DESTRUCTIVE DISTILLATION the university of Connecticut libraries iif Es''cAt™",5ed.st,uat,on 11 3 ^153 OOOBOSbO T o ui 0) liJ -J / OH Z j GQ is /.^d Dook may be k TWO WEEKS i •3 subjeGt to a f ymTS a day ther*- '>? j '111 "be due on t , .ted below. 1 OC"^ 9 ^ V"* DESTRUCTIYE DISTILLATION : ' \^ A MANUALETTE OF THE PARAFFIN, COAL TAR, ROSIN OIL, PETROLEUM, AND KINDRED INDUSTRIES. BY EDMUND J. MILiS, D.Sc. (Lond.), F.KS, FOTJI^TH EilDITIOlSr. lo:n"dok': , > GUKNET & JACKSON", 1, PATERNOSTEK EOW (mr. van yooest's successoes). MDCCCXCII. All Riyhis Reserved. to^ LONDON : HARRISON AND SONS, PRINTERS IN ORDINARY TO FER MAJESTY, ST. martin's lane. Sl^'S PREFACE TO THE FIRST EDITION. Destructive distillation is a very ancient industry, whose intricate and numerous problems have been from time to time investigated by the ablest chemists. Its study has thus had a prominent influence in developing the science of Chemistry. This little book is the first to present as a whole the industry of destructive distillation. Its contents are the substance of a course of lectures delivered in Anderson's College, Glasgow, in 1875-76, and illustrated by actual inspection of many of the processes to which it refers. Students will profit most from its perusal who have such illustration at command ; and manufacturers will, it is hoped, be interested in the modern principles of the science that underlies their processes, and reap some advantage from learning how others treat the very same problems that are presented to themselves. The author begs to express his sincere thanks to the managers of works and other friends who with much kindness, and sometimes with much trouble, have con- tributed to his information on this important subject. Glasgow, November IsL 1887. A 2 •«*'«. / '^^^:5 PREFACE TO T]IE FOURTH EDITIOX. Since the last edition of this work was issued, increased attention has been bestowed upon the theory and practice of destructive distillation. It may now be regarded as demonstrated that cellulose and its kindred, or its immediate derivatives, tend to break up in terms of a Cg unit. The output of Russian and American petroleum continues to increase very largely, and has adversely alfected the economical conditions of the home produc- tion. New wells have been found in many parts of the world, and are attracting the attention of capitalists. Among tliese Peru, Canada, and Galicia contain probably the most important. Tar and sulphate are now among the regularly collected products of blast furnaces, coke-ovens, and gas producers. 1 have again to express my indebtedness to several technical friends for information very freely placed at my disposal. I have also much pleasure in acknowledging valuable literary aid referred to in the terminal Biblio- graphy — more especially the classical papers of Messrs. Topley and Redwood. E. J. M. Glasgow, October 1st, 1892. DESTRUCTIVE DISTILLATION. GENERAL CONSIDERATIONS. Destructive distillation is the decomposition of a sub- stance in a close vessel, in such a manner as to obtain liquid products. By a product is meant a body not originally present in the substance distilled. A body merely extracted with- out change by distillation is termed an educt. Manufactured ozokerite consists in parts of educts from the native mineral, but this is an almost singular case in the industry of destructive distillation. If an extended list of substances volatile without de- composition be examined, it will be found that the nume- rical values or "numerics" of their chemical symbols, or formulae, are, on the whole, comparatively low; while bodies that do not volatiHse without decomposition have, on the whole, comparatively high numerics. These laws are both comprised in the more general one — that chemical activity increases, on the whole, with symbolic value. The apparatus employed in destructive distillation con- sists essentially of a retort, followed by a condenser and a receiver. The substance to be operated on is placed inside the retort, to which heat is applied : the volatile products pass over and are condensed in long straight or hehcal tubes, which are kept more or less cooled. The average contraction from heated vapour to liquid may be taken at about 1000 : 1. The retort or still has various forms, and may be set either in a horizontal or vertical position ; in b MANUALETTE OF DESTEUCTIVE DISTILLATION. the latter case the bottom may consist of water. Its material may be glass, iron, clay, or brick. Heat is apphed directly either to the sides or bottom, or both ; or super- heated steam alone may be driven in at one end. Steam of varied initial temperature, and direct heat, are some- times used together. The nature of the products depends (a) on the composi- tion of the substance heated; (b) on the degree of heat applied; (c) on the state of division of the material; (d) but not to any serious extent (on the large scale) on the material of the retort. A rough surface, however, will not unfrequently facilitate chemical change; and, according to Ramsay and Young, ammonia is far more completely decomposed (at 760°) in contact with iron than with copper. (a.) If an organic substance contain much infusible mineral matter (as, for instance, in the case of ordinary bituminous shale, which contains a great deal of aluminic sihcate), the latter will hold down the former, and compel recourse to a higher temperature. Thus gum-benzoin, when distilled alone, yields benzoate; when mixed with sand, it furnishes benzol. In cases of this kind, the fine state of division or porosity of the earthy constituent con- tributes, with the higher temperature, to a change in the nature of the prevailing reaction. Thus, the later products in the preparation of coal-tar consist in part of dehydro- genated fatty hydrides. Again, cannel coke may resist a low red heat without loss of nitrogen, while shale coke readily parts with it. The presence of chlorine, sulphur, oxygen, nitrogen, and hydrogen, in carbon compounds, gives rise to chlorides, sulphides, oxides, etc., in the distillate. Oxides generally precede hydrides in the condenser, as is strikingly seen in the destructive distillation of wood. Excepting plants GENERAL CONSIDERATIONS. < known as Cruciferce and the like, animal compo-imds give the most highly sulphm^'ised distillate. When shale is mixed with slaked lime, and distilled as usual for oil at the most suitable temperature, there is little gain in ammonia, but the crude oil is more easily refined. According to Beilby, nitrogen is more easily steamed out of coal or shale at a high temperature when the amount of fixed carbon in the coke is greater. (b.) The natm-e of the decomposition which takes place on heating is indicated by the term cumulative resolution- Instances of this are very common in inorganic chemistry. Thus, three units of manganic dioxide decompose in partnership, yielding a unit of trimanganic tetroxide and a unit of oxygen ; SMnO^ = Mn3 0, + 0,. When glycerin is heated, polyglycerins are formed by the union of n units of glycerin, which lose (n— 1) units of water ; nC3H303 - (n - 1) Efi = C3,H,„^ ,0,„+,. This last expression, when divided by w, becomes— n n so that the ulthnate stage of this accumulation, when n becomes indefinitely gi'eat, must be a polymer of glycide, CgHgOg. Pursuing the same course with glycide, &c., we have the following table of results : — Glycerin Alcoliolo'ids. Extreme Accumulation. c,,HA C^Hp, C3IIA C3H,0 C,H,0 C3H, 8 iMANUALETTE OF DESTEtJCTIVE DISTILLATIOTT, The above mode of resolution is common to all poly- alcohols. In the important case of Woody fibre (whose •minimum formula is CgHj^O^) we have the two series — Cellulose Alcoholoids. Extreme Accumulation. GflA . .. C,HA c.flA ■ •• C.H.O, CcHA C,HA Cflfi, . .. Cflfi Cfifi c. In this or essentially similar ways, we eA^entually anive at carbon as the result of retort operations upon wood; the gentler process of nature furnishes coal. The theory of cumulative resolution was first proposed by the author of this work. Most authorities are agreed that coal has been derived from more or less impure woody fibre or cellulose, nCfl-^fi^, under the influence of heat, pressure, and time. The effect of heat is at first to dehydrate cellulose. By interpolation among Violette's well-known results on the heating of wood (Ann. Ch. Phys. [3], xxxii, 304), it appears that nQ^fi^ corresponds to a temperature of about 185°, and nQ^f)„ to about 220^, in the absence of pressure ; in presence of pressure, the latter temperature corresponds to nOfifi^. At a point somewhat below 430°, and without pressure, the residue has the composition wCgH^O. The final stage nC^. is probably not attained under ordinary experimental con- ditions. According to these results, the composition and reac- tions of coal should turn upon the value of n, the losses of HgO, and the collateral kinetic changes wliich, occurring in the course of these definite transactions, lead to the formation of isomeric (or even of polymeric) coals. The organic matter in coal or shale, if we agree to represent its GENERAL CONSIDERATIONS. 