. In Twingoung, of 236 productive wells, only 30 
were 300 feet, the deepest being 310 feet. In Beme, of 
72 productive wells, the deepest was 270 feet. 

Some of the wells have been productive for 100 years, 
but with pumping no doubt this duration would have been 
considerably reduced. 

The maximum production is under five barrels per day ; 
most produce only about one barrel. 

Along the Arakan coast, from Cheduba Island north- 
wards, there are mud volcanoes with hydrocarbon gas. 
Petroleum there occurs at Baranga Island and Ramree 
Island. 

The rocks, of tertiary age, are crushed together and 
greatly folded. Wells have been drilled to a depth of 
over 1,200 feet; for a few weeks one well yielded 1,000 
gallons daily, but the total production from 11 wells for a 
year was only 234,300 gallons. 

Petroleum also occurs in Pegu. 

Just south of Akyab lie the Baranga Islands, and 
still further south the islands of Ramree and Cheduba. 



rElEOLEUM. 139 

In Ramree petroleum occurs at Minbyin, on the western 
side, at Leedaung and Leikmaw, on the south-western 
and western coasts respectively, and at Kyauk Phyn. It 
is also found in Chednba, in the Barangas (principally in 
the eastern of the three islands), and elsewhere in smaller 
quantities. 

Specimens of the oil from the Eastern and Western 
Barangas were analysed by Redwood in 1878. 

The Eastern Baranga oil was dark brown in colour, 
and had a pleasant odour. Its sp. gr. was -835 and 
he obtained from it 66 per cent, of excellent kerosene of 
sp. gr. '810, besides from 2—3 per cent, of more volatile 
products. About 3 or 4 per cent, of paraffin, together 
with lubricating oils, could be obtained from it. 

The Western Baranga oil was of similar colour and 
odour, but of higher sp. gr., viz., '888, and it yielded only 
7 per cent, of kerosene of sp. gr. -815. The residue, how- 
ever, yielded an excellent lubricating oil. 

About the same time Redwood examined samples of 
oil from the mud volcanoes near Kyauk Phyu, and from 
the wehs (10 — 20 feet deep) at Minbyin. The former was 
an oil of pale colour, and of sp. gr. -818. It yielded 56 per 
cent, of kerosene of remarkably high quality, but almost 
the wliole of the material was available for use as burning 
oil. The Minbyin oil had a sp. gr. of -866, and yielded 
only 15 per cent, of kerosene of sp. gr. -810. 

The oil district of Yenangyoung (Creek of Oil, or, 
literally, Creek of Stinking Water) has recently (June, 
1889) been officially reported upon in elaborate detail by 
Dr. Fritz Noetling, Paleontologist, Geological Survey of 
India, who points out that the district comprises two oil 
fields situated about 1 J miles to the east of that place, 
near the villages of Twingoung (Hill of Wells) and Beme. 
It lies on the eastern side of the river Irrawaddy, and is 



140 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

distant about 300 miles from Rangoon, or about 80 miles 
from the terminus of the railway at Allanmyo. The 
country forms a tolerably level and flat plateau, rising to 
2 GO feet above the low level of the Irrawaddy at Yenang- 
young. 

The superficial area of the T^vingoung oil-field, which 
lies between the villages of Twingoung and Enausu, is 
about 90 acres. The total number of the wells of all 
kinds, new and old, is 375, and of these 166 (44*3 per cent.) 
are utterly unproductive. The remaining 209 (55'7 per 
cent.) may be called productive, but these are divided by 
Dr. ^Noetling into "productive wells,'' of which there are 
120 (32 per cent, of the whole), and " scarcely-productive 
wells," which number 89 (23*7 per cent, of the whole). 

One of the wells is 310 feet deep (the greatest depth 
reached by a Burmese dug well), and another 305 feet ; 
the majority of the finished producing wells do not, how- 
ever, exceed 252 feet deep, the difficulties of digging 
beyond this depth both on account of the presence of 
petroleum vapour and because of " caving " being very 
great. It follows, therefore, that these wells drain but a 
small depth of the oil-bearing sandstone. 

The whole area of the Beme oil-field is about 35 acres, 
and the total number of wells does not exceed 151. Of 
these not more than 72 (47 '6 per cent.) are productive. 
Fifty of the productive wells yield more than 20 viss per 
day, and 22 less than 20 viss per day, the daily average 
amounting to 60 to 70 viss. The depth of the Beme wells 
is not as great as that of the Twingoung wells, and, 
according to Dr. Noetling, their yield is smaller, not a 
single well producing more than 165 viss per day, while 
those giving more than 100 viss are scarce. 

The wells are shafts 4 — 4J feet square. Over the 
mouth of the well a cross-beam on uprights is erected. 



PETROLEU-M. 



141 



^Messrs. Finlay, Fleming and Co. estimate the present 
total production of the Yenangyoung fields at 200,000 — 
250,000 gallons per month. 

Much of the crude petroleum from the Yenangyoung 
field contains from 10 — 12 per cent, of solid hydi'ocar- 
bides ; but in consequence of the unfavourable conditions 
under which the work is necessarily conducted, Messrs. 
Finlay, Fleming and Co. do not practically obtain from 
the average raw material more than 4-J per cent, of 
paraffin. The " melting-point " (English test) of the crude 
is 125J° F., and of the refined is no less than 132° F. 
The compa^ny has a candle-making department, but finds 
it impossible to compete against the Dutch stearin candles, 
which are sold at an extremely low price, and the paraffin 
is accordingly exported to London. The other products 
include "naphtha" of sp. gr. '813 and flashing point 
67° F. (Abel test) as well as intermediate and lubricating 
oils. 



Locality. 


Specific 
Grravity. 


Setting- 
Point. 


Flashing- 
Point 
(Abel Test). 






°F. 


°F. 


Yenangyoung (from Tw^inzas 


•887 


82 


110 


wells). 








Yenangyoung (from Twinzas 


•937 


Eemains 


150 


wells). 




fluid at 0° F. 




Yenangyoung (from Finlay, 


•869 


80 


62 


Fleming and Co.'s old No. 1 
bore) . 
Yenangyoung (from Finlay, 








•870 


78 


80 


Fleming and Co.'s American 








bore No. 2, at a depth of 








260 feet). 








Yenangyoung (from Finlay, 


•875 


82 


83 


Fleming and Co.'s American 








bore No. 4, at a depth of 272 








to 330 feet. 









Redwood subjected a portion of the sample from No. 2 



142 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

well to fractional distillation, and found that under atmo- 
spheric pressure it begins to distil at 260° F., but less than 
30 per cent, distils within the range of the mercurial ther- 
mometer. The sp. gr. of the first tenth by volume is "7 79. 
Tlie total distillate amounts to 9'") per cent., and the last 
hah' of this soHdifies at 50° F. Twenty-seven and a-half 
per cent, by volume (equal to about 26 per cent, by 
weight) of kerosene of sp. gr. '823 and flashing-point 
73° F. is obtainable, and about 1*4 per cent, of the more 
volatile hydrocarbides has to be eliminated in order to get 
an oil of this flashing-point. The kerosene is easily refined 
and is of good quality. The heavy oil contains paraffin 
amounting to fi'om 10 — 12 per cent, of the crude oil, and 
the carbonaceous residue, when the distillation is conducted 
to dryness, amounts to 2-15 per cent., the loss (incondens- 
able gases, &c.) being equal to 2*75 per cent. 

Illuminating oil is obtainable from " Rangoon tar " by 
the transmission of low-pressure steam ; paraffin of high 
melting-point and lubricating oil by higher heating. The 
distillates are purified by the successive action of caustic 
soda and oil of vitriol. The light oil has a sp. gr. 0*62 — 
0-89, and boils at 27° — 200° ; it amounts to about 25 per 
cent, of the tar. The natural tar is in use as a lubricant ; 
when partly pmified it is employed as an anti-rust, but its 
entire consumption is exceedingly small. The yield 
amounts — or can amount — to 412,000 hogsheads annually. 

De la Rue and Miiller distiUed crude Rangoon tar in a 
current of steam (which was superheated when the 
boiling-point rose above 100°), and obtained the follo^ving 
fractions : — 



PETROLEUM. 



143 



Below 100° 
110^—145° 
145°— 360° 
About 360° 
Above 360° 



"1 

10 >Ligbt oils. 

20J 

31\ Heavy oils containini 

2 1 J mucb paraffin. 

3 Pitch. 

4 Coke. 

100 



Warren and Storer's very careful researches (1867) 
yielded the numbers detailed below : — 



[Melting-point 
Sp. gr. 



38°_40° 
875] 



Educts. 



Decylene 

Undecylene. 
Duodecylene 
Naphthalin . 
Tridecylene 




B.P. 
175-8 
187-4 
195-9 
208-3—219-5 

232-75 



The fractions below 175° were small in amount, and 
consisted chiefly of heptyhc and octylic hydrides (con- 
taminated Avith defines and perhaps also toluene), xylene, 
nonylic hydiide, nonylene, and cumene successively. 

The following numbers represent much more recent 
(1883) results (Sp. gr. -885) :— 



144 MAXUALETTE OF DESTRUCTIVE DISTILLATION. 

Refined Products. 

Per cent. 

Burning oil (sp. gr. -832) . . .. 30-38 

Lubricating oil (sp. gr. -901) . . 51*24 

Scale (melting at 51-4°) . . . . 10-74 

Bottoms 1-40 



93-76 



Setting-point, 7*2^ 



The only otlier locality in Upper Burmali where petro- 
leum has been actually collected in notable quantity is 
Pagan-Kyet, about 10 miles above Pagan, or about 50 
above Yenangyoung, on the opposite or west bank of the 
River Irrawaddy. Here there are 14 wells which about a 
year ago were officially stated to yield about 8,000 viss of 
oil per month. For some time past Messrs. Finlay 
Fleming and Co. have refined the produce of these wells 
together with the Yenangyoung oil at Rangoon, but the 
yield of the Pagan wells has been steadily diminishing, 
and is now very small. The firm in question have, how- 
ever, obtained a concession, and are about to commence 
drilling in the Pagan oil-field. The oil from this locality 
has a sp. gr. of -837, a setting-point of 60° F., and a vis- 
cosity of 5-91 at 90° F. (rape oil at 60° F. = 100). It is, 
therefore, of considerably less density than the Yenang- 
young oil, and it yields a larger percentage of kerosene, 
but a very much smaller percentage of paraffin. 

In the Ferghana district of Turkestan there were (in 
1883) 200 valley wells, in two chief ranges, 27 and Qh 
miles long respectively, and situated in the limestones 
and slates of the local *' chalk " formation. Sp. gr. of the 
oil, 0-95. 

Persian petroleum yields 87 per cent, of burning oil. 

The pitch lake of T7inidad is well known. The 



PETROLEUM. 145 

bituminous matter comes from the " Newer Parian " 
formation of G. P. Wall, which is probably upper 
miocene. 

Petroleum is recorded from Cuba and from St. 
Domingo. 

In Columhia, the existence of petroleum in some 
quantities has been reported at Tubara, twelve miles from 
Barranquilla, near the mouth of the River Magdalena. 

Mexico. — Petroleum occurs in tertiary beds on the east 
coast, in the State of Vera Cruz, between the Panuco and 
Tuxtan Rivers. The wells so far sunk are mostly near 
the coast. Around Lake Culco there are said to be forty 
oil-springs. 

Algeria. — Petroleum springs were discovered about ten 
years back in Algeria, in the eastern part of the province 
of Oran, at Ain Zeft, nearly midway between Cassaigne 
and Renault. Here the beds are of lower tertiary age ; 
they dip at a high angle from N.N.W. to S.S.E. The 
petroleum, with salt water, comes out of grey and blue 
marls with g^^sum and sulphur. 

Very little has yet been done to explore these deposits. 
The importance of any considerable amount of petroleum 
near the shores of the Western Mediterranean is obvious. 
As regards local consumption, there is the protection duty 
on imported petroleum, which may allow workings to be 
made at a profit. 

In Poland^ petroleum occurs at Wojeza, in the govern- 
ment of Kielce ; it is found in sandstone, intercalated with 
shales, in miocene beds. 

In south-west Hungary^ Croatia, and Slavonia, Dr. J. 
Noth describes the petroleum as occurring in folded 
strata ; sometimes along anticlinals, sometimes where 
these anticlinals have been bent over to the north-east, 
so that a boring goes twice through the same bed. 

£ 



146 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

Further south, petroleura is known in Bostiia. Bitu- 
minous matter also occurs in phocene gravels of Selenitza 
in Albania. No petroleum is yet known in Bulgaria or 
Servia (cf. p. 159) ; but in the latter country the eocene 
strata are rich in bituminous schists, and contain thin beds 
of salt. The whole geology of this country is said by 
Dr. A. B. Griffiths to resemble that of the Galician area. 

