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DESTRUCTIVE DISTILLATION

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DESTRUCTIYE DISTILLATION : ' \^

A MANUALETTE

OF THE

PARAFFIN, COAL TAR, ROSIN OIL, PETROLEUM,

AND

KINDRED INDUSTRIES.

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

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)

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

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.

0-5

•90968

142 -48

Spirit begins.

•92308

131-56

1-5

•92890

128 -70

2 0

•92342

119-24

2-5

•93863

109 ^62

3-25

•951U0

107 -18

Spirit ends. Oil begins.

4-0

•98400

85-31

Not quite clear. More
viscous.

4-75

•98429

77-27

5-50

•99601

71^20

6-25

•99792

63-37

7-00

•99820

60^74

7-75

•99621

63-50

8-50

•99621

61-28

9-25

•99621

61^62

Darker coloured.

10-00

•99332

59-61

StUl darker.

10-75

•99241

57-28

» j>

11-50

•99181

52-60

Less dark.

12-25

•99920

43-46

Dark layer at sui-face. Less
viscous.

13-00

•99880

50-76

Darkest of all.

13-75

1 ^03038

38-83

Dark and turbid.

14-50

1 -01731

41-89

j> j>

15-25

•99122

32-30

Verv dark.

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.

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

0 "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 : —

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.

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

^S.

-^5.

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

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.

lbs.

]

1 6

25-62

12-89

116-91

15-07

II. ..

0 11

25-55

10-64

70-21

7-47

III. ..

0 6

18-49

12-00

85-08

10-21

IV. ..

1 0

19-26

10-88

105-97

11-53

V. ..

1 0

24-39

12-59

140 -90

17-74

VL ..

1 0

24-06

13-76

135 -32

18-62

Vll. ..

1 0

31-91

12 83

73-73

9-46

Till. ..

0 11

27-07

12-90

82-48

10-64

IX. ..

0 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 0 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

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.

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).

MANUALETTE OF DESTRUCTIVE DISTILLATION.

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

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

.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"

^'5^82

.0000

. CO rH (N 0

§00..

0 (N 0 . .

. 0 0 ^ 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

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.

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 0
19 0
21 0
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 0

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.

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 : —

MAXUALETTE OF DESTRUCTIVE DISTILLATION.

p^'

I— J

1—1

•

r-i

T-i

Tfl

,^^

■^

I— 1

1—1
1— 1

,_^

f=i

1—1

1— 1

\rt

1—1

/— N

1—1

h- 1

-<?

I— 1

Tf<

!>.

1— 1

I— 1

0
I— 1

,—1

I— 1

»o

l-O

1—1

I— 1

r-i

T— 1

•

;

»o

■|

■3

Sjd

d.
so

PARAFFIN INDUSTRY.

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

Seam. Gals, crude oil per ton.

"Fells" (thick)

. 37

„ (inferior)

19-22

Broxburn 0 (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

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.

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

Distilled.

. 1
Washed with acid tars.

1
Washed with soda
1

tars.

1
Distilled.

Light oil.

Heavy oil (''Green ").

1
Washed with 1| per cent, acid,

170^ T.

Cooled to 2° C.

Washed with 1 per cent, soda,

72^ T.

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.

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.

—

Melting
point.

Boiling-point.
H = 15 mm.

Density at
the melting-
point.

Heptadecane

CirHgg

22-5

170 0

0-7767

Octodecane

^isHss

28-0

181-5

0 -7768

Nonadecane

C19S40

32-0

193-0

0-7774

Eicosane . .

^20^42

36-7

205 -0

0 -7779

Heneicosane

C21IT44

40-4

215 0

0 -7783

Docosane . .

C22H46

44-4

224-5

0 -7782

Tricosane . .

C24H48

47-7

234-0

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.

2 S

i g

"• ^I^?