9 composition bj a formula, should correspond to an initial symbol nC^ or 2nC^, In constructing equations to represent the transforma- tions of coal and other complex bodies, collocations of symbols will be hereafter employed to indicate mean com- position ; it will be understood that these collocations are not intended to suggest separate chemical compounds. The preceding theory is practically modified by the law of decomposition already given. The numerical values of the cumulative formulae increase nearly by powers of n : hence the bodies represented are pro tanto more prone to decompose, and to vary in their kind of decomposition. Accordingly it is observed, that the number of by-products and subsidiary reactions increases, but more slowly towards the last, with the degree of heat appHed. Precisely similar considerations hold good for hydrides, chlorides, and all other bodies susceptible of cumulative resolution. Hence the presence of homologous series in tars. The process of decomposition by means of heat is most completely realised in the sun's atmosphere, which consists of the resolved weights of our common elementary, and perhaps some more simple, bodies. At the next lower temperature, that of the voltaic discharge, hydrogen unites with carbon to form acetylene, and with oxygen to form water, i^'rom these two products most organic bodies can be obtained by synthesis ; benzol, for instance, by keeping acetylene for a long time just below a red heat; naphthalin, by passing a stream of benzol or one of its homologues through a red-hot tube ; ethylene, by hydrogenating acety- lene ; alcohol, by hydrating ethylene. Hence naphthahn, hydrogen, and acetylene, with less benzol, are found in coal-tar products when a very high temperature is used; at a red heat they are absent, more benzol and chrysene being found. At a very high temperature the products 10 MANUALETTE OF DESTRUCTIVE DISTILLATION. from coal and shale are carbon and carbonised gases of low illuminating power, with but little liquid distillate, much ammonia, and few bases ; at a low temperature there is much liquid product (rich in bases, but poor in ammonia), and gas of high illuminating power. The greatest amount of liquid product of low boihng-point is found in American^ Russian, and Persian petroleums, which have probably been produced by the long-continued application of a very gentle natural heat. When coal is slowly heated (as must be to a great extent the case when it is broken fine or when a large retort is used), its oxygen is chiefly converted into water; when rapidly heated the oxygen is expelled as carbonic oxides. (c.) In the case of bituminous or caking coals, compara- tively large lumps are usually distilled, so that heat may freely traverse their interspaces. If the coal were in very fine powder, with all the particles in close contact, there would be very imperfect conduction and a low temperature product. Thus, in an experiment upon 30 grammes of coal by the present writer, particles 3"75 millimetres wide gave off with great freedom 9,437 cubic feet per ton ; par- ticles -375 millimetre wide gave off only 3,280 cubic feet, and that with much slowness. The retort was doubtless originally derived from the clay bottle, which in its turn was modelled on an animal skin or vegetable seed-case. In the sixteenth and seven- teenth centuries destructive distillation came to be the principal work in chemical laboratories. Most animal substances — sometimes the entire body (as, for instance, of the viper) — as well as plants, were so examined, or, as it was termed, "analysed." It was, however, seldom that any detailed investigation was made of the products. These were classified, according to L emery (1686), into GENERAL CONSIDERATIONS. 11 five groups ; three active : " spirit " or " mercury " (most volatile), "oil" or "sulphur" (less volatile), and "salt" (least volatile, or even fixed), soluble in water ; tioo passive : " water " or " phlegm " (passing over before the spirits when they are fixed, after them when volatile), and " earth," " terra damnata " or " caput mortuum," a dry unin- flammable residue. From this epoch the terms " oil " and " spirit " still survive in their ancient sense. The phlogistic, oxygenic, and atomic periods in chemical history have not been specially characterised by attention to destructive distillation. Much light, however, has been incidentally thrown upon it by the gi-eat modern revival in organic chemistry. By a study of the reactions of a number of individual definite substances, a skeleton theory of the process has at least been rendered possible. It is in the systematic researches of Reichenbach, Runge, Stenhouse, and Anderson, in connection with destructive distillation, that the basis of all our exact knowledge is to be found ; while the investigations of Gerhardt and Wiirtz into the behaviour of polyacids and polyalcohols have furnished the lucid superstructure. For much suggestive work on synthesis and inverse reactions we are indebted to Berthelot. Coal-gas came into use in about the year 1820 as an illuminating agent. Paraffin was discovered by von Reichenbach in 1830, in beech-tar. The low-temperature industry was commenced, as such, by James Young, in 1851. In the process of refining crude distillates, advantage is taken of the fact that the diff'erent constituents of such mixtures boil and pass over at diff'erent temperatures. This process of separating is termed "fractional distilla- tion/' for the theory of which we are chiefly indebted to Wanklyn. In 1863, that author showed that " the quantity 12 MANUALETTE OF DESTRUCTIVE DISTILLATION. of eacli ingredient whicli distils will be found by multiply- ing its tension at the boiling-point of the mixture by its vapour-density." Thus, methylic alcohol boils at 6Q°, methylic iodide at 72° ; but from a mixture of the two the latter distils even in greater quantity. The liquid with the highest vapour-tension will thus not necessarily distil the quickest ; for what the accompanying liquids want in tension they may make up by the greater density of the vapom-s they give off. If t represent tension, and d density, then for various liquids ic — ^j = kjt^d^ ; .2?2 = ^^^2*^2 5 -^3 = ^'3^3^3 ; &c. ; k being a constant of condition, calculated from the experi- ments. If the vapour-densities and tensions are inversely proportional, and the values of k equal, the products kj^d^ will all be equal, and the mixture will remain unchanged in composition while distilling. Homologous bodies, that is, those members of the same series whose common dif- ference is CH^, are thus difficult to separate; because, though the tension sinks with each increment of CHg, the vapour- density rises. Many oils distil over more rapidly in a current of steam (one of the lightest vapours) because their vapours are usually heavy; hence one reason for the introduction of steam into paraffin retorts. Under diminished pressure, the differences between the vapour- tensions of liquids are increased, and their separation is so far facilitated ; to this principle the use of exhausters in gas-works is for the most part due."^ In a recent memoir (Phil. Mag. [5] xvii, 173) it has been shown that the boihng-points of all known normal * For a further development of the theory of fractional distillation, see Wanklyn, Philosophical Magazine (4), xlv, 129 ; Glashan, ibid., 273 ; Brown, Chem. Soc. Journ., 1879, i, 547 j and KonovalaflF, ibid., 1881, ii, 1093. GENERAL CONSIDERATIONS. 