In North-Eastern Hungary, along the southern flanks 
of the Northern Carpathians, petroleum occurs in neocomian, 
middle eocene, upper oligocene, and in more recent strata. 
Exceptions to the general rule as to the occurrence of 
petroleum in ordinary cretaceous or tertiary beds are said 
by Noth to occur in parts of this district. To the south- 
east of Nagy-banya, in the Szatmar country, petroleum 
is found in dolomitic limestone, underlying mica-schist. 
In the Nagy-banya basin, and also in the Matra Range, 
it occurs, impregnating trachytic tuffs of miocene age. 

Germany. — Attention has hitherto principally been 
directed to the Liinberger Heide district, known as the 
Oelheim Belt, three miles north of Peine, on the Hanover 
and Brunswick Railway. 

At the eastern part of Oelheim the oil is stored in the 
gault. There seems, also, to be some in the wealden 
beds, and in the upper Jurassic strata. To the west there 
are triassic beds ; but these seem to be mostly barren of 
oil, although Piedboeuf believes that the fossiliferous 
middle trias {Musehelkalk) is the true source of the petro- 
leum, which has been stored in the overlying beds. 

At Horst, petroleum was first found in the gault; 
recent borings passed into lower strata — probably wealden 
— and then obtained oil in larger quantities. Here, as is 
frequently the case, the lighter oil came from the lower 
bed. Petroleum idso occurs at Wietze and Steinfiirder, 
near the River Aller, some miles ncirth of Hanover: here 



I'ETROLEUM. 147 

it lies in the keuper beds, in the immediate neighbourhood 
of rock salt. 

This belt comprises about 25,000 acres, but the borings 
are at present confined to about 20 acres. In 1881, there 
were twelve pumping wells in operation here, yielding 
1,250 barrels per Aveek. At present there are in this 
district 14 pumping wells in operation, with an aggre- 
gate production of 60 to TO barrels of crude oil per day ; 
and 9 wells are in process of boring. Dr. Kramer 
states, that at a recent date the production of the 
Oelheim district had fallen to 50 barrels per day, but had 
since been slightly increased. Petroleum has also been 
found in Alsace, on the Lower Ehine, at Schwabweiler, 
Pechelbronn, and at Lobsan; also near Carlsruhe, in 
the Grand Duchy of Baden. 

At the beginning of the year 1888 there were two 
borings only at Hiinigsen that had been made for the 
purpose of obtaining raw petroleum, and during the course 
of the year eight more borings were undertaken. 

Of these ten oil-wells, six yielded petroleum, three had 
to be given up as useless, and one was still being experi- 
mented upon. 

The output of the two older wells at Hiinigsen has not 
appreciably diminished. At the beginning of 1888 there 
were twelve wells being pumped at Oelheim ; of these, 
four had to be given up, while six became more productive 
during the course of the year. 

At the commencement of 1889 there were no less than 
14 wells being pumped from. 

The following figures exhibit a comparison between 
the outputs for the years 1887 and 1888 : — 



f2 



148 MANUALETTE OF DESTRUCTIVE DISTILLATIOX. 



Hanigsen 54,342 

Oelheini 982,092 



Total (1888) .. .. 1,036,435 

Kgs. 

Total (1887) .. .. 1,003,023 

In the refinery at Peine tlie amount of raw oil Avorked 
up was as follows : — 

Kgs. 

1887 2,323,904 

1888 2,968,828 

The petroleum of Hanover has been known for a long 
time. It escapes from the gault and other beds, to which 
it properly belongs, into the drift sands, and then appears 
at the surface. 

Hanoverian petroleum somewhat resembles coal-tar. 
It contains paraffins, olefines; pseudo-cumol, mesitylene, 
and other aromatic hydrocarbides, in not inconsiderable 
quantities; resins, and sulphur compounds, and their 
hydrides. The lubricating fraction is thin. 

Bavarian petroleum is found comparatively near the 
surface. Colour, greenish-brown; sp. gr. -811. On dis- 
tillation, it yields at 180° 14 per cent, of light naphtha 
(sp. gr. -731) ; at 320°, 39 per cent, of a yellow illuminant 
(sp. gr. -786) ; and thereafter, 16 per cent, of a reddish- 
yellow lubricant (sp. gr. '834), and 25 per cent, of 
lubricant rich in paraffin. 

Oelheim and Wietzer crude petroleum yield nothing 
below 150°. 

In Bavaria, petroleum occurs to the south of Munich, 
on the shores of the Tegernsee. Borings have been made 
to the depth of nearly 650 feet. The quantity of oil is 



PETROLEUM. 



149 



not large ; it occurs in the Flysch (here of lower tertiary- 
age), a series of hard shales, grits, and impure limestones, 
which form a zone along the northern flanks of the 
Bavarian highlands. The beds are sometimes nearly- 
vertical, or they dip at a high angle to the south, in which 
case they may be reversed. 

Beds of asphalt and bituminous schists occur in the 
district. Dr. V. Giimbel states that these by distillation 
yield an oil like that of the Tegernsee. He concludes 
that the petroleum has been thus produced. 

In Elsass, petroleum occurs at Schwabweiler, impreg- 
nating beds of sand and sandstone, which are mainly of 
lower oligocene age, but perhaps partly middle oligocene. 
Borings have been made to a depth of 950 feet. iVt 
Hirzbach the oil occurs in dark-coloured clays, in the 
lower part of the middle oligocene. All the petroleum 
strata yield brine. Dr. Andrae thinks that the petroleum 
here was formed in the rocks in which it is now found. 
Piedboeuf and Strippelmann think that it has impregnated 
them from underlying strata. Petroleum also occurs at 
the foot of the Eastern Vosges, from Worms to Basle. 

The crude oils of the three leading German districts 
have been compared (by Kraemer and Bottcher) Avith the 
ordinary standard oils. The results are as follows : — 











go 








Jd « 






Locality. 


be 


o 


^ 


^ 


i 


be 




u 


i 






a"' 




? 




o 


p. 


s ^ 


p. 


O) 




M 


w 


to 


Ph 


tc 


H 


w. 


35-91 


«3 

-856 


« 


1. Tegernsee 


•812 


20-04 


•726 


26^12 


•782 


14^02 


•825 


3-07 


2. Pechelbram 


•888 


1-.30 


•720 


16 ^37 


•778 


17-07 


•824 


47-88 


-893 


16-28 


3. Oelheim 


•885 


•74 


•750 


11^05 


•805 


9-75 


•852 


73-91 


-900 


3-92 


4. Pennsjlvaaia ... 


•814 


14-34 


•725 


25^35 


•811 


13 ^75 


•820 


40-99 


•850 


5^57 


.=). Galicia 


•842 


14-21 


•723 


16 -93 


•786 


12-30 


•83 1 


47-58 


•882 


8 -95 


6. Baku 


•880 


•63 


•762 


21 -73 


•811 


15-55 


•853 


57-97 


•903 


4-10 



From 1 and 4 (fraction above 250^') 4 per cent, of good 



1^ 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



paraffin was obtained; 2 and 5 pelded 1*5 per cent. The 
percentage of sulphur was in (2j, -14; (3), '08; and (6), 
'0(>. {See also Engler, Dingl. polyt. J., pp. 207 and 268). 

Italy. — Petroleum springs are widely distributed along 
tlie northern flanks of the Apennines, from near Bobbio on 
the west to near Imola on the east ; oil impregnates the 
rocks, which are mostly of eocene age, so that wells are 
frequently contaminated. Petroleum has long been worked 
at Monte Gibbio. Gas, petroleum, and salt water issue in 
small mud volcanoes ; the Salsa di Sassuola and the Salsa 
di Querzola being perhaps the best known. The natural 
gas of Barigazzo has long been famous ; but gas issues at 
many otlier points. 

The foUomng are the most important statistics : — 



Production. 


Importation. 




■s.s 






g-^* 




Year. 


** 


Tons. 


Value in 
Lire. 


II 


Tons. 


1878 . . 


4 


602 


62,000 


98 


Not given. 


1879 .. 


4 


402 


50,000 


70 


55,660 


1880 . . 


2 


283 


88,595 


24 


57,571 


1881 . . 


2 


172 


76,540 


24 


59,571 


1882 . . 


4 


183 


86,844 


121 


61,500 


1883 . . 


5 


225 


58,387 


92 


67,630 


188i . . 


6 


397 


135,452 


110 


73,603 






2,26i 


557,818* 




375,625 



* Equivalent to 22,312^. sterling. 



In 1887, Italy produced 208 tons of petroleum, and 
18,507 tons of asphalt and bitumen. 

Ancona is the chief oil-producing district; Tocco, in 



PETROLEUM. 



151 



Abruzzo (Cliilti Province), being the precise locality of the 
industry. 



Year. 


Mineral 


Production 


Value 


Persons 


Active. 


in Tons. 


in Lire. 


Employed. 


1878 










1879 






— 


— 


— 





1880 


. 


. 




80 


12 000 


11 


1881 


. 


. 




58 


8,700 


12 


1S82 








74 


27,160 


72 


1883 




. 




125 


16,650 


]3 


1884 


• 


• 


Totals . . 


90 


43,900 


17 








427 


108,410 





The position of the Tocco Wells is 400 metres above 
the level of the sea, and belongs to the miocene (superior 
formation). In 1867 we have the first authentic record 
that in boring at Tocco the strata consisted of marl and 
gypsum, until the calcare nummilitico was reached, at a 
depth of 110 metres. The Societa Francese passed the 
calcare nummilitico and part of the calcare cretaceo. 

The dug wells of Montechino, Piacenza, have been 
worked about 80 years; they have a depth not exceeding 
240 feet, and yield 160 — 180 lbs. of a very pure oil per 
day. 

Other Itahan locaHties are Vorghera, Piacenza, Parma, 
Modena, and Caserta. In Sicily, oil has been found in the 
province of Girgenti. 

Porro has examined four specimens of Italian petro- 
leum from Petralio Montanaro (Piacenza), Rivaunazuno 
(Vorghera), Tocco Casiona, and St. Giovanni Incarico. 
The first was of sp. gr. '7849, and gave 44*7 per cent, of 
light oil ; 19-8 at 127°— 150°, 22 at 150°— 203°, 14-4 above 
203°, and 6*9 residue. The second had the sp. gr. -9132, 
and gave 22 per cent, below 220°, 33 at 230°— 270°, 37 



152 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

above 270°, and 7*7 residue. The third and fourth had the 
sp. grs. -951 and '974 respectively; they furnished severally 
63*5 and 69*6 per cent, of oil, 32*2 and 28*3 of pitch, and 
12 and 20 of gas. 

India. — The petroleum of India occurs in middle or 
lower tertiary rocks along the flanks of the Lov^er Hima- 
layas, generally where the beds are highly inclined. 
Frequently it occurs in the neighbourhood of salt deposits, 
or is associated with saline water. 

Throughout India petroleum occurs in the tertiary 
formation, as in Russia and Galicia. The strata in the oil- 
producing localities are greatly disturbed, and drilling is 
everywhere in India more or less difficult. 

Apparently petroleum occurs in the greatest abundance 
in the Khatan oil-field in Baluchistan, but the oil is not of 
satisfactory quality, even regarded as liquid fuel ; the 
locality of production is comparatively inaccessible, and 
the climate is bad. 

Undoubtedly the best oil from the point of view of the 
kerosene refiner is that which is obtained in the Arakan 
islands (the eastern Baranga and Rami, p. 139). 

Petroleum seems to be unknown in Peninsular India. 
The petroleum field of Baluchistan lies in the Mari Hills. 
At Khatan, in a boring 524 feet deep, oil was obtained on 
seven horizons. The petroleum of the Punjab, of which 
great things were once expected, seems to be of small 
value, and Mr. Medlicott thinks it the least productive of 
the Indian areas. 

The petroleum of Assam seems to be of some import- 
ance. It is generally found in the coahbearing beds of 
the middle tertiary. At Makum, oil-springs occur, and 
borings were here made to a depth of nearly 200 feet, 
when oil rose to within 44 feet of the surface. From one 
bore-hole 1,500 gallons were drawn in 12 hours, after 



PETKOLEUM. 153 

which the flow varied much, occasionally reaching the 
original rate. In one hole, 200 feet deep, the oil spurted 
for a time with a pressure of 30 lbs. to the inch. 

Punjab. — Accounts of the Punjab oil-springs were 
published by Mr. A. Fleming in 1848,^ and in 1853 t ; 
by Mr. Maclagan in 1862 1; and by Mr. A. Fenner in 
1866.§ 

A few years later Mr. Lyman was deputed to examine 
the deposits, and liis reports were issued collectively in 
1871.11 From these it appears that in the Rawalpindi 
district there are some 16 spots at which indications of 
petroleum are met with in the tertiary rocks. 

Baluchistan. — The oil-field of Khatan is situated on the 
Mari Hills of Baluchistan, about 40 miles in a direct line 
to the east of Sibi Station on the Quetta branch of the 
North-Western Railway running fi-om Ruk Junction to 
Quetta. 