^^^ s? g ^

8 CO O CD rH

cot.^ : : ^ :o

-"g

co"

J (jq

o o

. . T' ^

X '"'

q-J

■IS

O -« CD
O CO o

-5

6 xo c<i ri
^ CO ^ i2

O CO l> O Tfi

iCi o o

a «^

M rH Tf( 1

1—1

CO O

Cf^

00 A-

»o ^

-Q

d 05 O CO

CO CO Oi O lO i '~'

Q Tfl 00 (N p

-i

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rH (N 1

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00 (M

CO CO
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CD CO

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

S ^ rH-O^c^*- ,

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. 00

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I— 1

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8
8

Tft J> »0

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lO Tfi CD

00 \fi

O TTi -"T I— 1

l>^ -^ iH rH

^
^

(N CO t^ I !

o ! c<i

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rH 1 ^ -CD 1

r-( 00

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lO lO 1 O

S+H ^

.H 00 1 O
M 1^ O

r— 1

CO CD O

^ ?^ t^.Hi«00

lOOTjtCiiMlCOiO-'T' *"*

*r ,:, °° 2° ^ : : : :

cptrOOOiOO riOCO

g ?? ^^ 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

^'>-

o r

"c3 ®

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

1 "

OccPm

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

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

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

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.

Melting Point.

Boiling Point.

—

+ 2-35*

11_

39-13*

—

70-68*

—

98-66*

—

124-00*

-52-35* .

145-81

31-24*

166-76

25-79*

184-09*

11-38*

201-80*

5-85*

215-79

+ 4-37*

231-06

9-67*

242-47

n-16*

255-84

22-09*

• 265-22

27-75*

277-11

MANUALETTE OF DESTRUCTIVE DISTILLATION.

Melting-Point.

Boiling-Point

32-26*

284-87

36-67*

295-57

40-73*

302-01

44-28*

311-70

47-91*

317-08

50-86*

325-99

54-06

330-43

57-24

338-68

59-39*

342-36

.62-40

350-04

64-06

353-08

66-99

360-27

68-18*

362-75

71-09

369-54

71-84

371-52

74-78

377-96

7542*

379-53

oc (odd)

134-18

552-58

oc (eveD

) 140-56

555-67

COAL TAIi

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.

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.

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.

Cubic feet.
50

1-084

8-69

1-103

11-92

1-149

15-53

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.

11,620

.. 44-17

10,772

. . 36-93

9,431

. . 26-75

8,370

.. 19-16

6,896

. . 13-91

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

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

Newcastle . .

Staffordshire

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

COAL TAR.

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

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

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.

MANUALETTE OF DESTRUCTIVE DISTILLATION.

<
D

o
<

a; o

o a~

— lO

,c "^

,sl

O CO

;:: to

— -o q

-s-?-

-w

t/2x:

g J2

fil

^ ft

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

& != ^

— O 2
M

— s §9 .
1 ^og*

COAL TAR.

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

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

Hexylene

CeHjs

Heptylene

C7H14

Acetylene

C2H2

Crotonylene

C4H6

Terene . .

C5H8

Hexoylene

CeHio

Styrolene

CsHg

145

Indene . .

C9H8

Thiophene

C4H4S

Thiotoluene

CsHeS

113

Thioxene

CfiHsS

137

Benzene . .

CfiHe

Parabenzene* .

CeHe

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

•5

Terpene . .

C10H16

171

Naphthalin

C,oH8

218

Methylnaphthalin

CiiHio

242

-x8

Naphthalin liydride . .

CioHio

210

Naphtols, — o &

CioHsO

279, 288

94, 33

Phenyl

CiJI,o

254

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

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°

Picene . .

C22H14

519

338

Water ..

H2O

100

Hydric sulphide

H2S

-85

„ cyacide . .

HCN

-18

„ sulphocyanide .

HCNS

Carbonic oxide . .

-193

, ,

„ dioxide

CO2

--78

. ,

„ disulphide .

CS2

-110

Sulphuric dioxide

SO2

-10

Hydric acetate . .