13 parafiSns having an even coefficient ^ of C are comprised in the equation _ 39'3156r - 3-94) ^ ~ 1 + •070753(^ - 3-94) Similarly, when the coefficient of C is uneven, the equation is 38•992(.^^ - 3-92) y 1 + •070564(.c - 0-92) When X is made exceedingly large in these equations, y (the boiling-point) becomes 555-t37° and bb2'b%° respec- tively. These values very nearly agree ; and we may take their mean, 554°, as a working number. The normal paraffins have the highest boiling-points of any substances which it is the object of the shale-distilling industry to attain. Tliis number represents the highest or limit- ing temperature required in the interior of a shale retort during the evolution of paraffins. The course of destructive distillation admits of quan- titative admeasurement in various ways. The usual method is to determine gravities ; but no chemical method has ever been systematically followed at works. The destructive distillation of rosin furnishes an excel- lent illustration of the ineffectiveness of the physical, as compared with the chemical, examination. While the extreme range of gravities in the distillate is only from •90968 to 1*03038, the range of bromine absorptions is from 32*02 to 142*48. A distinguished firm of Glasgow distillers very kindly placed at the author's disposal a series of samples representing a complete distillation from one of their smaller stills. The samples were carefully sealed, and allowed to rest in a warm place for about eight months, at the end of which time the separation of the water was regarded as practically at an end. Two 14 MANUALETTE OF DESTRUCTIVE DISTILLATION. bromine absorptions (by the titration method) were then made for each sample, and the gravities determined at 9° C. The rosin used for distillation was American. It was blackish-brown in colour. Specific gravity at 15° C = 1*065; bromine absorption (determined colori- metrically) 101-66 per cent. [Pure rosin absorbs nearly 112-96 per cent] The following table contains the whole of the results: — No. of Sample. Hours. Sp. ar. Bromine Absorption. Eemarks. per cent. 1 0-5 •90968 142 -48 Spirit begins. 2 10 •92308 131-56 3 1-5 •92890 128 -70 4 2 •92342 119-24 5 2-5 •93863 109 ^62 6 3-25 •951U0 107 -18 Spirit ends. Oil begins. 7 4-0 •98400 85-31 Not quite clear. More viscous. 8 4-75 •98429 77-27 9 5-50 •99601 71^20 10 6-25 •99792 63-37 11 7-00 •99820 60^74 12 7-75 •99621 63-50 13 8-50 •99621 61-28 14 9-25 •99621 61^62 Darker coloured. 15 10-00 •99332 59-61 StUl darker. 16 10-75 •99241 57-28 » j> 17 11-50 •99181 52-60 Less dark. 18 12-25 •99920 43-46 Dark layer at sui-face. Less viscous. 19 13-00 •99880 50-76 Darkest of all. 20 13-75 1 ^03038 38-83 Dark and turbid. 21 14-50 1 -01731 41-89 j> j> 22 15-25 •99122 32-30 Verv dark. 23 16-00 •96960 32-02 Nearly as dark as 19. From these experiments some interesting inferences may be drawn. In the first place, it is evident that neither the specific gravity nor bromine absorption follows a perfectly regular course ; this is very possibly due to GENERAL CONSIDERATIONS. 15 unavoidable errors in firing, and to some superheating at the sides of the still, which did not contain more than about 1,000 gallons. On the whole, however, the bromine absorption quite evidently decreases as the specific gravity increases, and from sp. gr. -90968 to 1*03038 (the extreme range) 1 per cent, of bromine corresponds to about -00058563 sp. gr. There is some indication of a break in the series, where spirit ends and oil begins. The extremely heavy bodies formed towards the close of the distillation split up at last into lighter ones ; but as shown by the bromine absorption, these are probably of nearly the same chemical order as the heavy ones. As the course of the distillation proceeds from a great to a small bromine absorption, it involves the formation of more and more saturated bodies; in other words, an approximation is continually in progress towards the composition of the paraffin series. The relations of bromine absorptions to time are — y = 158-5('86406)^ and y = 62-4 - 2-2657(l-3689)^-^ t being the number of hours, and y the bromine absorption. The first curve is in fair agreement with the actual work, and indicates that the bromine absorption could not exceed 158'5 per cent. This cm^ve terminates at about the seventh horn-, after which the absorption alters very little imtil the tenth hour, when it decidedly begins to fall. The exact position of the second curve is much more difficult to find, and lies less close to the experimental points. This, indeed, might have been reasonably expected from the diminished content of the still, the increasing eff'ect of the heat, and the consequent magnifying of every irregularity that occurred. Better results could, doubtless, be attained with a still of greater capacity. IG MANUALETTE OF DESTEUCTIVE DISTILLATION. PARAFFIN INDUSTRY. Paraffin oil can be prepared from coal, bituminous shale, cannel, lignite, wood, peat, Kimmeridge clay, and the like, on the one condition that a very low red heat is employed. It is certain that the greater part of the decomposition and distillation takes place below 427° C. The highest possible boiling-point of any normal paraffin is 554° C ; and Rowan's investigations have rendered it probable that this is the extreme limit practically required in a shale retort. The material originally used in this country was boghead coal, or the Torbanehill mineral, exhausted in 1872 ; this jdelded 33 per cent, of crude oil, and 1-1^ per cent, of crude paraffin. At present, selected mid-vein shales are used, which furnish about 13 per cent, of crude oil, somewhat above the average yield of good foreign shales. Certain authorities quoted by Wagner {Technology, pp. 687-8, 1872), give the results of the examination of forty different kinds of coal, peat, &c., as treated for low- temperature tar. The means are, omitting boghead : — — Oil per cent. Sp. Gr. Paraffin. 23 kinds 17 „ 8-1 0-79 "6 per cent. The kerosene shale in New South Wales covers a vast area. It is found at Lake Macquarie and Greta, in Cum- berland County; at Mount Magallon and Mount York, in Cook County; at Joadga Creek, Cambewarra Ranges, Broughton Creek, and Toenail River, Burragorang, in Camden County, and at Blackheath, the Vale of Hartley, and other places in the Blue Mountains. The mineral PARAFFIN INDUSTRY. 17 was known to exist in New South Wales as early as 1827. It has no characteristic lamellar or fatty structure, but the reverse ; being very compact, and breaking with large, smooth conchoidal surfaces with equal readiness in every direction, and without any tendency to follow the planes of stratification. The mineral does not differ very widely from cannel coal and torbanite. Sp. gr. 1*098. The seams are from 1 foot to 2^ feet in thickness. It is much more difficult to mine than coal, and is usually won with iron picks and pointed rods. It does not run down readily into blocks, but has to be separated piece by piece, and splintered off into sharp thin pieces. It is easily lighted with a match, and burns with a steady flame like a candle, and emits a strong odour of kerosene. AVhen mixed with ordinary coking coal, 3 per cent, will yield gas of 18 candles, and 6 per cent, with the same coal 22 candles. The New South Wales shale is said to yield 100-150 gallons of crude oil per ton, and 18,000 cubic feet of 39-candle gas. The oil yields more than 60 per cent, of refined kerosene, in addition to gasoline, benzoline, phenoids, and lubricants. The composition of the shale is approximately : — Water .. 0-5 Hydrocarbides .. 81-0 Fixed carbon . . 10-0 Ash .. 8-0 Sulphur .. 0-5 100-0 Coke . . . . 18-0 The subjoined table shows the quantity and value of shale produced in the colony of New South Wales for each year, from 1865 to 1884 inclusive : — B 18 MANUALETTE OF DESTRUCTIVE DISTILLATION. Year. Quantity. Value. tons. dols. 1865 . . 570 11,750 1866 . . 2,770 40,770 1867 . . 4,079 76,244 1868.. 16,952 240,080 1869 . . 7,500 93,770 1870 . . 8,580 137,850 1871 . . 14,700 170,250 1872 . . 11,040 253,275 1873 . . 17,850 143,500 1874 . . 12,100 136,500 1875 . . 6.197 77,500 1876 . . 15,99S 229,970 1877 . . 18,963 232,620 1878 . . 24,371 286,055 1879 . . 32,519 334,650 1880 . . 