The oil occurs in the eocene formation, and is found 
exuding in many places, much of the oil which has thus 
escaped having been converted by exposure into a hard 
mass. 

Borings were first made here on behalf of the Indian 
Goverment by Mr. R. A. Townsend, Superintendent of 
Petroleum Explorations, in the cold season of 1884-85, 
and it was found that immense quantities of petroleum 
were obtainable at moderate depths. The wells drilled 
by Mr. Townsend are five in number, and are situated in 
a valley surrounded by mountains about 4,000 feet high. 
Their diameter is only 4J inches, and their depth does not 
much exceed 500 feet. The geological features of the 

* Journ, Asiat. Soc, Bengal, xvii. f Ibid., xxii. 

X Supplement to the " Punjab GoAcrnment Gazette." 
§ Proc. Punjab Government Public Works Department. 
II Reports on the Punjab Oil Lands bj B. S. Lyman, " Government 
Press," Lalioi'e. 



154 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

locality liave been carefully dealt witli by Mr. Townseud 
in an official report.* 

Unfortunately the oil obtained is of remarkably high 
specific gravity and viscosity. Its density is, accord- 
ing to Redwood's recent results, practically identical 
with that of water, and it is in consequence freed with 
very great difficulty from the water with which it is 
associated as it comes from the well. Even when the oil 
is warmed the water does not readily subside. If an 
attempt be made to distil the oil containing water, the 
contents of the still froth up and pass over bodily. By 
prolonged exposure in a capacious vessel to a temperature 
somewhat above the boihng-point of water, the oil can be 
sufficiently dehydrated, but a far better system has been 
suggested, and will probably before long be announced. 
The oil is black or extremely dark-brown in colour by 
transmitted Hght, with comparatively little fluorescence, 
and it possesses very little odour. Its flashing-point is 
280° F. (Abel test), and it contains no hydrocarbons 
available for use as ordinary burning oil. 

According to the official report of Colonel Conway- 
Gordon, experiments made by pumping four of the wells 
(the fifth had not then been drilled) showed that the yield 
of each well was from 400 to 600 barrels of oil in the 
24 hours. " Thus any one of the existing wells is 
more than competent to deliver the entire supply of 50,000 
barrels of oil a year, which is estimated to be the amount 
required for the Sind-Pishin section of the North-Western 
Railway." 

An oil similar to that obtained at Khatan occurs at 
Shoran, in Kalat, in the province of Kach Gandawa, in 

* Keport on the Petroleum Explorations at Khntan, by R. A. Townsend 
Superintendent of Petroleum Explorations in Baluchistan {Records of the 
Geological Survey of India, vol. xix., Part 4, 18S6). 



TETROLEUM. 155 

Rind Baluch country. Slioran is about 42 miles from the 
railway at Belpat, and it is a question which of the two 
fields it w^ould be best to develop for fuel pui'poses. 

The prospect of an abundance of mineral oil in Assam 
has been proved. 

In his description of the coalfields of the Naga Hills, 
published in 1876, Mallet enumerated the places where oil 
has been observed in this district. In all cases the oil 
rises either on or close to the outcrop of the coal-bearing 
gToup, and usually near the outcrop of one or more seams 
of coal ; indeed, Mallet records one instance in which he 
saw the oil oozing out of the coal itself, though he points 
out that this may have been accidental, the coal being 
merely the last rock through which the oil passed on its 
way to the surface. Thick soft sandstone is the rock 
principally met with in boring, but blue clay also occurs. 
The strata, which are much disturbed, belong to the 
tertiary epoch. 

The most likely sites for productive wells appear to lie 
within the area of the immense concessions granted to the 
Assam Railways and Trading Company, and it is well 
known that this Company has for some time past been 
drilling at Digboy. 

Assam crude petroleum is dark-brown in colour, of rather 
high viscosity (the viscosity of a sample of sp. gr. -940 was 
14-2 at 90° F., rape oil at 60° = 100), and has a shght and 
not unpleasant odour. Its specific gravity appears usually 
to range from '933 to -940, and its flashing-point is some- 
times as high as 212° F. (Abel test). It begins to distil 
freely at 280° F., but considerably less than 20 per cent, 
volatilises within the range of the mercurial thermometer. 
The oil contains none of the kerosene hydrocarbides, but 
it yields by the ordinary process of distillation 89 per cent, 
by weight of lubricatmg oil distillates. The proportion of 



156 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

solid hydrocarbides is not large ; the carbonaceous residue 
varies, according to Eedwood's experiments, from between 
3 and 4 per cent, to over 8 per cent. 

Another sample had a specific gravity of -971, and 
commenced to boil at 460° F. 

Egypt. — Petroleum occurs in Egypt, in the vicinity of 
the Red Sea, at Gemsah, and Gebel el Zeit. It doubtless 
originates in the lowest Devonian sandstone (Mitchell), 
nowhere more than 300 feet thick, and resting directly on 
crystalline rocks. Above the sandstone, on the eastern 
slope of the plateau lying behind the crystalHne coast 
range, are layers of marl, alternating with fossiliferous 
breccias belonging to the upper cretaceous formation, 
about 250 feet thick. These are succeeded by more chalk, 
followed by upper miocene limestone about 300 feet 
thick. Oil occurs superficially throughout a district about 
40 miles long and 5 — 12 miles wide. The specific gravity 
of the oil is about -880 ; it has a dark-brown colour, and a 
disagreeable odour, due to the presence of sulphur com- 
pounds. The loss on treatment with vitriol is about 50 
per cent. It yields no burning oil, but a very large per- 
centage of lubricant of apparently good quality. 

Colour, dark-brown, almost opaque ; when diluted with 
petroleum spirit a green fluorescence was observed. 

Specific gravity at 17° C. = 0-9352. 

When cooled to — 15° C, the oil became thicker, but 
no solid separated out. 

The speed of flow, measured at 35° C. in Engler's 
viscosimeter, was 6 min. 40 sec. 

The extracts obtained by treating the oil with water 
and alcohol were neither acid nor alkaline in reaction. 

The ash consisted entirely of iron and lime, and equalled 
0-12 per cent. When the oil was distilled, the only gas 
evolved was sulphuretted hydrogen. 



PETROLEUM. 



157 



The amount of hydrocarbides soluble in a mixture of 
concentrated and faming sulphuric acid in the portion of 
the oil distilling up to 310° C. was found to be 24 per cent. 

The residue (76 per cent.) consisted of paraflfins and 
naphthenes, and gave figures for its refractive power 
closely agi-eeing with those obtained from Baku petroleum, 
which consists chiefly of the latter ; the Egyptian oil, 
however, contained sulphur, even after the treatment with 
acid. 

The oil was examined as to it commercial value by 
distillation from a copper still, superheated steam being- 
employed when the temperature reached 300° C, as is done 
at Baku. 





Per 


Sp. gr. 




cent. 


at 17° C 


Burning oil 


.. 11-3 . 


. 0-841 


Intermediate oil . . 


25-0 . 


. 0-880 


Machine II „ . . 


16-7 . 


. 0-927 


Machine I „ . . 


16-7 . 


. 0-949 


Cylinder 


17-0 . 


. 0-955 


Coke and loss . . 


13-3 . 


— 



100-0 

Peru. — Deposits of asphalt have long been known to 
exist in the north of Peru, near Payta. A tract of land 
20 miles long by 12 miles wide, at Talara, near Payta, has 
now six wells; and the refined product is in extensive 
demand on the west coast of South America. 

In the valley of Tucigal, about 4-7 metres from the 
coast, there are 28 wells, ranging in depth from 45—240 
metres, the daily output of which is 1,000—2,000 barrels. 

The shipments in 1891 from Zairetos amounted to 
2,324,219 kilos. crude oil; 1,190,161 illuminant, and 1,115,667 
lubricant. 



158 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

Salathe states tliat the crude oil from Zairetos yields — 



t° c. 


Per cent. 


Product. 


20°— 30° 


2-8 


Rhigoline. 


30^— 80° 


9-0 


G-asoline. 


80°— 150° 


11 1 


Benzoline. 


] 50°— 230° 


18-5 


Light kerosene. 


230°— 280° 


10-0 


Heavy kerosene. 




12-8 


Liglit lubricant. 


Above 280° 


4-8 


Heavy lubricant, free from 
paraffin, buttery at— 30°. 




31-0 


Pitch. 



There is a pipe line to the harbour of Paloena, which 
is 11 kilometres from the wells. 

Petroleum is known to occur over a tract 120 miles 
long by 60 miles wide on this coast. 

In Venezuela^ between the Rivers Zulia and Catutumbo 
and the Cordilleras, petroleum in considerable quantity is 
expelled from natural springs, together with boiling water. 

In Argentina the Jujuy product has been found to yield 
(from 100 litres) 90 litres of oil sp. gr. -861, and 10 kilos, 
of coke. On distillation, the 90 htres of oil furnished : — 



Naphtha, '740 sp. gr. 
Kerosene, -827 sp. gr. 
Heavy oils, '900 sp. gr. . . 



Litres. 

6 
34 
30 

70 



New Zealand. — Petroleum occurs on the east coast of 
North Island at Poverty Bay, and at Waiapu, East Cape ; 
borings to a depth of about 1,000 feet have been made. 
The rocks of these districts are cretaceous and tertiary. 
Here the crude product yields 84 per cent, of illuminant. 

On the west coast of North Island, at Sugar] oaf Point, 
Taranaki (New Plymouth), a heavy oil, sp. gr. 960—969 



PETROLEUM. 159 

oozes from cracks in a trachyte-breccia ; wells have here 
been bored to a depth of many hundred feet, but no con- 
siderable supply has been obtained. 

Servian oil shale (from Subotinci) yields on dry distilla- 
tion, oil, 34 per cent. ; water, 8 ; ash, 29^ ; carbon (in 
ash), 17-3; gas, 11*5. Purer specimens give as little as 
7 per cent, of oil. 

Japan. — This area has been described by Mr. Lyman. 
Petroleum occurs in tertiary strata probably pliocene. The 
oil-bearing rocks are folded, with the axes of the folds 
running nearly north-east and south-west, the folds being 
frequently reversed ; where so, the reversed dip is towards 
the neighbouring seashore — to the north-west in Echigo, 
and to the south-east in Tootoomi. This structure is 
further complicated by another series of folds, running 
nearly north and south. As would be expected in such a 
disturbed area, none of the wells flow, the oil is raised in 
buckets. The wells range up to over 700 feet in depth. 
The production in 1884 was about 4,750 tons; in 1882 it 
was nearly 3,530 tons. Petroleum has been recorded from 
Saghalien, the large island north of Japan. 

Indications of petroleum have also been recorded at 
Alexandi'etta {Syria), Vannes (Binttany), Miang Fang 
(Siam) ; in Java, Sumatra, and Borneo, There are bonngs 
for gas 3,000 feet deep in tlie district of Tsieu-Lum Taing 
{China). 

Petroleum occurs on the flanks of the Puy-de-la-Poix, 
east of Clermont {France), flowing from the calcareous 
peperino, of Avhich the Pay is composed. Borings, 
recently made near the village of Lussat, are said to have 
met with natural gas at a depth of 450 feet. Petroleum 
is also known near Gavian, in Herault, and near Grenoble. 
It occurs in numerous places along the nortliern flanks of 
the Pyrenees, in cretaceous and tertiarv beds. 



160 MANU ALETTE OF DESTRUCTIVE DISTILLATION. 

Petroleum is found near Burgos (Spain), and also in 
cretaceous beds in Catalonia. 



ASPHALT. 

Asphalt is solid at the ordinary temperature. It ap- 
pears to be formed by the oxidation of the unsaturated 
hydrocarbides in petroleum. The most remarkable deposits 
are in Cuba and Trinadad, the asphalt from which islands 
has been found to yield 1*75 per cent, of paraffin. Other 
noted localities are the Dead Sea, Seyssel (France), 
Limmer, the Abruzzo, aud the Yal de Travers. It occurs 
also, of every degree of consistence, and in immense 
quantity, along the coast of the Gulf of Mexico, chiefly in 
the States of Tamaulipas, Vera Cruz, and Tabasco, where 
not unfrequently it is associated with rock-salt and "salt- 
petre." Asphalt being, like resin and terpenes, somewhat 
acid towards lime, is frequently retained in limestone 
rocks, or contains much lime. Organic sulphur has been 
found in some American specimens to the extent of 10*85 
per cent. It is in gi-eat request for paving purposes. 

Strippelmann and Engler obtained from Bentheim 
asphalt (sp. gr. 1*092), when working on the large scale, 
burning oil, 12*72 ; " gas oil" and lubricant, 9*78 ; paraffin, 
1*50; paraffin grease, 0*65; coke, &c., 48*47; loss, 28*88 
per cent. The tar was free from phenol and kreasote. 

Asphaltic rock and bitumen in the form of conglomerate 
are found in various localities in Italy. 