C2H4O0

120

Acetonitril

C2H3N"

Ethylic alcohol (?)

CsHgO

-130-5

Phenol

CgHfiO

182

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

Pyridine..

C6H5N

115

')-Pieoline

CgH.N

144

a-a-Lutidine

C7H9N

142

0 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

.«

400

-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.

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.

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.

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.

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

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 : —

MAN U ALETTE OF DESTRUCTIVE DISTILLATION,

Water . .

6-2

Naphtha

to 120°

1-6

Below

210°

2-9

220°

1-3

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.

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.

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—

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

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 . .

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

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.

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°

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

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

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

B'^

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

iagara
iagara
[in ton
udson
edina
tica S

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

o
w
o

X
H

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

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

100^00 100-00 100-00 100

•67

3-12

2-90

2-45

31 ^52

39-97

19-35

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.

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"

•70

"B Naphtha"

2-5

•72

"A Naphtha"

. . 2—2-5

•74

16-5

lUuminant . .

. „ 50—54

•81

Lubricant

. .

17-5

Wax

Loss ..

••

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

0 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.

Degrees.

7121 1

425

1030

2040

2520

540 1

29 5i

680

1235

1980

405

225

485

820

1320

326

171

375

580

900

260

63i

136

262

426

640

100

213i

111

200

315

440

101*5

110

169

891

153

226

335

739^

120

147

126

174

245

531

130

123i

i4f

63i

101

135i

185

3981

140

105t

116

145

317^

loO

95i

37i

70i

115

250

160

63i

83^

93i

200

170

10\

77i

161

180

52i

67i

134i

190

64i

56i

1151

200

58^

481

99i

210

220

230

47i

. ,

70^

240

45i

641

250

43i

59i

260

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.

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

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) . .

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

Lubricating oil rich in paraffin . .

Tar

Charcoal . .

Loss

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.

43-5

33-5

22-9

•15

26-6

42-0

30-4

1-0

27-5

34-2

37-0

1-3

11-4

39-8

46-5

2-3

12-4

43-6

41-5

2-5

13-5

50-3

34-3

1-9

19 0

29-2

47-1

4-8

22-0

37-4

30-1

2-5

13-3

32-8

49-4

4-0

10-9

34 9

50-9

3-3

20-0

31-2

43-3

5-5

9-8

45-4

40-6

4-2

20-9

30-3

44-0

4-8

11-3

31-9

52-3

4-5

19-6

33 1

42 9

4-4

3-4

38-6

54-5

3-5

8-0

32-6

53-2

6-2

6-7

28-2

58-2

6-9

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

(Sp. gr. -824)

(Sp. gr. -864)

8
14

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.

Yenangyoung (from Tw^inzas

•887

110

wells).

Yenangyoung (from Twinzas

•937

Eemains

150

wells).

fluid at 0° F.

Yenangyoung (from Finlay,

•869

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

•870

Fleming and Co.'s American

bore No. 2, at a depth of

260 feet).

Yenangyoung (from Finlay,

•875

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°

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 : —

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 : —

Jd «

Locality.

a"'

s ^

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

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.

Tons.

1878 . .

602

62,000

Not given.

1879 ..

402

50,000

55,660

1880 . .

283

88,595

57,571

1881 . .

172

76,540

59,571

1882 . .

183

86,844

121

61,500

1883 . .

225

58,387

67,630

188i . .

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

12 000

1881

8,700

1S82

27,160

1883

125

16,650

1884

•

Totals . .

43,900

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

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

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

69-9

10-5

19 •e

58^7

14-7

26-6

63 •!

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.

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

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

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

1878

10,177

1879

8,922

1880

10,360

1881

10,478

1882

9,899

1883

10,459

1884

11,751

1885

12,818

1886

13,702

1887

7,921

1888

8,640

1889

7,439

1890

6,071

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 : —

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
0 03

80-96
5-13

12-50
1-41

—

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

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

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.

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

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