19,201 223,620 1881 . . 27,894 203,740 1882 . . 48,065 420,570 1883 . . 49,250 454,315 1884 . . 31,618 360,380 The following table shows the quantity and value of the export of kerosene shale from the colony of New South Wales, for each year since 1875 : — Year. Quantity. Yalue. tons. dols. 1875.. 3,527 51,915 1876 . . 8,154 106,570 1877 . . 4,667 70,815 1878 . . 12,202 117,105 1879 . . 11,436 141,375 1880 . . 10,880 120,845 1881 . . 17,846 191,155 1882 . . 35,975 398,575 1883 . . 22,657 236,925 1884 . . 12,804 119,870 The value of this shale raised in 1889 was 1,234,449/., and the amount 536,682 tons. Much of it is imported into England for gas- making. PARAFFIN INDUSTRY. 19 The gas occluded in cannel coal is chiefly carbonic dioxide, with which members of the paraffin series are associated. The presence of 40 — 50 per cent, of low-pressm'e steam increases the yield of crude oil by about 10 per cent. ; much superheated steam burns the shale, and converts the ordinary alkaline into an acid distillate. The bog-head oil was found comparatively difficult to purify; the more recent, or 13 per cent, oil, is easier to purify,' because the hot porous shale in the retort has itself done work of purification. Sulphur is well known to decompose paraffins. Shales such as the Kimmeridge clays, containing 5 — 15 per cent, of sulphur, yield scarcely any paraffin wax (the kind of paraffin most easily thus attacked) on distillation. Irvine has therefore proposed (1884) to pass ammoniated steam through the retort ; this, he states, protects the paraffins and so increases their yield. It is an inference from Irvine's result, that highly nitro- genised shales are likely to yield well in solid paraffin. Paraffin shale, when found in contact with igneous rock, is almost black; it then yields more hght oil and ammonia, but less total oil. Scottish oil shale occurs below the coal measures generally in the neighbourhood of marls, limestones, or sandstones. It contains, on the average, about 73 per cent, of ash. According to Cadell, avIio has reported in detail upon the oil shale in West Lothian, the calciferous sandstone, a lower carboniferous series, as developed along the great anticline of Mid-Lothian, consists at the base of a series of red sandstones with thin shales and marls, and occa- sional interbedded volcanic rocks at the top. Above the red rocks come the white and gray sandstones of Granton B 2 20 MAXTJALETTE OF DESTRUCTIVE DISTILLATION. and Craigleith, which are in turn overlaid by the black shales of Wardie and the sandstones and shales of Hailes and Redhall. Each of these tAvo great divisions has, accord- ing to the measurements of Mr. John Henderson, a thick- ness of over 3,000 feet. The oil shale gi'oup, which comes next, apparently begins with the Pumpherston shale, situated some 780 feet below the Burdiehouse limestone. It occupies the remainder of the calciferous sandstone series, and has in AVest Lothian a thickness of about 3,100 feet, so that the whole thickness of lower car- boniferous rocks in West Lothian probably exceeds 9,000 feet. The Dunnet shale is the lowest member of the upper group of oil shales, and lies about 400 feet above the Burdiehouse or Camps limestone. About 450 feet higher up comes the Broxburn shale, which is perhaps the most important of the West Lothian oil shales. The strata intervening between the Dunnet and Pumpherston shales, and including the limestone, are chiefly argillaceous shales, with thin calcareous bands and occasional sand- stones. Above the Dunnet shale they become more arenaceous, and thick sandstone beds are developed, one of which has long been quarried at Binny, near Uphall, for building and ornamental purposes. The Broxburn shale, which is several fathoms above the Binny sand- stone, forms a well-marked horizon, as it underlies a group of marls and thin limestone bands, varying in thick- ness from 80 to 270 feet. This calcareous zone, locally known as the "Broxburn Marl," passes under the Fell shale, above which comes another series of sandstone beds, about 240 feet thick, Avhich underhe the Houston coal. This is, perhaps, the oldest coal seam in Britain, as in the Broxbm-n district it is situated about 1,000 feet below the base of the carboniferous limestone series. The Houston coal is covered by about 200 feet of pale- PARAFFIN INDUSTRY. 21 green and red amorphous marl, sometimes containing pieces of volcanic ash, and is apparently a fine volcanic mudtone. A thin coal seam and some oil shale occur just above the Houston marl, and two other oil shales have been GENEfffiL SECTION OF THE BROXBURN DISTRICT. HUPLET uMEsrxms DO • COAL R/KBUffhIi SHALE. MUNML9 SMUi. CREY SHALE. r*io FBET CO/91.. //ouJJSk PTarl. 6RCr SHALK, Houston coal /a/Icy ^ancia/on^ Feu.^ SHALC. ^/WL^rn, /ffca-/ BftOXBUPN SHALE. Sum Awo nun 0/1 StASS At /ft/A/AtCr SHALE- Smjiy Sait^J/Snc Butsi, Lihutr fftea. Bahwkks SH/iLe. 3u/90ieHOUSB on ctiMn LtmesroNE Chie,ffu /3/ttcS. \,.ffy Pt/**p/rek5roN Shales 2S ^S. 0. 0. 3Z 0. 22 0. 0. ^0 0. /o ^ -^5. 7^ 6S o. Bi> /o. worked still higher up, the highest of which — Raeburn's shale — is some 400 feet below Ihe carboniferous limestone. The oil shales and underlying parts of the calciferous 90 MANUALETTE OF DESTRUCTIVE DISTILLATION. sandstone series have no regular strike, but are bent about into troughs, domes, and anticlines, and are dis- located by large faults, besides which there is great irregularity in the thickness and character of the rocks, so that to work out the geological structure of the ground without the aid of mining information would be an impossible task. The shales were evidently deposited extremely sloAvly in a large gradually subsiding estuarine or fresh- water area inhabited by numerous fishes, lamelli- branchs, and small crustaceans, whose remains, along with those of plants, were constantly being deposited on the sea-floor when mud did not dilute the organic preci- pitate too much. The section on page 21 of the shales in the Broxburn district is due to Mr. D. R. Steuart. The following results, for which the author is indebted to Mr. Snodgrass, are of interest as showing the changes that may occur in the value of a shale with its depth : — Results of ExpeinmeMs upon Dannet Shale from Bore. Strength Section No, Thickness. Oil per ton. AVater per ton. of water in lbs. of Am. Am. Sulph. per ton. Sulph. per 100 galls. ft. in. galls. galls. lbs. ] 1 6 25-62 12-89 116-91 15-07 II. .. 11 25-55 10-64 70-21 7-47 III. .. 6 18-49 12-00 85-08 10-21 IV. .. 1 19-26 10-88 105-97 11-53 V. .. 1 24-39 12-59 140 -90 17-74 VL .. 1 24-06 13-76 135 -32 18-62 Vll. .. 1 31-91 12 83 73-73 9-46 Till. .. 11 27-07 12-90 82-48 10-64 IX. .. 7 23-71 11 -C2 50-86 5-91 Average •• 25-15 12-33 102 -19 12-60 PARAFFIN INDUSTRY. 23 No steam was used in distilling. The amnionic sulphate obtained cannot, of course, be accepted as what would be got in actual practice, as the quantity varies greatly with the conditions of distil- lation. The retort is of varied form and capacity. It is con- structed of thin cast-iron, and may be either elliptic or circular, or semicircular in section ; horizontal or upright ; narrow and tall, narrow and long, or wide and short. Preference has been given in very large works to the narrow, elliptic, upright kind. The retort is either closed by a door, screwed down and rendered tight by moist clay, or, if vertical, closed at the bottom by mere immer- sion in water. The latter method allows the spent shale to be cooled and removed very conveniently. The charging is intermittent. The charge fills the retort, and weighs from 1 — 3 cwt. ; in a vertical retort it is introduced through a hopper, closed by an iron valve, which is rendered tight by sand. 25 cwt. are generally worked off in about 24 hours; the retorts are charged every three hours, and drawn every hour. Rolle's retort consists of a vertical cyhnder, 16 feet high and 6 feet wide. This contains a number of very short and very open funnels, having the narrow end upper- most, and separated from the cylinder by a distance of two or three inches. Through this interspace the shale or coal falls, touching on its way the red-hot walls of the cylinder. The volatile products are removed by two large conduits, one near the base, the other at about