In the Abruzzo there are two clearly-defined rocks — 
grey and black ; these are found in the miocene formation 
of the tertiary epoch. The calcare madreporico is con- 
sidered the true horizon of the asphalt. 



ASPHALT. 
Yields have been stated as follows : — 



16L 



Ancona. 


Caltanissetta. 


Napoli. 


Eoma. 




Tons. 


Value 
in lire. 


Tons. 


Value 
in lire. 


Tons. 


Value 
in lire. 


Tons. 


Value 
in lire. 


1878 


6,879 


244,581 


IVot 


given. 


Not 


given. 


100 


1,600 


1879 


6,163 


318,574 


4,000 


140,000 


1,9G0 


18,800 


50 


1,000 


1880 


1,660 


115,520 


4,000 


120,000 


150 


1,500 


450 


20.450 


1881 


3,380 


184,850 


4,000 


120,000 


1,500 


7.500 


50O 


22,500 


1882 


3,662 


81,052 


2,500 


30,000 


1,770 


8,850 


400 


16,800 


1383 


2,156 


177,850 


2,500 


37,500 


1,850 


9,250 


233 


11,750 


188 i 


9,100 


345,200 


6,000 


90,000 


2,000 


10,000 


250 


10,000 


Totals 


33,000 


1,467,627 


23,000 


537,500 


9,230 


55,900 


1,983 


84,100 



The Abruzzo bitumen yields on distillation : — 



Per cent. 


Sp. gr. 


Flash-point. 


Burning oil 

Intermediate 

Lubricant 


15 
33 

16^ 


•850 
•945 
•990 


54-5° 

121 •r 

157 -2° 



The shipments of asphalt from Trinidad amounted in 
the first six months of 1889 to 32,460 tons. 

Turkish asphalt from Albania (about 16 miles from 
Valona) is free from paraffin. 

On analysis its four qualities give the following re- 
sults : — 



— 


Volatile. 


Coke. 


Ash. 


Finest , r 


66-2 


29-0 


4^8 


A 


69-9 


10-5 


19 •e 


B 


58^7 


14-7 


26-6 


C 


63 •! 


51 


31^8 



162 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

The finest quality is insoluble in alcohol, slightly soluble 
in ether, but readily soluble in bisulphide of carbon, chloro- 
form, benzol, and turpentine — melting at 60° C. or 140° 
F. Neither bleaching agents nor carbon has any effect 
on the colour. The finest, on being distilled at a low 
temperature, gives off 50 per cent, of an oily substance, 
having a sp. gr. 0*905. On redistillation the oil begms to 
boil at 100° C, rising so on to 200° C, and at 300° C. will 
boil over. When the remainder of the high boiling-point 
fraction is frozen, no paraffin separates, whilst that of the 
lower temperature assumes the semi-solid appearance of 
vaseline. 

The following organic analyses of the finest and 
ordinary, or C kind, may be instructive, as the large 
amount of oxygen present shows that they do not belong 
to the ozokerite or paraffin series, but are true asphalts : — 





Finest. 


C. 


Carbon 


. . 78-8 


74-0 


Hydrogen . . 


. . 8-3 


7-5 


Oxygen 


7-5 


18-4 


Nitrogen 


. . 0-5 


• • 


Ash . . 


4-8 


-• 



99-9 

The better kinds are suitable for the best japans, while 
the most inferior can be used for inferior articles, such as 
Brunswick blacks, ironwork, &c. The commonest can be 
" sweated '^ and purified to be equal to the best. The 
cheapest can also be utilised for strengthening the rock 
asphalts, none of which can be used without such addition, 
the Trinidad bitumen having up to now ousted every other 
article from the markets of the world for that purpose. 

In 1888 the United States produced 3,800 tons of 
asphalt and 50,000 tons of serviceable bituminous rock. 



OZOKERITE. 163 



OZOKERITE. 



Ozokerite is a name applied to the solid or pasty 
varieties of petroleum. It occairs in England (Newcastle), 
Dairy (Scotland); Galicia, Ronmania (near Plojesti and 
Slavick), Hungary ; Wettin-on-Saal (East Frisia), Derbent 
(near), Baku, Islands of Tcheleken and Swatoi, Ekater- 
inoslav, Station of Kalocliinsky, and Truclimenia ; Egypt ; 
Utah, Texas, Arigona, Oregon, Canada, Manitoulin Island ; 
in the Kok-Tube Mountain (Namangan), Turkestan ; and 
elsewhere. The strata in which it occurs are chiefly 
tertiary and cretaceous. 

The principal seat of the ozokerite industry is at 
Boryslau (Moldau), where the ozokerite seems to have 
found its way into the miocene formation through a fault. 
The mineral is found in veins ranging in thickness from a 
quarter of an inch to several feet, over an area of about 
1,000 metres by 350 metres. The deposit narrows con- 
siderably with the depth. 

The density of ozokerite ranges from -85 — '95, and the 
melting-point from 58° — 100°. The ordinary Gahcian 
product melts at 62°. 

Boryslau ozokerite of sp. gr. -93 furnishes about 26 per 
cent, of kerosene and 54 per cent, of scale. Baku ozoke- 
rite of sp. gr. -903 (m.p. 79°) yields 81*8 per cent, of scale; 
the Persian variety (sp. gr. -925) 53-5D per cent. ; and the 
Newcastle kind (sp. gr. -890 ; m. p. 60^—70°; 64-95 per 
cent. 

There are many refineries of ozokerite and ozokerite 
oil in Austro-Hungary, where the latter is largely used. 
The Moldavian oils are mostly sent in tank cars to 
Itzkany-Suczawa on the Austro-Roumanian frontier ; 
those of Wallachia, in so far as they are not refined on 

l2 



164 MANUALETTE OF DESTEUCTIVE DISTILLATION. 

tlie spot, are tanked to Aiistro-RoTimanian refineries at 
Orsova on the Danube, Fiume, Vienna, Buda-Pestli, and 
the small refineries in Transylvania. Ozokerite oil is 
refined m the same manner as native petroleum. Solid 
brown ozokerite is refined by (1) distillation, usually with 
superheated steam — at 300° — 320° for parafiins (followed 
at 380° — 420° by yellow oxidised resinous bodies) ; (2) 
treatment of the sohd distillate with about 6 per cent, of 
strong oil of vitriol (about 1 per cent, by volume of soda 
of 1-2 sp. gr. being used when required) and washing 
with water ; (3) crystallisations from a low percentage of 
tlie light oil — or methyhc, ethylic, or amylic alcohol- - 
follo\^ ed by treatment with charcoal. In the last opera- 
tion the melted ozokerite may be preferably melted with 
animal charcoal, in the absence of a solvent, and the use 
of magnesic silicate has been patented as an efficient 
substitute for charcoal. The jield amounts to 60 per cent, 
of white scale. Fuller's earth also gives excellent results ; 
and aluminised charcoal might probably be very usefully 
employed. Ceresin is ozokerite bleached without distilla- 
tion, e.g., by heating to 200° C. with strong oil of \dtriol, 
washing, and filtering the melted mass through silicates. 
Another mode of " bleaching " consists in melting at 70°, 
decanting, melting with 5 — 15 per cent, of sulphur, and 
distilling in steam. The product is pressed at 35° — 50°, 
crystalHsed from amylic alcohol, and again similarly 
pressed. Native ozokerite may yield approximately — 

Petroleum. . . . . . , , . . 25 



Lubricating oil 

Paraffin . . 

Coke 

Pitch and loss 



21 

36 

8 

10 

100 



OZOKERITE. 



165 



At Swatoi Astrow, near Apscheron, ozokerite is distille I 
in flat-bottomed retorts, holding 1,500 — 2,000 pounds 
each. The results are, according: to Grabowski — 



"Benzol" .. 

Naphtha 

Paraffin 

Heavy lubricating oil 

Coke 



Per cent. 

2—8 
15—20 
36—50 
15—20 
10—20 



Having regard to the fact that native ozokerite is 
chiefly worked for the purpose of obtaining solid paraffinn, 
distillation in a vacuum might obviously be advantageous ; 
this would bo, facilitated by the circumstance that Uttle 
or no gas is given off in the process. Crude ozokerite, as 
ordinarily distilled, contains chrysene, but not naphthaliu. 
The still holds about three tons. 

The purification of ozokerite by oil of vitriol is attended 
with very appreciable loss, on account of the oxy-com- 
pounds which the mineral is now known to contain. 
These, unlike the paraffins, are attacked somewhat ener- 
getically by oil of vitriol. 

Ozokerite, after purification for candle-making, melts 
at 51° — 61°, is quite odourless and colourless, and has a 
waxy section. The kind prepared by Otto^ of Frankfort- 
on-the-Oder, is said to melt at 83°, and to be so hard as 
scarcely to yield to the finger nail. 

The natural undistilled hydi'ocarbides of ozokerite are 
of great value for lubricating purposes. 

The following table gives the quantity and value of 
ozokerite mined in Austria-Hungary in the years indi- 
cated ; — 



166 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



Years. 


Tons. 


Value per 
ton. 






£ 


1877 


. 


8,818 


22 


1878 






10,177 


26 


1879 


. 




8,922 


22 


1880 


. 




10,360 


29 


1881 


. 




10,478 


22 


1882 


. 




9,899 


22 


1883 






10,459 


24 


1884 


. 




11,751 


27 


1885 


. 




12,818 


26 


1886 


. 




13,702 


22 


1887 






7,921 


20 


1888 






8,640 


21 


1889 


. 




7,439 


20 


1890 


. 


6,071 


24 



In 1890 the United States produced 350,000 lbs. of 
refined ozokerite, valued at 6,563/. 

Among the by-products from ozokerite is the residue 
of the steam distillation. Since 1875, Field and Tailing 
have employed a vulcanised weld of this hard, black, 
waxy substance with india-rubber as an electrical insu- 
lator. 

Vaseline, paravasehne, and the like, are mixtures of 
iso-paraffins (e.g., C^g— C20) with lower hydrocarbides, 
and are taken from petroleum and ozokerite stills after 
some of the oil has volatilised ; their sohd paraffin is more 
or less removed, and the residue bleached without dis- 
tillation. Bleaching is effected by treatment at 30° with 
10 per cent, of oil of vitriol, stirring for half-an-hour, and 
separating the carbonised layer. The clear portion is 
treated ^vith aqueous potassic dichromate, washed, heated 
to 80° with granular spodium (bone-black), and filtered 
hot. Another method consists in passing the oil through 
thirty charcoal filters (as constructed for sugar-refimng). 
After the bituminous matters have been removed, there is 



OZOKERITE. 



1()7 



a steaming at 250^, followed by filtrations. Vaseline is 
white, odourless, and tasteless, and has the sp. gr. 0-848. 
It is much in request as a lubricant, anti-rust, and basis 
for ointments and perfumes. 

The following table, due to Boussingault, shows the 
composition of a number of combustible substances from 
South America and other localities : — 






1 


2 


3 


4 


5 


6 


7 


Carbon . . 
Hydrogen 
Oxygen . . 
Nitrogen 


86-82 

13-16 

0-00 

0-02 


82-85 

13-09 

4-06 

0-00 


85-29 
8-24 
6-22 
0-25 


77-84 
8-93 

11-54 
1-70 


82-7 

10-8 

6-5 

0-0 


71-89 
6-51 

21-57 
03 


80-96 
5-13 

12-50 
1-41 


— 


8 


9 


]0 


11 


12 


13 


14 


Carbon . . 
Hydrogen 
Oxygen . . 
Nitrogen 


87-05 
5-00 
6-56 
1-39 


87-81 
3-88 
7-67 
0-61. 


93 -05 
3-35 
3-43 
0-17 


92-25 
2-27 
4-94 
0-54 


94-83 
1-27 
3-16 
0-74 


97-6 
0-7 
1-7 


97-87 
0-37 
1-70 
0-06 



1 and 2 are analyses of hitmnen from the fire-pits of 
Ho-Tsing, in the province of Szu-Tchuan, China. This 
bitumen is dark-green by reflected light, brown by tj-ans- 
mitted light. It is liquid at ordinary temperatures, but 
cooled deposits a crystalline granular mass of naphtlialin. 
1 gives the analysis of the portion remaining liquid 
2, the analysis of the semi-solid portion. 3, Egyptian 
asphalt^ which left an ash consisting of ferric oxide. 

4, Bitumen of Judea^ found floating on the Dead Sea. 