the middle of the cylinder. Holmes's retort is in principle similar. In some horizontal retorts, more especially adapted to utilise " small " material, a hollow rotating screw is used to urge the shale forward ; in others a chain is employed ; and some retorts are revolved. On account 24 MANU ALETTE OF DESTEUCTIVE DISTILLATION. however, of the difficulty with which heat traverses small shale, such processes, especially when mechanical power is used, must involve considerable expense. Hollow cylinders, moreover, suddenly expose the whole of the shale to great heat, and the jield of solid paraffin is then materially reduced. Horizontal retorts yield lighter oil (sp. gr. '84 — '86) but less paraffin than vertical retorts (the oil from which is of about •H9 sp. gr.). Much attention has been devoted in recent times to the improvements of retorts. Henderson, for example, constructs retorts of cast-iron, 1:^ inch thick, holding about 18 cwt. of shale, and makes them in groups of four. Somewhat superheated steam is led in at the top, and the distillate removed at the bottom. When the distilla- tion is complete (ordinarily in 16 hours), the spent shale is, by the disengagement of a catch, dropped into a fii'e. This shale, together with the scrubbed gas, is adequate fuel for the distillation, excepting in cases where the retorts are much exposed, as in corner sites. This method of working leads to a great economy in fuel. The result in ammonia is about 16 lbs. of sulphate per ton. In this retort the temperature averages about 360° ; the temperature of the exit gases is about 290°. The yield of sulphate corresponds to one-fourth of the nitrogen of the shale. The permanent gas amounts to 2,000 cubic feet per ton. On the other hand. Young and Beilby take off their distillate from a chamber near the top of the retort. As this portion is only moderately hot, the dis- tillate cannot practically exceed a certain gravity ; a con- dition amounting to much the same thing as redistillation. So great, in fact, is the improvement in the oil produced in this way, that the ordinary first distillation can be dis- pensed with. Such oil, as might be expected, is about PAEAFFIN INDUSTRY. 25 •02 sp. gr. ligliter than ordinary tar. The retort itself is compound, consisting in its lower portion of firebrick, in its upper portion of cast-iron ; in the lower the charge is heated white-red, and superheated steam mixed with car- bonic oxide from a contiguous coal-tower (" gas pro- ducer ") is drawn in. The retort is charged on the top, and the spent shale and scrubbed gas are employed to heat it. From the gas-producer, a rather " dry " coal- tar and ammonic sulphate are obtained as by-products. The effect of the superheated steam is to convert the final portions of shale nitrogen into ammonia and pre- serve it after formation.* It may be questioned, however, whether a very high temperature is ever really required for this. This method of treatment has been tried, and yielded promising results, with ironstone shale; and the skilful handling it requires should be more tlian compen- sated by the large return (stated as sometimes a hundred- weight per ton, and ordinarily 65 per cent, of the possible ammount) of ammonic sulphate.! In the Couper-Rae retort, steam injects air into a large brick fire-chamber which receives spent shale. On this chamber an oval iron retort is set, in which the distillation takes place ; the retort is heated externally by the gases resulting from the injection, aided by a little extraneous firing. About 80 — 90 gallons of water are usually steamed through a ton of shale, as is the case with other retorts. The distillate is removed from the top of the retort. The Henderson retort and Young or Young and Beilby retort are noAv in extensive use. Both with these and * This important discovery is claimed by Grouven, nf Leipzig (1877). t Tervet (1883) finds that as much as 83 lbs. of sulphate per ton can be obtained by passing hydi'ogen over coke ; the ammonia thus made having the gi'eat advantage of being dry. Hydrogen sufficiently pure for the purpose can be obtained in the later stages of the distillation of the coal itself. 26 MANUALETTE OF DESTRUCTIVE DISTILLATION. the older forms an exhauster is invariably employed. \_See Appendix A.] Heat is applied directly and laterally from below, to six, fonr, or fewer retorts at the same time ; four being the usual number. The exit-tubes from the retorts are 4 — 8 inches in diameter, and feed into a main ; this may or may not be cooled, and may or may not be connected with a tar- tower to condense very volatile products. From some position in this main the gas always formed is led off; from 13 per cent, shale about 3,000 cubic feet per ton are obtained. The order observed in the distillation is (I) gases, (2) light oils, (3) oils containing solid paraffins, (4) dark and tarry alkaloidal oils. The liquid distillate is collected in large tanks which are sometimes steam- jacketed, sometimes not ; the latter is the English practice. Here the ammoniacal water settles to the bottom. In order to accelerate the process of separation, various salts have been tried {e.g., sodic chloride and sulphate), as in the extrusion of essential oils from plants ; but these have been abandoned on account of their cost aud the cost of recovery. A temperature of 50° C, imparted by a steam- jacket, answers very well ; or the distillate may be im- perfectly cooled. As a rule, the operation is left to itself. {a.) Gas. — Under the influence of extreme cold and pressure, Mr. Coleman has proved that the 3,000 cubic feet of gas which a ton of shale yields can be made to furnish three gallons of gasoline of sp. gr. -670. Rather less than this quantity is now cheaply obtained by passing the gas, preferably much cooled, through a coke tower down which heavy oil is trickling. This oil absorbs the light hydro- carbides of the gas, which are afterwards (but perhaps never completely) steamed out. Crude gasoline is rich in polysulphides ; it is reined by treatment with strong sulphuric acid and caustic soda of sp. gr. 1*36, followed by PAEAFFIN INDUSTRl:, 27 distillation, in which process much free sulphur is observed to accompany the lighter portions. (fi.) Watery Liquor. — This, which constitutes about one- third to one-half of the bulk of the crude distillate, but much more (say 120 gallons per tonj when steam is led into the retorts, is pumped out as a lower layer after coohng and subsidence ; it is maintained at a uniform sp. gr. of 1*03 (6° Tw.) by passing through the gas-scrubber, distil- lation, another transit throngh the scrubber, and conversion into steam for the retorts, thus never requiring to be discharged from the works, so as to pollute a contiguous stream. The liquor contains, in addition to ammonia, pyridine and similar amines in the caustic state (probably derived from shale nitriles, paracyanogen, or allied bodies), and as carbonate, sulphide, cyanide,* and sulphocyanide.* It is introduced into horizontal cylindrical stills, capable of holding 1,000 — 3,000 gallons, and is heated either directly or by means of an interior steam-coil, so as to fractionally distil off the ammonia. Lime (5 per cent.) is sometimes added before boiling, sometimes after partial boiling, but often not added at all ; it should, liowever, be, as a rule^f employed, so as to prevent the appearance of cyanides in the distillate. Amnionic cyanide, in presence of air, rapidly corrodes iron fittings, and the sulphate afterwards prepared has a distinct blue colour, owing to the presence of ferric ferrocyanide (Prussian blue). Olive oil and charcoal have both been used aspimfiers of the gaseous ammonia ; but the former absorbs ammonia, the latter oxidises it to nitrate ; the proper purifier is lime placed in the still. Very great advantage also is derived from distilling the ammonia in some form of the Avell-known Coffey's still (long used in * Not in the Broxburn liquor (Steuart), • t An exception to this is when the spent liquid has to be afterwards passed through scrubbers, which lime is apt to foul. 28 MANUALETTE OF DESTKUCTIVE DISTILLATION. the manufacture of alcohol) ; or by passing it through a tall tower filled with coke or pebbles, into the bottom of which steam is introduced (steam at 10 lbs. pressure will frequently sufiice). The gaseous ammonia, with sulphide and carbonate and some steam, passes onward, in some works, through a condenser and wash-bottle to a lead- lined or copper trough, the back of which is screened by a curtain inside : the ciu'tain is parallel to the front of the trough, which is closed behind it, but open in front of it. The bottom of the trough slopes somewhat towards the front. The ammonia and steam enter behind the curtain, through a perforated pipe or " cracker," and encounter oil of vitriol of sp. gr. 1*4 (80° Tw.) ; crystals of amnionic sulphate soon form, and are removed in perforated ladles. The steam is kept hot by a coil, and returned* to the retorts. The vitriol, which is preferably prepared from pure sulphur is renewed from time to time, as soon as a smell of ammonia is perceived, or the scum becomes brown. If pyrites vitriol be used, it must be kept more acid, and the crude solution retamed above crystalhsing point for a few hours, in order to deposit impurities. Sometimes this vitriol is at first only partially saturated with the ammoniacal sulphide vapours, in order to throw down arsenious sulphide, which can be removed by skim- ming; the acid is afterwards completely saturated, in order to remove iron, which settles out. Acidity is gained dui'ing the evaporation of the aqueous sulphate, which loses some ammonia by dissociation. The crystals are dried by mere draining ; they then contain a little free hydric sulphate, with traces of un- crystallisable pyridinic sulphates, and some water. They could undoubtedly be decidedly improved by the use of the centrifugal machine. Rigorously pure ammonic salts cannot be prepared by any direct process from the watery PARAFFIN INDUSTRY. 29 liquor. Sulphate prepared from liquor obtained in the low- temperature process is less liable to organic impurities than that which is similarly prepared from ordinary gas- liquor. The hydric sulphide which escapes from the crystal- lising or receiving boxes is generally burned under a tall chimney ; sometimes it is collected in a " purifier " con- taining ferric oxide. The amount of sulphate obtained in a Young and Beilby retort averages about twice as much as in the Henderson retort ; in highly carbonaceous shales the proportion is very much greater. (7.) Oily liquor^ " crude oil,'^ or tar proper. — This (which is of sp. gr. -89 from the old forms of retort, and -87 from the new kiuds) is pumped into cast-iron stills holding 250 — 2,000 gallons^ and protected beneath by perforated biick arching, so that the heat plays round the side of the still rather than on its base. The stills are short upright cylinders, whose bases are convex upwards. Gaseous hydi'ides first come off, and are caught in a tar-tower: some amnionic sulphide generally accompanies them. At or near 100° some strong ammoniacal liquor and light oil pass over; after this the temperature rises rapidly, and may exhibit an approximately stationary point. The operation is pushed to dryness, and furnishes a vesicular coke, from 7 — 12 inches thick; it is very free from sulphur and ash, and worth on those accounts about 30s. per ton. During the earlier part of the process, the condenser, which, like most large condensers, is separated from the still by a wall, is cooled by a stream of cold water ; but as soon as the distillate becomes so rich in paraffin as to Sulidify, the worm is allowed to heat up. The worm is made of lead. Water comes over during nearly the whole of the distillation, but especially towards the close, when 30 MANUALETTE OF DESTEUCTIVE DISTILLATIOX. a new destructive distillation of oxygenous pitch occurs. The residual coke amounts to 5 — 10 per cent, of the tar, its amount being less from purer tars.* This contains 3 per cent, of nitrogen. The operation is not unfrequently aided by introducing from the commencement steam at 12 — 30 lbs. pressure — a pressure which ought not to be exceeded in steaming paraffin, that substance being much more easily " burned " than is usually supposed. [After this operation Henderson interposes a continuous distillation through three stills ; he has also of late applied the principle of continuous distillation to the stills for crude oil. Very clean distillates are thus obtained.] The mixed distillates (for the paraffin magma is gene- rally added) have now lost about '016 in gravity and possess a green colour. They were formerly stirred with 2 per cent, by volume of caustic soda solution, in order to take up phenol and its analogues (" kreasote "), acetic bodies, and perhaps some terpenes.; the sodic extract was drawn off beloAv, and the supernatant fluid, sometimes after washing with water, agitated with 5 per cent, of oil of vitriol of sp. gr. 1-7 (14° Tw.). [A metal stirrer, or an air current, produces the required agitation.] This latter liquid has but little action on the fatty hydrides proper ; but on hydrides containing less hydrogen it acts powerfully, resinifying and polymerising them as it * Eeilby distilled a litre of the crude oil, weighing 882 grammes, to dryness in a glass flask (a current o£ low-pressure steam being passed through the oil during distillation), with the following results : — Kesidue in the flask lO'SS grammes. Oil distilled in the condenser . . . . 860'00 „ Gas 7-93 Unaccounted for . . . . . . . . 3'49 „ 882-00 grammes. The gas consisted mainly of parafllns without hydrogen. PAEAFFIN INDUSTRY. 31 does turpentine. AYeak acid, sometimes used at this stage, is comparatively inefficient for the purpose. Schorlemmer has isolated three of these polymers from cannel paraffin oil; he finds them to have the formulse C^^B.^^^, ^u^q^^ and CjgH2g respectively, corresponding to a range of 210° — 280° in boiling-point. These are polymers of acetylene (C^H2n_2).2 ; before the action of the oil of vitriol, they have half the above formulae. Now, fatty hydi'ides or paraffins proper have the general formula CJi^^ + ^. It may fairly be presumed that crude paraffin oil contains several orders of degraded paraffins ; the wliole of them are summarised in the general expression C^Hgn-x-* ^^ being or an even number. They should evidently be treated Avith some hydro geniser, not with oil of vitrei. The mixture of soda or vitriol ^dth crude oil generally takes only a few minutes ; but the subsequent separation of the lower layer may take several hours, especially when the oil is heavy. The action of the soda is sometimes aided by a steam jacket, or steam coil. In modern practice the soda and vitriol are added in three successive alternate portions with intervening dis- tillations, and ultimate washing with water; the vitriol treatment coming first, as this plan involves considerably less loss. The first liquids are weak, and the last strong. Thus the vitriol ranges from sp. gr. 1-3 to 1*83, the soda from 1-05 to 1*3. The first vitriol treatment is generally effected (by acid tar from a later stage) at about 43°, an account of the setting point of the oil ; but the tempera- tures in acid treatment should always be as low as possible. Soda treatment is generally carried out at 3G°. Crude light oil and blue oil are treated with acid at about 13°. A temperature of 22°, however, does not injin*e the blue oil, and the tar then separates more easily ; but the acid is then of less value for treating the crude oil. 32 MANUALETTE OF DESTRUCTIVE DISTILLATION. Ill finishing both illuminants and lubricants the tempera- tnrs should always be low with acid. With soda, it is the practice— after stming the oil with 3° — 4° Tw. soda — to steam the mixture to 54° ; the oil keeps colour better in this Avay than when finished cold. The mixing tanks are of varied capacity, and have been constructed to hold as much as 8,000 gallons; mix- ture is efi*ected by means of rotating vanes, carried on a vertical axle. The necessary degree of fluidity may be imparted by a steam coil, giving a temperature of about 50° C. It is usual to separately refine the illuminating and lubricating oils. For some kinds of crude oil, the small propoi-tion of 2 per cent, of vitriol sufiices throughout the purification. The " soda-tar " is treated with carbonic dioxide under pressure: this sets free the "kreasote," and the heavier aqueous hydrosodic carbonate is run off and recausticised with lime : or it may be merely heated and " settled." The " vitriol-tar," rich in leucoline bases, may be distilled with lime or chalk, or even with the soda-tar, to recover the acetylenic polymers and the like above referred to ; or, as is more usual, diluted with hot water, and steamed open, whereby those polymers are raised to the surface, the lower layer of weak vitriol being used for making super- phosphate, or, more usually, ammonic sulphate. The steamed tar contains about 7 per cent, of vitriol. The polymers are also to a great extent contained in the later soda-tars, and have a green colour on distillation. Like most imperfect hydrocarbides they combine with alkaline bodies, forming in this case a grease. \_See RosiN Oil.] Sonstadt recovers quinoline and its homologues, and acridine, from the acid tar by addition of potassic ferro- cyanide. It may be observed that the treatment of crude light PARAFFIN INDUSTRY. 