5, Fossil resin, from the auriferous alluvium at Giron, near 
Bucaramanga, New Granada, resembling amber in appear- 
ance. 6, Fossil 7'esin, from the auriferous alluvium of 
Antioquia, New Granada. 7, Coal from Canoas, plateau 
of Bogota (height, 2,800 m.). It occurs in grit connected 



168 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

with Neocomian limestone. 8, Fibrous coal from Antioquia. 
9, '' Fusain'' from Blanzi. 10, '' Fusain" from Montram- 
bert, Loii'e. Fusain is a variety of coal resembling 
wood-charcoal in appearance. Some stalks, the interior 
of which is composed of fusain, are covered with a bark 
which has been converted into coal. It is apparently 
the fossil form of wood which was dried by exposure to 
air before becoming embedded, and which has not under- 
gone the same changes as vegetable debris, which decom- 
poses in swamps. 11, Anthracite from Chih. 12, Anthra- 
cite from Muso, New Granada. It occurs in masses in the 
schists in the emerald mines. It is hard, brilhant, and 
takes on a very high polish; sp. gr. 7*689. 13, Anthra- 
cite, supposed to come from Brazil. 14, Graphite from 
Kaison. 



PEAT. 

Peat consists of the cumulatively resolved fibrous parts 
of certain mosses and graminaceae. It gradually darkens 
from brown to black with increasing age. Judging from 
Dr. Angus Smith's results, it grows at the rate of about 
an inch in the year. A pectinous substance and a complex 
hydrocarbide fichtelite, have been found among its con- 
stituents. As a fuel it is most economically used at the 
spot where it is grown. It has been, however, destruc- 
tively distilled at a low temperature for tar, a branch of 
industry now scarcely profitable. The process gives a 
very porous, friable charcoal, possessed of great deco- 
lorising power; gas rich in carbonic dioxide is also given 
off. A ton of good peat may yield more than 5,600 cubic 
feet of gas. The purified gas contains about 11 per 
cent, of vaporised hydrocarbides, 37 per cent, of marsh 



BROWN COAL OR LIGNITE. 169 

gas, 31 per cent, of hydrogen, and 19 per cent, of car- 
bonic oxide ; it is thus (as its mode of formation suggests) 
less oxygenated than wood gas, but more oxygenated 
than coal gas. 

The liquor is rich in hydric acetate, which amounts to 
about '2 per cent, on the peat ; ammonic sulphate, taken 
similarly, exceeds 1 per cent. 

Good peat yields about 3 — 6 per cent, of tar proper, 
which is comparatively easy to purify by the usual method. 
A specimen in the writer's museum had the sp. gr. -954. 
According to Vohl, 100 parts of peat tar from six sources 
fm-nished, on the average, 20-1 per cent, of paraffin oil 
(sp. gr. -82), 21*8 per cent, lubricating oil (sp. gr. -86), and 
3*4 per cent, of paraffin. This last estimate seems doubtful. 
Wagenmann found as a mean, 2*1 per cent, of paraffin ; 
Kane and Sullivan about 1 per cent. ; other experimenters 
have obtained from -75 to '5, and even -1 per cent. 

Peat yields from 5 to 50 per cent, of ash, one-third of 
Avhich may consist of ferric oxide. To this source may 
not improbably be due the occasional ferruginous charac- 
ter of peaty waters, and the decolorising power of peat 
charcoal. 



BROWN COAL OR LIGNITE. 

Brown coal is intermediate between wood and coal 
proper, which latter it succeeds in geological time. It 
sometimes retains the fibrous structure of wood, has a 
yellow or brown colour, and pasty consistence, and is 
easily fusible ; at others it is quite black, and closely 
resembles coal. The better kinds retain much moisture. 

One of the common constituents of lignite is pyropis- 
site, a crystalline mineral, more or less soluble in petroleum. 



170 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

ether, and alcohol, melting at 79° — 82°, and closely related 
to a formula CgHjgO. 

According to Thomas, the greater part of the gas 
occluded in lignite consists of carbonic dioxide, with which 
olefines, oily aromatic compounds, and appreciable quan- 
tities of carbonic oxide are associated. 

Lignite coke is in use as a substitute for bone- 
black. 

Brown coal has been worked for many years at Weis- 
senfels, in Saxony, where it has yielded by the ordinary 
treatment, the ordinary products of the low-temperature 
process. At these works, according to a report of Dullo 
(1862 ?), the brown coal fm-nishes 17*8 per cent, of buttery 
tar, which yields 20 per cent, of paraffin, and 43 per cent, 
of illuminating oil. The means of Vohl's more recent 
figures, which refer to 13 sources, are — 18*6 per cent, of 
paraffin oil (sp. gr. -82), 32*4 per cent, of lubricating oil, 
and 4*1 per cent, of paraffin — reckoned on the tar, which 
may be taken at 11 per cent. In gravity and other 
respects, this tar very closely resembles shale tar. A 
geocerate, C26H52O2, is among its constituents. It also 
contains a remarkable hydrocarbide, picene, (^22^u^ 
melting at 335°, but obtainable in larger quantities by the 
destructive distillation of the residues of Californian 
petroleum. 

The above numbers refer to distillates obtained in 
horizontal cast-iron retorts. If steam be introduced 
during the process, the tar yields, it is said, as much as 30 
per cent, of paraffin. 

The product is purified with some difficulty from 
sulphur and nitrogen. 

Although brown coal in many respects resembles peat, 
it much surpasses that substance in the value of its pro- 
ducts of destructive distillation, furnishing, in fact, about 



BONE OIL. 171 

three times as much iar, and three tunes as mnch paraffin 
as peat. 

Such of the brown coals as most closely resemble avoocI 
contam but little nitrogen, and yield, of course, an acid 
distillate ; such as are akin to coal give an alkaline distil- 
late, being more nitrogenous. 

[According to Albrecht, the brown coal industry 
yielded in 1871 about 4,921 tons of paraffin, and double 
that weight of illuminating oil. He also states that a ton 
of medium quality yields 60 — 65 per cent, of finished pro- 
ducts, consisting of : — 

15 — 17 per cent, paraffin. 

29 — 35 „ illummating oil. 

10 — 15 „ heavy oil. 

2 — 4 „ kreasote. 

4_ 6 „ pitch.] 

For the action of heat upon lignite oils and other oils 
of high boiling-point, see JowrTiaZ of the German Chemical 
Society, xi, 723, 1210, 1222, 1431 ; or London Chemical 
Society s Abstracts, 1878, 1860-63, 961. 



BONE OIL. 

Bones consist of about two-thirds mineral ingi-edients, 
not altered by heat (tricalcic phosphate), and one- third 
osseine, which is destroyed by heat. The latter substance 
has the following composition : — 

Carbon .. .. .. .. 50-4 

Hydrogen . . . . . . . . 6*5 

Nitrogen .. .. .. .. 16*9 

Oxygen .. .. .. .. 26*2 



172 MANU ALETTE OF DEbTKUCTlVE DISTILLATION. 

Thus bones yield about 6 per cent, of nitrogen. When 
they are soaked for several days in dilute hydric chloride, 
their calcic salts dissolve, leaving a mass of flexible osseine, 
which retains the shape of the original bone. 

Osseine dissolves in boiling water, being thereby trans- 
formed without change of composition, into an equal 
Aveighfc of gelatine ; hence it is an isomer or polymer of 
gelatine. In the destructive distillation of bones it is the 
osseine alone that furnishes distillate. The manufacture 
of bone oil is an industry that survives from mediaeval 
times. 

The bones are submitted to a preliminary treatment in 
order to remove fat. This is effected by prolonged contact 
with hot water, or, much better, by steaming in vertical 
cyhnders. The cylinders hold about 5 tons of bones, and 
the operation of steaming lasts about 12 hours. At the 
end of that time cold water is admitted from below in 
quantity more than sufficient to cover the bones ; the fat 
is thus brought to the surface, and is then skimmed off. 
During the operations of steaming and watering, some 
gelatine solution is of course formed in the cylinders ; this 
is removed, concentrated, and sold as " glue substitute." 

The bones are preferably distilled as thus saturated 
with moisture ; dry bones furnish a partially solid distillate, 
which would inevitably choke an exit-pipe of moderate 
length. The distillation is performed in horizontal cylin- 
drical retorts made of cast-iron ; a convenient size is 9 feet 
long by IJ feet in diameter. The retort is completely 
filled with its charge, and then closed after the fashion of 
a gas retort ; the addition of an exhauster has also been 
proposed. It is next heated to the lowest possible degree 
of redness, during eight hours. The residue in the retort 
consists of " animal charcoal " or " bone-black ; " this 
consists approximately of: — 



BOXE OIL 173 

Charcoal . . . . . . . . 10 

Calcic phosphate . . . . . . 84 

„ carbonate . . . . . . 6 

100 

According to some authorities, it invariably retains 
nitrogen in greater proportion as the temperature has 
been lower. 

Seven retorts can be heated at one time. 

Another and less manageable method is applied to the 
distillation of dried bones. The retorts, preferably five in 
number, are charged as before, and their distillate con- 
ducted while gaseous, and through a very short exit-pipe, 
into rectangular leaden chambers. Here a great deal of 
the amnionic carbonate solidifies; it is purified by 
sublimation. 

Both methods furnish a liquid distillate, containing, as 
in the case of coal, an aqueous and an oily portion. The 
aqueous portion is a solution of ammonic carbonate, 
cyanide and hydrosulphide, together with methylamme 
and its homologues, pyridine and its homologues (of at 
least two series), pyrrhol and ethylic alcohol. The oily 
portion is also charged with these, and contauis in addi- 
tion, fatty nitriles, C2 — Cg (not, however, when fat is 
absent), fatty and aromatic hydiides, naphthalin, aromatic 
dihydro-hydrides, CgH^^ — C^H^g, pyrroline and its first 
two homologues. The sp. gr. of the oil is -914 — '945 ; it 
begins to boil at about 80°. This product was formerly 
known under the name of Oleum animale Dippeli. 

The aqueous distillate is treated for ammonia in the 
same manner as the aqueous distillate from coal, excepting 
that weaker vitriol (sp. gr. 1*2) is used, on account of the 
richness of the ammoniacal liquor. The resulting sulphate 
is apt to be coloured with pyrrhol-red. 



174 MANU ALETTE OF DESTRUCTIVE DISTILLATION. 

A ton of bones yields 10 — 12 gallons of oil, and 130 — 
140 gallons of liquor of sp. gr. 1*03 — 1*04. Attempts to 
purify the oil for illuminating purposes have hitherto 
resulted in faihu'e. The exhausted ammoniacal liquor has 
been used as a sheep-dip. The oil, when distilled, yields 
an elastic pitch, in request for vamish-making. 

In addition to the above products, the destructive dis- 
tillation of bones furnishes a very decided amount of gas. 
Unfortunately this gas contains too much sulphur, and in 
too intimate a state of combination, to admit of economical 
purification. It is, however, possessed of very consider- 
able illuminating power, and is therefore somewhat used 
to light the more open parts of works ; but the greater 
part of it is burned under the boilers or retorts. Bone oil 
is easily utilised in the same way. 

The extent of this industry depends in a great measure 
upon that of sugar-refining. Some conception of its mag- 
nitude may be formed from the fact that for every ton of 
refined sugar more than a ton of animal charcoal is used ; 
the charcoal is then re-burned and used again, thus under- 
going a loss of value to the amount of 40 per cent, per 
annum. 

Horn^ hair and Uatlier yield a liquid distillate, very 
similar to that from bones. 

Weidel and Ciamician distilled gelatine, and found 
among the products pyrocoll, C,oHgN202 (a crystalline 
sohd), pyrrhol, homopyrrhol, CgH^N, and dimethylpyrrhol, 
together with methylamine_, butylamine, and perhaps 
quinoline. 



WOOL. 



175 



WOOL. 

Tlie following special experiments on the destructive 
distillation of wool have been made in the author's 
laboratory. 

The sample, which consisted of well-scoured yarn, 
contained 14-93 per cent, of moisture, and yielded -84 per 
cent, of ash ; 50 grm. of it were distilled during six hours. 
A suitable tower, containing standard acid, was placed to 
intercept any ammonia that might pass off with the gas. 
The first products observed in the course of the distillation 
were hydric sulphide and water; crystals of ammonic 
carbonate were observed next, and these were succeeded 
by a pale yellow oil. The distillate smelled very strongly 
of members of the pyridine series, and a very pungent 
body, probably acridine, occurred in the latest stages of 
the operation. 

Analyses of wool by Marcker and Schulze, and Scherer, 
are given in Watts's Gmelin, xvii, 351 [an unfortunate 
exchange of H for N in this analytical statement led 
the w^'iter (Trans. Chem. Soc.^ 1883, 142) to an erroneous 
formula for wool]. Their .percentages agree fairly well 
with the expression adopted below : — 



Carbon 


Marcker and 
Schulze. 
(Mean.) 

49-54 . . 


Scherer. 

50-65 


CagHesNnSO 

. 50-49 


Hydrogen 
Nitrogen 


7-29 . . 
15-60 .. 


7-03 
17-71 . 


7-01 
. 16-61 


Sulphur 


3-44 . . 


.. 


3-45 


Oxygen 


2413 .. 


•• 


. 22-44 



100-00 



100-00 



The " fixed carbon " contained a considerable quantity 



176 MANUALETTE OF DESTRUCTIVE DISTILLATION. 

of nitrogen. The following equation corresponds with 
the determinations so far as made : — 

^30^65^11^013 = C21N3 + C10H39 
" Fixed carbon." G-as and tar. 

+ 5 (NH3CO2) + 3HCN 4- H2S + 3H2O. 





Percentages 
found. 


Calc. 


Water . . 


5-4 . . 


5-8 


Residual carbon. . 


. 24-9 . . 


26-1 


Nitrogen therewith 


4-3 . . 


4-5 


Ammonia 


8-6 .. 


9-2 



It must, however, be added that the sulphur was not 
entirely evolved, as '24 per cent, was found in the fixed 
nitrogenous carbon. Portions, also, of CO2 and HON 
ought doubtless to be credited to the gas and tar ; but it 
would have been a matter of extreme difficulty to deter- 
mine the free cyanide and carbonate. The actual tar 
amounted to about 2*5 cc. per 50 grm. of wool ; it was 
lighter than water. 



FIXED OILS. 
a. Vegetable. 



These bodies are mixtures of solid and liquid glyce- 
rides. They were first destructively distilled, on the 
industrial scale, by Taylor, in 1815. The retort consisted 
of a horizontal iron chamber, filled with coke, and heated 
to low redness, or a little higher. Above this was placed 
the oil reservoir, by which the gas was washed. From 
90 — 96 per cent, of the oil was converted into gas. 
Sp. gr. '604 — '710; defines, 16 — 32 per cent. Analysis 



FIXED OILS. 177 

showed 37 per cent, marsh gas; carbonic oxide, 14 per 
cent. ; hydrogen, 21 per cent. 

Castor Oil is destructively distilled at Jeypore for the 
production of illuminating gas. The seed, pressed at the 
works, yields 33 — 40 per cent, of oil, which is distilled 
without purification. A maund (82 lbs.) of oil yields about 
800 cubic feet of purified gas, at an average cost of 35s. IQd. 
per 1,000 cubic feet. The illuminating power of the gas 
is such that the burners in use consume only IJ cubic feet 
per hour, corresponding to 17 — 18 candles. Some tar is 
formed in the process. 

p. Animal. 

These oils, in their general chemical deportment, much 
resemble the vegetable fixed oils. Warren and Storerhave 
made a detailed examination of the distillate from the hme 
soap of Menhaden oil, which is prepared from a kind ot 
herring {^Alosa menhaden). The oil was saponified with 
one-fourth of its weight, i.e., an excess of caustic lime, and 
the dried soap distilled from iron retorts. The brown 
malodorous distillate was rectified in a steam current, which 
left a thick residue, containing much crystalline matter. 
After purification with vitriol and soda, and by distillation 
in steam, the oil exhibited the general aspect of a petro- 
leum. The following table gives the relative yield, in a 
total distillate of 6,400 cc. of the substances indicated — 
intermediate fractions, in which the boiling-point was not 
constant, not being taken into consideration : — 



r cent. 


Substance. 


B.P. 


0-8 


^'Amylene 
LAmylic hydride 


. , 34-5— 35-1) 
.. 39 


3-9 


Hexylene 


.. 65 


2-1 


Hexylic hydride 


. . 68-5— 69-5 


3-1 


Benzene 


. . 79-9 



78 



MANUALETTE OF DESTRUCTIVE DISTILLATION. 



er cent. 


Substance. 


B.P. 


4-7 . 


(Enantliylene. . 


. 95 


7-6 . 


Heptylic hydride 


. 97-8 


6-9 . 


Toluene 


. Ill 


12-5 . 


r Octylene 
LOctyHc hydride 


. 123-8— 125-2 
. 128—129 


13-3 . 


Xylene 




7-8 . 


Nonylene 


. 153 


23-5 . 


^Cumene 
LDecylene 




. 174 175 


10-2 . 


Undecylene .. 


. 195-4 


3-1 . 


Duodecylene . . 


. 212-6 



Thus the distillate, while well characterised by the 
presence of olefines and hydrides of the fatty series, is 
remarkably rich in aromatic products. The latter are 
mainly due to the high temperature requisite for the 
decomposition of the lime soap. 



SUINT. 

Suint, the dried sweat of sheep, constitutes about 15 
per cent, of the weight of the fleece. It dissolves in the 
water in which the raw wool is washed. The evaporated 
residue consists of 50 per cent, organic matter, and yields 
one-third of its weight of pm-e potassic carbonate, the 
remainder being sulphate and chloride, very free from 
sodium. One-third of the potash used in France is derived 
from this source (6,000,000 kilos, of wool). The distillation 
of the solid suint gives rise to gaseous hydrocarbides and 
a good deal of ammonia ; the residual coke is lixiviated 
for potassic salts. A kilo, of suint furnishes 210 litres of 
gas of very high illuminating power. 



BEET-ROOT RESIDUES. 179 



BEET-ROOT RESIDUES. 



The jiiice of the beet is somewhat rich in nitrogenous 
bodies, among which aspartic salts and betaine (trimethyl- 
glycocine) are especially noticeable. Potassic salts are 
also present in considerable quantities. Fermented beet- 
juice, after removal of the alcohol, is termed *' vinasse " by 
the French distillers, who evaporate and ignite it, thereby 
producing about 2,000 tons of potassic carbonate annually. 
A process devised by Vincent has been now for some time 
employed, whereby the nitrogenous constituents are 
also recovered. The spent wash is concentrated until it 
has the sp. gr. 1-81, run into cast-iron retorts and distilled, 
each charge taking four hours to work off. The gaseous 
products are passed through condensers, and then burned 
under the retorts. The aqueous portion of the distillate 
contains ammonic sulphide, carbonate, and cyanide ; 
methylic hydrate, sulphide, and cyanide, abundance of 
trimethylamine, and many of the fatty acids. The tar, 
when again distilled, yields more ammonia, series of oils, 
and pyridines, phenol, solid hydrocarbides, and pitch. The 
aqueous distillate is neutralised with hydric sulphate and 
evaporated to crystallisation; the mother liquid retains 
trimethylamine sulphate, which can be utilised for the 
manufacture of methylic chloride, and in the production of 
alkaline carbonates. Vincent has observed that, while the 
wash is concentrating in the retort, the quantity of 
ammonia increases, mono- and di-methylamines gradually 
taking the place of the trimethylamine. 

Commercial trimethylamine contains, among other 
bodies, isobutylamine, propylamine, mono- and di-meth}^- 
amine (sometimes 50 per cent, of the latter) ; the tri- 
methylamine itself being occasionally as low as 5 — 10 per 

cent. 

M 2 



180 MANUALETTE OF DESTRUCTIVE DISTILLATION. 



CELLULOSE. 

The following experiments on the destructive distilla- 
tion of cellulose were carried out in the author's laboratory. 
The still used was a glass flask holding 1,130 cc, and 
gradually heated to redness during six hours. The 
material used for distillation was well-scoured "hand- 
kerchief cloth." It contained 5*99 per cent, of water, and 
yielded '65 per cent, of a^h. By means of a piece of 
combustion tubing about 1-3 m. long, the still was con- 
rected with a two-necked receiver, on the outside of 
which cold water was constantly playing. The top of 
the still was covered with sheet asbestos. Heat was 
applied by means of a Fletcher burner. The distillation 
lasted six hours, during which a red heat was gradually 
ttained. The following are the particulars of an experi- 
ment (substance taken 100 grm.) : — 

Grammes. 

Wate?' measured after drawing from receiver 42*5 
„ in substance . . . . . . . . 6*0 

36-5 
Hydric acetate (sp. gr. 1*06) in water . . 2*4 



34-5 



Acetate : water : : C^B^fi^ : 2H2O . . . . 1*2 



35-7 
Experimental drainage correction .. .. 1*1 

Total water . . 36*8 
= 39*4 per cent, on dry organic cotton. 



CANNOSE. 181 

Grrammes. 
Fixed carbon in retort. . , . . , . , 26*5 

Ash correction , , •? 



2/)- 



= 27-6 per cent, on dry organic cotton. 
Tar (heavier than water), about 2*5 cc. 
Hydric acetate, 2*040 grm. 
= 2*20 per cent, on dry organic cotton. 



The equation is 




SCeH.oOj = 12C + 

Fixed carbon, 

(Calc.) 100 .. 29-fi .. 
(Found) — . . 27-6 . . 


Gras and tar. Organic water 

29-6 . . 40-8 
30-0 . . 39-4 



In this case the weight of (gas and tar) is about equal 
to that of the fixed carbon. The C2 from the acetate, 
added to the tar, amounts to about 3-6 per cent. Hence 
the gas, saturated with moisture, must have amounted to 
about 26*0 per cent. [In this and similar experiments, all 
the acid in the distillate is reckoned acetic] 



CANNOSE. 

The following are the particulars of an experiment 
carried out by the author on the destructive distillation 
of cane sugar. The sample contained "15 per cent, of 
moisture, and yielded -03 per cent, of ash. The same 
apparatus was used as in the case of cellulose. I'lie 
operation is extremely liable to fail, owing to intumes- 
cence. Accordingly, only 25 grammes were distilled, 
the time taken being eleven hours. The corrected results 
were as follows : — 



182 MANUALETTE OF DESTRUCTIVE DISTILLATION. 



^12^22^11 


= 9C + 


C3H2O + lOH^O 




Fixed carbon. 


Gas and tar. Organic water. 


(Calc.) — 


.. 31-(^ .. 


15-8 .. 52-6 


(Found) — 


.. 31-5 .. 


17-7 .. 50-8 



Sugar furnishes 2*42 per cent, of acetate when thus 
distilled, and very little tar. The gas probably amounted 
to about 17 J per cent. 

W. Foster has found high-temperature cane-sugar coke 
to contain 95 per cent, of carbon and 1*1 per cent, of 
hydrogen ; the low-temperature coke contained 94.1 per 
cent, of carbon and 1*2 per cent, of hydrogen. Fischer 
and Lay cock found the distillate to contain propylaldehyde 
and dimethylfurfuran. 



STARCH. 

Horvat {Chem, Centr., 1887, pp. 38—39) distilled starch 
with lime, and found among the products acetone, 
mesityhc oxide, and isophorone (207°). The fraction 
128° — 207° comprised a series of ketones of the formula 



SUMMARY. 183 



SUMMARY. 

The application of heat to cellulose and kindreii bodies 
leads to cumulative resolution; and the process is in 
principle the same, whether performed by nature or by 
human contrivance. At each stage in such resolution 
pecuhar products may be given off. At a high tempe- 
rature the liquid distillate is characteristically " aromatic;" 
at a low temperature " fatty." In either case the persist- 
ence of the TiCg group can be freely traced throughout 
the products of destructive distillation. 

Inasmuch as a chemical equivalent for much of the 
" temperature " can be found in " time," petroleum ma}' 
appear in rocks never actually igneous; and we can 
understand the occun-ence of degraded hydrides, such 
as turpentme with other " aromatic '* compounds, in living- 
trees. 



APPENDIX A. 



Shale Ketorts. 

The accompanying folding plate is intended to illustrate, 
by typical instances, the development of requirements in 
the construction of retorts. 

Old Vertical TyiM. [Fig. A]. — This kind of retort was 
largely used by Young's Paraffin Company. It was about 
10 feet high and 2 feet in diameter.; the section being 
sometimes circular, sometimes oval. The line of the water 
seal, and the method of firing, are indicated in the 
diagram. 

Hendersons Retort. [Fig. B]. — " The products of dis- 
tillation pass off at the bottom of the retort by pipe (19) 
to the condensers. When the shale is exhausted the 
bottom plate (11) of the retort is removed by a hand lever 
apparatus (15), which at the same time folds back the 
little door (13) upon the furnace arch, and this door acts 
as a shoot to guide the spent shale into the furnace below. 
The carbonaceous matter left in the shale acts as fuel for 
the next charge. 

" Four retorts are built into the one retort oven (2). 
One of these is discharged into the furnace every four 
hours, and thus the heat is kept up. The furnace is 
divided into two by the partition (4). At the bottom of 
this partition, the non-condensable gases of the distillation 
are introduced to help the combustion of the spent shale 
and to increase the temperature. After the spent shale is 
thoroughly burned the bottom plate (17) of furnace is 



186 APPENDIX. 

relieved of its counterpoise weight, and folds down to dis- 
charge the burned spent shale into the hutch below, to be 
passed (through a pond of water requiring evaporation) 
to the spent shale heap. 

*' The products of combustion pass from the furnace up 
through the flue (7), which protects the bottom of the 
letorts from overheating, into the oven (2). The new hot 
products displace the previous cooler ones at the top of 
the arch, and the colder products pass off from the bottom 
of the oven by the exit-pipes (8), which either (as in 
drawing) let off the products of combustion direct into the 
atmosphere, or, as is always done now, into a common 
flue Avhich passes along the side of the retort bench, and 
carries the gases to the chimney-stalk. 