33 oil and blue oil produces certain sulphonic acids, which are removed by the subsequent action of soda. And when the resulting soda tar is used — as it frequently is — to neutrahse crude oil after its acid-tar treatment, some of these are set free, and so return to the crude. Probably most of the phenoids are removed by the acid treatments. Rave treats the acid tar with scrap iron (which removes the vitriol as ferrous sulphate), washes, and distils. When half the substance in the retort has distilled over, the residue consists of an elastic bitumen suitable for varnish- making. The distillate contains a considerable quantity of Hght oils. The products of Rave's process may have been partly influenced by nascent hydrogen. According to Beilby's researches, the nitrogen in the " alkaloidal " (" vitriol ") tar is constantly about one-fifth of the total present in the original shale. The refined tar is fractionally chstilled. The more volatile portions ('6 — '68) are chiefly used for carburating air, thereby making an illuminating gas ; the naphtha (sp. gr. -68 — -76) is used by painters as a substitute for turpen- tine, by indiarubber manufacturers as a solvent, by parafiin manufacturers themselves as a medium from which to crystallise parafiin, and as " benzoline " for sponge lamps. The succeeding fractions (-800 — -820) are sold as illumi- nating oil (" paraffin oil ") ; but in some cases — as, for instance, in hot localities — the sp. gr. taken is "845. Lubricating oils succeed these ; the author has met with them of gravities ranging from 'Sij5 — '900. The next distillate solidifies on cooling, yielding brown crystals of hard paraffin, whose mother-liquid, removed by a filter press and hydraulic press, is "blue-oil," whence more, but soft, crystals can be obtained by artificial refrigeration. This is always conducted sloAvly, so as to C 34 MANUALETTE OF DESTRUCTIVE DISTILLATION. yield large crystals. The motlier-liquid of these is again treated with vitriol and soda, and distilled : the earlier fractions constitute heavy illuminating oil, the later lubri- cating oil. As the press rooms are seldom artificially cooled, summer-made lubricant is apt in colder weather to deposit solid paraffin. The normal paraffins are unsuitable for use as lubri- cants. The lubricating properties belong to one or more series of iso-paraffins. It has frequently been observed that products of destructive distillation are improved in coloiu' by re- distillation over lime, soda-lime, or soda. Lubricating oils are distilled over 1 — 2 per cent, of caustic soda with good eff'ect. This reagent removes acid and sulphonates. The addition of zinc dust would be of further advantage. Crude paraffin may be purified by two meltings with 10 per cent, of oil of vitriol (more heat, but under 60°, being applied on the second occasion) ; there is an inter- vening pressure of the cake, and it is finally melted with aqueous caustic soda, which must be entirely removed, on account of the greasiness it imparts to the wax. The more general process consists in dissolving the paraffin in about an equal bulk to as little as 10 per cent, of the light paraffin oil, crystallising, and pressing very strongly; this is done thrice at least, with a pressure after each crystal- lisation, the solution being sometimes filtered through 3 — 5 per cent, of animal charcoal (and paper), fuller's earth, spent shale, or magnesic silicate, and finally steamed. Lundy (1850) and A. Taylor (1864), used prussiate char- coal with considerable success, and it is still employed in Scottish works. White clay, dried at 350° and used immediately, has also been employed with good effect. Carbonic disulphide (10 — 20 per cent.) has sometimes been used as a solvent instead of light paraffin oil. PARAFFIN INDUSTRY. 3r> Another method of purification consists in pressing hot in upright or horizontal presses, whereupon soft paraffin oil, and brown colouring matter are removed ; bleaching is completed by agitating with animal charcoal for some time. Lastly, the paraffin cake is made to undergo liqua- tion on mats of cocoa-nut fibre, and finished as above described. [For a general account of liquation processes see Tervet, J". Soc. Cli. Incl, 1887, 355.] The loss on refining paraffin scale amounts to about 16 per cent.; if the extracted oil be credited, 3 per cent. Tbe products wbich leave the retort after the solidifi- able paraffin, are thick or buttery. These are sold after *" treatment,"' for lubricating purposes, with or without addition of vegetable oil. Much of their colour can be removed by exact reaction with hydric peroxide, or (which is the same thing) exposure to light and moist air. The total working loss in this manufacture is usually about one-third of the weight of the crude oil. Solid paraffin is used chiefly for making candles, for which it is admu'ably fitted, by reason of the great lumi- nosity with which it burns : more or less stearate is in this case added. The softer kinds, when dissolved to saturation in naphtha, and mixed with about 5 per cent, of vegetable oil, are, as Stenhouse has shown, excellent waterproofers of wood, e.g., for matches and bari-els, cloth, paper, indiarubber Lose, leather, and other fabrics, to which they also impart greater tensile strength; and in this state they are in extensive use as lubricating " creams,'* when great durability is required. The imperfect hydrocarbides in the lighter liquid paraffin oils act somewhat energetically on lead and zinc, less upon brass and iron, very slightly on tin and copper. Vegetable oils, when mixed with even as littk' as 10 c 2 36 MAXUALETTE OF DESTRUCTIVE DISTILLATIOX. per cent, of lieavy paraffin oil, are far less liable to imdergo spontaneous combustion on " waste " tissue. Within recent times, considerable attention has been bestowed on the production of highly illuminating gas from the less valuable liquid products of the paraffin industry. Thus " Green " oil of sp. gr. '894, from the acid tar, has been found to yield 87 cubic feet per gallon of such gas. An oil of sp. gi*. '844 has, however, furnished 88 cubic feet per gallon ; a gravity of '822 corresponds to 90 cubic feet, with less tar, and that of a thinner quality. The produce of tar from the lighter oils is in general about one-half to one gallon of tar of sp. gr. 1-081 for every five gallons of oil ; from the heavier oils, about one-and-a- half gallons. It is, of course, neither acid nor alkaline. After passing through condensers and a washer, the gas traverses two purifiers, containing layers of chopped straw, sawdust, and lime. It is admkably adapted for compres- sion; the original compression being 30, the working pres- sure 6 — 10 atmospheres. Before such treatment it has the sp. gr. -700 ; during the process it deposits one gallon of light " gasoline " per 1,000 cubic feet — thereby losing 20 per cent, of its illuminating power — the eventual illuminat- ing power being 25*9 candles, and the consumption (in a railway carriage lamp) -78 cubic foot per hour. According to Armstrong and Miller, the gas is practi- cally free from acetylene, but contains ethylene and crotonylene. The gasoline contains normal defines to C^; the acetylenes C^ and C., as well as benzene and toluene. The steam distillate from the tar yields members of the series C^, H2n_2, the three xylenes, mesitylene and pseudocumene, naphthalene, and some pseudolefines, with traces of paraffins. Greville Williams has analysed several samples of gasoline with the following results : — PAEAFFIX INDUSTRY. 