" Superheated steam is carried in by a pipe (18). Very 
Httle air is required to burn the spent shale. The bottom 
plate (17) of furnace is solid, and allows air to pass only 
at its edges, and the suction through the oven from exit, 
being at the bottom, is only gentle." 

Young's Retort. [Fig. C]. — Vertical sections of two 
forms of this retort are given in the figure. Low red-heat 
distillation takes place in the upper portions. A, B ; the 
under portions A\ B^ being at a cherry-red heat. D, D^ 
are outlets for oil vapours and ammonia. A damper d can 
be slid inwards to form a division between the two 
portions A, A^ of the left-hand retort. E is a circular 
chamber furnished with numerous openings e into the 
retort ; into this steam is introduced through F placed 
preferably in a coil in the main flue G leading to the 
chimney-stalk. The heated products of combustion pass 
from the combustion chambers H through the ports h into 
the chamber or oven, and around the lower part of the 
retorts, as shown by the arms ; then through ports h^ in 
the partition wall C^ into the upper chamber or oven, and 



APPENDIX. 187 

round the upper part of the retorts. A brick damper A'^ 
regulates the relative temperatures of the upper and lower 
retorts. The retorts are charged at the top, and dis- 
charged at the bottom, by means of a trap and shoot, 
into the combustion chamber. In the right-hand fonii of 
retort the steam, ammonia, and gases from the lower 
retort have to pass up through the shale ; in the left-hand 
form this is not the case. 

Young and Beilby Retort. [Fig. D], — The left-hand 
diagram shows the retorts proper; in the right-hand figure 
a superheater S and gas-producer are combined. The 
retorts are charged at the top, from which part also oil 
vapours and ammonia are led away. The upper part A 
of each retort is of iron, the loAver parts are of fire-clay, 
and these are subjected to a very high temperature. 
Steam is introduced internally below at S^, in order to 
destroy residual nitrogenous compounds and generate 
" water-gas," and the retorts are heated partly by " pro- 
ducer " gas, partly by the internal combustion due to the 
steam. In order to prevent fusing, not quite all the 
carbon of the shale is burned off. 

In this retort a very high temperature is employed 
below, in order to obtain an exhaustive yield of ammonia ; 
hence the need for a producer. " This gas-producer is a 
vertical retort, built of brick, closed by a door at the 
top, and provided with an exit-pipe which connects the 
retort with a system of mains and condensers. At its 
lower end the retort terminates in a closed fire-place and 
ash-pit, Avith regulating doors or dampers. The dross or 
small coal is introduced by the top door, and, resting 
on the fire-bars, fills the retort from top to bottom. The 
upper part of the retort, being surrounded by flues 
through which fire-gases are led, is kept at a full red 
lieat. The coal at this part of the retort is distilled, and 



ISS APPENDIX. 

parts Avith gases and vapours whicTi pass away by the 
exit-pipe to be cooled and condensed. As the coke 
passes down into the retort it is met by a current of steam 
which is partly decomposed, burning the carbon, and 
producing ammonia and "water-gas," which pass off 
along with the other volatile products. When such coke 
as has escaped the action of the steam reaches the fire- 
bars, it is burned into carbonic oxide by a regulated 
admission of air. This red-hot carbonic oxide passes off 
by ports at the lower end of the retort, and is burned in 
the flues surrounding the shale retorts. The gases from 
the upper part of the retort, after having been depiived of 
their condensable constituents, are also returned." 

It has been found an advantage to give each retort a 
separate hopper and valve. Moreover, in recent forms, 
the superheater S is dispensed with, and the gas-producer 
is in duphcate ; so that the left portion of Fig. D (2) is 
now the same as the right. Total yield of gas about 
15,000 cubic feet per ton of shale. 

Couper-Rae Retort. [Fig. E]. — Below each retort A is 
a chamber B of fire-brick, and having about twice the 
capacity of the retort. This chamber is built solid — i.e., is 
not surrounded by flues. A jet of steam at C also injects 
air — a pecuharity of this retort. The retort A is exter- 
nally fired and surrounded by flues, as well as heated by 
the gases from B. The figure shows a pair of retorts. 

Stanrigg Retort. [Fig. F].— (Neilson, Patent 9783, 
1889). The vertical section shoAvs the construction of this 
very simple form of retort. Upon a core bed lies a 
charge of about 60 tons of shale, the daily charge being 
about 12 tons. The retort is of 9-inch brick, in a casing 
of iron ; and is about 46 feet high by 7^ feet at the top 
and 11 feet at the bottom. Low-pressure steam (weighing 
about 100 lbs. per ton of shale) is introduced at G ; air 



APPENDIX. 189 

also leaks in at the discharging door, as required. A 
Root's blower pulls over all gaseous products at E, where 
the temperature does not exceed 82°. The oil thus 
obtained from Stanrigg shale amounts to 40 gallons (ep. 
gr. -860) per ton; and the sulphate to 30 lbs. per ton 
(nitrogen in shale = 1*2 per cent.). It is found that a 
less height than 46 feet fails to give the maximum yield 
of ammonia. Gas, 60,000 cubic feet per ton. 

This retort has the disadvantage of producing less 
benzoline by reason of the large volume of gas which it 
makes, from which scrubbing cannot completely remove it : 
half a gallon of benzoline, perhaps, may be taken through 
in this way. But the cost of construction is so small (say 
200/.), the heat is so well kept within it, aixl the manage- 
ment so extremely simple, that it mil probably be largely 
adopted in future. 



190 APPENDIX. 



APPENDIX B. 



Bibliography. 



[The following list of Memoirs and Works has 
reference to the leading points in the development of 
modern Destructive DistiUation. The student consulting 
it will find it afford a convenient starting-point for the 
voluminous bibliography of this subject.] 

a. Memoirs. 

1825. Faraday, M. On New Compounds of Carbon and 
Hydrogen, &c. Philosophical Ti^ansactions, 1825, p. 
440. 

1826. Unverdorben, 0. Ueber das Verhalten der organ- 
ischen Korper in hoheren Temperaturen. Poggendorff's 
Annale?i, viii, 253 and 477. 

1830. Reichenbach, C. Beitrag zur nllheren Kentniss der 
trocknen Destination organischer Korper. Schiveig- 
gei^'s Journal, lix, 241. 

1832. Reichenbach, C. Ueber das Kreosot, &c. Schweig- 
gers Journal, Ixv, 461. 

1834. Runge, F. F. (Jeber einige Produkte der Stein- 
kohlendestillation. Poggendorff' s Annalen, xxxi, 65, 
513, and xxxii, 308. 

Runge, F. F. Kyanol und Pyi'ol, zwei neue 
Produkte der trocknen Destination. Oken, Isis, Col. 
608. 

1835. Dumas, J. B., and Pehgot, E. Sur I'esprit de bois, 
&c. Annales de Chiniie et de Physique, Iviii, 5. 

1836. Klauer, C. Ueber das Oleum animale Dippelii der 
Alten. Liehig's Annalen xix, 135. 



APPENDIX. 191 

1842. Zinin, N. Beschreibung einigerneiien organischen 
Basen, dargestellt durcli die Einwirkung des Schwe- 
felwasserstoiFes auf Verbindungen der Kohlenwasser- 
stofFe mit Untersalpetersaure. 

1843. Hofmann, A. W. Chemische Untersuchung der 
organischen Basen im Steinkohlentheerol. Liehig's 
Annalen^ xlvii, 37. — Ueber eine sichere Heaction auf 
Benzol. TAehig's Annalen, Iv, 200. 

1848. Brodie, B. C, An Investigation on the Chemical 
Nature of Wax. Philosophical Transactions^ 1848, 
p. 147. 

1849. Brodie, B. C. (On the same.) Philosophical Trans- 
actions^ 1849, p. 91. 

Anderson, T. On the Products of the Destructive 
Distillation of Animal Substances. Ed. Philosophical 
Transactions, xvi. 

Mansfield, C. B. Researches on Coal Tar. Journal 
of the Chemical Society, i, 244. 

Stenhouse, J. On the Nitrogenated Principles of 
Vegetables as the Sources of Artificial Alkaloids. 
Philosophical Transactions, 1850. 
1851. Violette, Memoire sur les charbons de bois. 

Ann. Ch. Phys. [3], xxxii, 304. 
1854. Bechamp, A. De Taction des protosels de fer sur 
la nitronaphtaline et la nitrobenzine. Annales de 
Chimie et de Physique, xlii, 18(5. 
1856. Wagenmann, C. Ueber die Destillation des Pho- 
togens und Paraffinols im Vacumn. Dingier^ s Journal, 
exxxix, 43. 

Vohl, H. Ueber die Produkte der trockenen Des- 
tillation des rheinischen Bliitterschiefers (Schiste 
bitumineux), &c. Liehig's Annalen, xcvii, 9. 
1856 (8), Vohl, H. Ueber die Destillationsprodukte der 
Braunkohle und des Torfs. Journal filr praktische 
Chemie, Ixviii, 504; Ixxv, 289. 



192 APPENDIX. 

1857. Williams, C. G. On some of the Products of the 
Destructive Distillation of Boghead Coal. Philo- 
sophical Transactions^ 1857, pp. 447 and 737. 

1858. Kekule, A. Ueber die Constitution und die Meta- 
morphosen der chemischen Verbindungen, und ueber 
die chemische Natur des Kohlenstofis. Liehig's 
Annalen, cvi, 129. 

Hlasivvetz, H. Ueber Buchentheer-Kreosot und die 
Destillationsprodukte des Guajakharzes. Journal fur 
Ijraktische Chemie, Ixxv, 1. 

Pelouze, J., and Cahours, A. Recherches (sur les 
petroles d'Amerique). Comptes rendus, Hv, 1241 ; Ivi, 
505 ; Ivii, 62. 

1867. Warren, C. M., and Storer, F. H. Researches on 
Volatile Hydrocarbons. Memoirs of the American 
Academy^ ix, 177. 

1868. Gill, C. H., and Meusel, E. On Paraffin and the 
Products of its Oxidation. Journal of the Chemical 
Society, xxi, 467. 

1872. Schorlemmer, C. On the Normal Paraffins. Philo- 
sophical Transactions, 1872, p. 111. 

Thorpe, T. E., and Young, J. On the Combined 
Ac lion of Heat and Pressure upon the Paraffins. Pro- 
ceedings of the Royal Society, xx, 488. 

1877. Mills, E. J. On Cumulative Resolution. Piiiio- 
sophical Magazine. 

1883. Foster, W. The Behaviour of the Nitrogen of Coal 
during Destructive Distillation. Chem. Soc. Journ. 
(Trans.), p. 110. 

Piedboeuf, L. Couches petroliferes d'Europe Meri- 
dionale. Bcv. Univ. des Mines, xiii, 3. 

Tervet, R. On the Production of Ammonia from 
Coke. Journ. Soc. Chem. Industry, p. 445. 

1884. Renard, A. Sur les essences et huiles de resine. 
Ann. Chim. Phys. [6], i, 223. 



APPENDIX. 193 

1885. Beilby, G. The Production of Ammonia from the 
Nitrogen of Minerals. Journ. Soc. A^^ts. 

Carnegie. The Gas Wells of Pennsylvania. Mac- 
millans Magazine. 

Mills, E. J. Destructive Distillation. Journ. Soc. 
Ch. Industry, iv, 325. 

Redwood, B. The Russian Petroleum Industry. 
Journ, Soc. Ch. Industry^ iv, 70. 

Fawsitt, T. A. Wood Naphtha. Ibid., p. 319. 

Morgan, T. On the Treatment of PyroHgneous 
Distillate. lUd., p. 730. 

1886. Armstrong and Miller. The Decomposition and 
Genesis of Hydrocarbons at High Temperatm-es. 
Trans. Chem. Soc, 1886, p. 74. 

1888. Wright, T. L. Coal Distillation. Journ. Soc. Ch. 
Industry, p. 59. 

Ayi'es, A. Compressed Oil Gas and its Applica- 
tions. Proa. Inst. C. E., xciii. 

1889. Steuart, D. R. The Manufacture of Paraffin Oil. 
Journ. Soc. Ch. Industry, p. 100. 

1890. Peacock, D. L. Consular Report (Batoum). 
Redwood, B. The Oil Fields of India. Journ. Soc. 

Ch. Industry, p. 359. 

1891. Topley, W. The Sources of Petroleum and Natural 
Gas. Journ. Soc. Arts, p. 421. 

Mills and McMillan. Destructive Distillation. 
Journ. Soc. Ch. Industry. 

1892. Redwood, B. Galician Petroleum. Journ. Soc. 
Ch. Industry, 1892, p. 91. 

/3. Works. 

1598. Artis avriferae quam chemiam vocant, volume n 

primum; pp. 239-240. [Notions on Distillation.] 
1658. Glauber, J. R. Miracuh mundi (continuatio), p. 13 



194 APPENDIX. 

[Wood vinegar, with drawing of plant] ; and Furni 
novi philosophici ; pars prima, p. 26 [Rosin oils]: — 
pp. 47-52, [Destructive distillation in general.] 

1686. Lemery, N. A Course of Chemistry, translated 
from the 5th French edition, pp. 3-12 [Principles] et 
seq. [Operations.] 

1730. Quincy, J. Lexicon Physico-Medicum, or a New 
Medical Dictionary. Art. Destination. [Physical 
theory, by Freind ; also various special distillations.] 
See also, Freind, J., Chemical Lectures, 2nd edition, 
Lect. iii (1737). 

1764. Macquer, M. Elements of the Theory and Practice 
of Chemistry, 2nd edition. A Translation. [Oils, 
Charcoal, &c., from a phlogistic point of view.] 

1786. Higgins, B. Experiments and Observations re- 
lating to Acetous Acid, &c. 

1800. Watson, R. Chemical Essays. Vol. iii, Essay i : On 
Bitumens and Charcoal. 

1863. Hofmann, A. W. International Exhibition, 1862 : 
Report on Chemical Products and Processes. [Nume- 
rous details on the Principles and Processes of Destruc- 
tive Distillation.] 

1865. Wright, W. The Oil Regions of Pennsylvania, 
showing where Petroleum is found, how it is obtained, 
and at what cost, &c. N. Y. 

1865—1871. Zincken. Die Braunkohle. 

1867. Payen, A. Chimie industrielle, vol. ii (organique). 

1868. Wurtz, A. Dictionnaire de Chimie pure et ap- 
pliquee. [Special articles.] 

1872. Wagner, R. A Handbook of Chemical Technology 
(Translated by Crookes). 

1874. Albrecht, M. Das Paraffin und die Mineralole. [A 
pamphlet containing very numerous manufacturing- 
details.] 



APPENDIX. 195 

1874-5. Watts, H. A Dictionary of Chemistry, 2nd 
edition. [Special articles.] 

1875. Ure, A. Dictionary of Arts, Manufactures, and 
Mines, 7th edition. [Special articles.] 

Wrigley, H. E. Special Report on the Petroleum 
of Pennsylvania : its Production, Transportation, 
Manufacture, and Statistics. Maps and illustra- 
tions. 

1877. Hofer, H. Die Petroleum-Industrie Nord Americas. 
[History, economics, geology, and technology.] 

1878. Pechar, T. Coal and Iron in all Countries of the 
World. [Statistics.] 

1878-9. Strippelmann, L. Die Petroleum-Industrie Oester- 
reich-Deutschlands. [Geology, mining, economics, 
technology.] 

1881. Burgmann, A. Petroleum and Erdwachs. [Pro- 
cesses, plant, and testing.] 

Brunton, B. H. The Production of Paraffin and 
Paraffin Oils. {Proc. Inst, C, E,) [Processes and results 
of manufacture.] 

1882. Schultz, G. Die Chemie des Steinkohlentheers. 
[Materials, plant, references.] 

Meade, Richard. The Coal and Iron Industries of 
the United Kingdom, comprising a description of 
the Coal Fields and of the principal Seams of Coal, 
with returns of their produce and its Distribution, and 
Analyses of special varieties; also an account of the 
occurrence of Ores in Veins and Seams; Analysis of 
each variety ; and a history of the Rise and Progi-ess 
of Pig-Iron Manufacture since the year 1740, exhibit- 
ing the economies introduced in the blast furnaces for 
its production and improvement. 

Lunge, G. A Treatise on the Distillation of Coal 
Tar and Ammoniacal Liquor, and the separation from 



196 APPENDIX. 

them of Valuable Products. [Also in a German 
edition.] 

Reinsch, P. F. Microphotographien lib. die Struc- 
turverhaltnisse der Steinkohle dem Carbon. 13 plates. 
4to. Leipzig, 1883. 

1883. Grouven, H. A New Method for the Determina- 
tion of Nitrogen in all its Combinations. Translation 
by G. Beilby. 

1884. Marvin, C. The Region of the Eternal Fire. [The 
Petroleum Region of the Caspian in 1883.] 

Schaedler, C. Die Technologie der Fette u. Oele 
der Fossilien [Mineralole]. Illustr. Plates. Leipzig. 

1885. Peckham, S. F. Report on the Production, Tech- 
nology, and Uses of Petroleum and its Products 
(1879-80). [An exhaustive treatise on the subject, 
with voluminous bibliography.] 

1886-7. Schaedler, C. Die Technologie der Fette und 

Oele der Fossilien [Mineralole], &c. Leipzig. 
1887. Crew. — Practical Treatise on Petroleum. 



Wagner's Jahreshericht. (Annual.) 

Kerl's Reperto7'ium der technischen Literatur. (Annual.) 

Hastings's Gas Worhs Statistics. (Annual.) 

Sto well's Petroleum Reporter. (Monthly.) 

Journal of Gas Lighting. (Weekly.) 

The Petroleum World. (Weekly.) 

Journal of the Society of Chemical Industry. (Monthly.) 

The Oil and Colourman s Journal. (Monthly.) 

Neue Wochenschrift fur den Gel und Fettwaarenhandel. 

(Weekly.) 
Report of the Geological Survey of Pennsylvania. (Annual. 

See years 1885-86, for detailed maps and section.) 
Mineral Resources of the United States. (J. D. Weeks. 

Annual.) ^ 



APPENDIX. 



197 



APPENDIX C. 



Weights and Measures. 



Foreign. 
Centimetre 
2*5399 centimetres 
Metre . . 



0-304794 metre . . = 

0.914383 „ .. = 

Litre . . . . • • - 

4.543458 litres . . ■- 

Gramme . . . . - 

0-064792 gramme . . : 

Kilogramme . . . . - 

0-453523 kilogramme : 
50-802377 kilogi-ammes: 

1016*04754 kilogrammes : 
Kilogramme . . 
Centner 

Pood 



Barrel . . 

Chaldron (coal) 
Burmese viss . . 



■•{: 



English. 

0-39371 inch. 

inch. 

39-370 inches. 

3-2809 feet. 

1-0936 yards, 
foot, 
yard. 

0-220097 gallon, 
gallon. 

15-43235 grains, 
grain. 

2-204621 pounds (lbs.) 
pound. 

hundredweight (cwt.). 
ton. 

•0009842 ton. 
110-231 pounds. 

16-25 kilos. 
35-82 lbs. 

Barrel (42 gals. American). 

35 gals. Imp. 

53 cwt. 

3*65 lbs. 



198 APPENDIX. 

Temperature. 
Deg. C = f (Deg. F. - 32). 



Specific Gravity. 
^ *_ Peg. Twaddell x 5 + 1000 

Sp.gr. X 1000-1000 ^ ^^^ ^^^^^^^j^ 





* Water being taken as 1,000. 



INDEX 



Acid, acetic, 87. 

tar, Eare's treatment, 33. 

Albama, petroleum in, 146. 

Algeria, petroleum in, 145. 

Amber, 99. 

Ammoniacum, 99. 

Anthracene, 66. 

Apple tar, 89. 

Argentina, petroleum in, 158. 

Asphalt, 160. 

Assam, petroleum in, 155. 

Astatki, 129. 

Baluchistan, petroleum in, 153. 
Barangas, petroleum of, 139. 
Beet-root residues, 179. 
Bibliography, 190. 
Bitumen, 160. 
Blast-furnace tar, 77. 
Bone, liquor from, 173. 

oil from, 171. 

Bosnia, petroleum in, 146. 
Brown coal, 169. 
Broxburn, section in, 21. 
Burmah, petroleum in, 138. 

California, petroleum in, 120. 
Canada, petroleum in, 131. 
Cannose, 181. 
Caoutchouc, 100. 
Cellulose, ISO. 
Ce resin, ] 64. 
Chenall's process, 47. 
Coke, Coal, 58, 59, 61. 
Coal, composition of, 55. 

• coiirse of distillation of, 57, 60. 

distilled in varied time, 57. 

distilled with lime, 60. 

gas, composition of, 73. 

organic matter in, heated, 71. 

output of, 74. 

yields from, 59. 

Coal tar, 54, 61. 

composition of, 65, 67. 

refining, operations in, 69. 

treatment of, 61. 

constituents of, 69. 

Coke ovens, products from, 78. 
Colorado, petroleum in, 119. 
Columbia, petroleum in, 145. 
Cork-tar, 91. 
Cracking, 48. 



Crude oil, 16, 29. 
Cumulative resolution, 7. 

Deblooming, 94. 

Depth and quality of shale, 22. 

Distillation, destructive, defined, 5. 

fractional, 11. 

Dragon's blood, 99. 

Educt, defined, 5. 
Egypt, petroleum in, 156. 
Elemi, 99. 

Galicia, output of petroleum in, 137. 

petroleum in, 134. 

G-as from paraffin oil, 36. 

Canadian, 75. 

Gras, Coal, cyanide in, 60. 

Paris, 75. 

scrubbed, 59. 

sulphur in, 61. 

United States, 75, 

Gas, natural, 109. 

natural, analyses of, 114, 

occluded, 19. 

oil, 36, 176. 

in shale distilling, 26. 

Gas- tar, nitrogen in, 61, 

Gas, Wood, 85. 

Gelatine, 174. 

Germany, petroleum in, 146, 

Guaiacum, 99. 

Heats, high and low, 49. 
Hungary, petroleum in, 145. 

India, petroleum in, 152. 
Indiana, petroleum in, 110. 
Italy, petroleum in, 150. 

Japan, petroleum in, 159. 
Jute, distillation of, 90. 

Kentucky, petroleum in, 119. 

Lignite, 169. 
Liquor, parallin, 27. 

rosin, 93. 

wood, 85. 



200 



INDEX. 



Mexico, petroleum in, 145. 

Naphtha, wood, 87. 

New South Wales shale, 16. 

statistics of, 18. 

New York, petroleum in, 110. 
New Zealand, petroleum in, 158. 

Oils, fixed, distUled, 176. 

Ohio, Findlay, section through, 112. 

petroleum in, 110. 

Ozokerite, 163. 
output of, 166. 

Paraffin industry, 16. 

operations in, 45. 

statistics of, 38, 41. 

jelly, 47. 

nature of, 46. 

Paraffins, normal, boiling-points of, 

53. 
Paraffins, normal, melting-points of, 

53. 
Paraffin oil, refining, 30. 

solidified, 47. 

still, coke, 130. 

wax, liquefied, 47. 

refining, 34. 

Peat, 168. 

Pennsylvania, petroleum in, 110. 
Persia, petroleum in, 144. 
Peru, petroleum in, 157. 
Petroleum, 100. 

composition of, 115. 

Burmese, analysed, 143. 

Canadian, composition of, 133. 

production of, 133. 

Gralician, composition of, 135. 

heating power of, 129. 

occurrence of, 100. 

pipe-lines, United States, 113. 

E/Ussian, 121. 

wells, United States, 113. 

United States, 108, 117. 

Poland, petroleum in, 145. 
Products, conditions influencing, 6. 
Product, defined, 5. 

Eefining, Russian, 127. 
Refineries, Russian, 122. 
Retort, 23. 

Couper-Rae, 25, 188. 

Henderson's, 24, 185. 



Retort, Holmes's, 23. 

Rolle's, 23. 

shale, described, 185. 

Stanrigg, 188. 

• Taylor's, 37, 176. 

Young's, 186. 

Young and Beilby, 25, 187. 

Rosin, distillation of, 13, 91. 

oil, 91, 93. 

oil, composition of, 94. 

• grease, 97. 

• refining, 98. 

oil, siccative, 98. 

spirit, 93, 97. 

Roumania, petroleum in, 137. 
Russian oil, coke, 130. 

oils, composition of, 129. 

oil, statistics of, 125. 

refining, cost of, 124. 



Scottish shales, geology of, 19. 

results from, 43. 

variations in, 42. 

Servia, oil shale in, 159. 
Spirit, wood, 88. 
Starch, 182. 
Suint, 178. 
Sulphate, 28. 

prices of, 40. 

Sulphur and paraffins, 19. 
Summary, 183. 

Tar, gas producer, 80. 

hydrochloric, 80. 

wood, 81, 88. 

Tennessee, petroleum in, 119. 
Turkestan, petroleum in, 14 i. 
Trinidad, 144. 



Vaseline, 166. 

Yenezuela, petroleum in, 158. 

Yiscosities, 128. 



Weights and measures, 197. 
Wells, Galician, 137. 

Russian, 123. 

Wood, distillation of, 85. 

products from, 82. 

retorts for, 83, 85. 

Wool, 175. 

Wyoming, petroleum in, 119. 



HABKISON AND SONS, PB1NTEB3 IN OBDINAKr TO HEB MAJESTY, ST. MABTIN'S LANE, LONDON. 



L 



"si^BJrcT r "" ' -^ '^"T'-r^^ 



\