37 Percentage of benzene Sp. gr. and toluene. •850 65-6 •835 54-2 •840 52-0 •830 45-2 •840 44-4 •800 37-8 •760 24-G The retort employed in manufacturmg oil gas is essentially identical with that of Taylor. It consists of a cast-iron D-shaped chamber, having a capacity of ah out 4;^ cubic feet, and acting as an upper retort ; the oil is led through this into a similar one placed below, and both are kept at a bright red heat. The pressure in the retort is equal to about 5 J inches of water, diminishing to IJ inches in the gas-holder. Two pau'S of retorts make about 420 cubic feet of gas per hour. The cost ranges fi*om 5s. 6d. to 16s. per 1,000 cubic feet. In another arrange- ment, the retort is one-chambered and constricted at the middle. The working temperature is 900° — 1,000°, and the oil is distilled at the rate of about 12J gallons per hour. The accompanying statistical table of annual working- comprises the returns made by twenty Scottish manufac- turers to the Rivers' Pollution Commission (1872). 38 MANUALETTE OF DESTRUCTIVE DISTILLATION. GO ^ 5 ^ O O o o o o o o o o o o o o o ^ . o .0000 e S ra 903 j= o o •8 888 :888 :8 o o CO i-l CO Tfl rH OCO . .OOCD .0 .OW5 W3 . . CO CO CO • kO . ?0 00 00 O) (KJ r^ lO O O 05 o O O r-l O o^ o^ o o^ 0~ O" Oi" o" CO 1-1 Oi o CO o o . lO o . ^ o 00" .000000 . U3 o^ o^ o o o^ lo o' o'~ o" crHT-H3 ^ . .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" i> 10" co" 00" i;d" cc" o' i> (M CO ^ -* -^ (M PARAFFIN INDUSTRY 39 Omitting tlie figures relating to cannel, we liave the follow- ing results, calculated (I) from the percentages given by corresponding returns, (II) from (I) and the total shale. I. 11. Total shale 100-00 tons 663,587 tons Spent shale. . 34-73 „ 230,464 „ Coal 34-87 „ 231,393 „ Caustic soda •343 ton 2,276 „ Oil of vitriol 1-63 „ 10,826 „ Steam •20 (H.P.) 1,327 (H.P.) Crude paraffin • 3 -20 tons 21,235 tons Illuminating oil . •4424 ton 2,936 „ Lubricating oil •880 „ 5,842 „ Blue oil . . •19 „ 1,261 „ Naphtha . . •37 „ 2,455 „ Ammonic sulphate •32 „ 2,123 „ (Equal to ammonia •08) „ 535 „ The "horse power" does not probably include that which is required at the pits. The mean results above given are probably too low, and must be received with considerable reserve. Production of Shale in Scotland from 1873 to 1891. Year. East. West. Total. 1873 1874 1875 1876 1877 1878 1879 1880 1881 1882 1883 1884 1885 1886 1887 1888 1889 1890 1891 tons. 439,615 277,210 377,108 454,892 581,351 535,626 «24,912 730,777 840,259 898,754 1,043,499 1,365,157 1,665,667 1,655,427 tons. 84,480 84,700 46,314 86,381 102,767 110,313 87,516 63,060 71,912 93,733 87.230 104,492 76,083 43,717 tons. 524,095 361,910 423,422 541,273 684,118 645,939 712,428 793,837 912,171 994,487 1,130729 1,469,649 1,741,750 1,699,144 1,390,320 2,052,202 1,986,990 2,180,483 2,337,932 40 MANUALETTE OF DESTRUCTIVE DISTILLATION. Other data are as follows : — Shale (tons) Crude oil (gals.) . . K^ aphtha and burning oil. . Lubricating oil .. ,, Paraffin scale (tons) Amnionic sulphate (tons) 1885. 1,609,920 48,297,600 brls. 495,050 „ 30,665 18,974 12,950 1886. 1,699,144 49,275,176 492,751 33,241 21,118 15,171 1891.* 2,337,932 54,119,249 498,848 165,003 24,518 22,000 There are at present 13 works, employing about 11,000 men. The cost (1882) of production (including repairs) was 0'50d.; of refining. 1*226?. ; of depreciation, •25<:/. ; tot^l, 1-97 d. per gallon, excluding ammonia. According to another estimate, the total cost was 2-lOd, In an individual work, the returns were (1885) 38 per cent, burning oil, 24 per cent, lubricating oil, and 13 per cent, paraffin scale. The cost of refining the crude gallon was l'21d. Taken on the refined gallon, the cost was I'Q'dd. This has been reduced (1889) to 1 cwt. of coal per ton of shale in making ci'ude oil; and -lid. per gallon for refining. Tlie average price of ammonic sulphate per ton is given on the authority of Messrs. Bradbury and Hirsch, of Liverpool, in the following table : — Year. 1868 1869 1870 1871 1872 1873 1874 1875 1876 1877 1878 1879 Price. £ s. 14 10 15 15 16 19 21 18 3 17 2 18 10 18 12 19 16 20 5 18 8 Year. 1880 1881 1882 1883 1884 1885 1886 1887 1888 1889 1890 * The amount of naphtha was 2,429,056 gallons ; il gallons J and " gas oik" (-840— -865), 5,647,423. Price. £ s. d. 19 20 4 20 8 16 11 14 9 11 9 11 3 11 17 11 18 12 1 11 9 uminant, 18,522,533 PARAFFIN INDUSTRY. 41 The total production in 338 works in the United King- dom during 1891, from all sources, they estimate at 143,500 tons, viz. : — Gas works Iron „ Shale „ Coke and carbonising works Tons. 107,000 6,500 27,000 3,000 143,500 The production during the previous five years, adjusted from the report of the Chief Inspector under the Alkali Works Regulation Act, was : — 1890. 1889. 1888. 1887. 1886. Gas works Iron Shale .. Coke and car- bonising works 102,150 5,050 24,750 2,300 100,700 6,150 23,950 2,800 93,000 5,300 22,000 2,500 85,000 5,000 21,000 2,700 82,500 4,000 18,000 2,000 Total 134,250 133,600 122,800 113,700 106,500 About 80 per cent, is exported. The totals of the quantities of Scotch and American solid paraffin consumed were : — Tons. 1887 35,042 1888 1889 1890 1891 39,230 43,804 50,774 52,340 The following are some examples of individual varia- tions among oils from different Scottish shales : — 42 MAXUALETTE OF DESTRUCTIVE DISTILLATION. ^ p^' (M * 1— 1 lO w 10 \rt Id ^ ? Oi t^ j> CO 1—1 CO iH CO T? 6 rH 10 (M CO /— N P^ lO (M 1—1 hH h- 1 8 ? ? ? 8 ? ? 8 (M -. 9 1— 1 . (M 10 CO T? CO I— 1 I— 1 4f ^^ pR ,—1 cq I— 1 M O »o l-O 9 x> 1^ IP CM t- rH xa 10 (N i CO 10 1^ 1—1 I— 1 CO r-i T— 1 • • • ; »o CO Oi 00 00 OO , ■| '1 1 . , 1 .u . . 1 rj -* CO 00 r2 ^ =e CO 00 00 m ■3 ti . g oc S3 Sjd d. so 1 m PARAFFIN INDUSTRY. 43 The following are working results usually obtained from various Scottish shales : — Seam. Gals, crude oil per ton. "Fells" (thick) . 37 „ (inferior) 19-22 Broxburn (Broxburn seam) . . . 31 Young's (Uphall) Broxburn seam . 31i Young's Newliston (Dunnet seam) . 27 Dalmeny (Broxburn seam) . 32 Pumpherston . 18 W. Lothian (Dunnet) . . . 19 Caledonian (Tarbrax) . 26 ,, (Cobbinshaw) . 30 Stanrigg . . . 40 Burntisland . 30 At the works of Young's Paraffin Light and Mineral Oil Company, the following has been an average yield of the various products from the crude oil : — Per cent. Gasoline 0-25 Naphtha— sp. gr. -TOO— -760 5-75 Burning oils — No. 1, sp. gr. -802— -804, F.P. 110° (Abel test) >| No. 2, sp. gr. •810--812, F.P. 110° (Abel test) j Crystal (No. 1 chemically treated) . . . . ;>38.00 Lighthouse oil, sp. gr. '810 -'820 F.P. 140° | (Abel test) J Lubricating oils of various specific gravities . . 14.50 Paraffin (solid) ll'OO Loss 30-50 100-00 The percentages given are only approximate, and are 44 MANUALETTE OF DESTRUCTIVE DISTILLATION. often purposely varied by alterations of the processes to suit the requirements of the markets. The loss is no doubt frequently considerably smaller than the proportion stated. At the Broxburn works an average yield has been as follows : — Per cent. Naphtha — sp. gr. -730 500 Burning oils — Petroline— sp. gr. •800/-802 -| No. 1 oil— sp. gr. -SOS/'SIO > 37-28 Lighthouse oil — sp. gr. -810 - Lubricating oils . . 17-40 Solid paraffin . . .. 12-52 Loss . . .. 27-80 100.00 e Broxburn shale furnishes : — Per cent Crude oil .. 12-5 Water 8-5 Gas 3-0 Ash . . 67-0 Carbon in spent shale . . V)-0 100.0 The Burntisland Company produce 30 gallons of crude oil, sp. gr. '865 and 8 lbs. of sulphate per ton. The oil yields : — Illuminant Lubricant Scale . . [Loss . . Per cent. 37-50 18-75 16-75 27-00] 100.00 PARAFFIN INDUSTRY. 45 The following conspectus of operations and quantities (variable with the oil and the state of the markets) will render the whole process of refining more intelhgible : — Operations and Quantities. Crude oil. 1 1 Distilled. 1 . 1 Washed with acid tars. 1 1 Washed with soda 1 tars. 1 Distilled. Light oil. Heavy oil (''Green "). 1 1 Washed with 1| per cent, acid, 170^ T. Cooled to 2° C. Washed with 1 per cent, soda, 72^ T. a 1 Filtered and pressed. Distilled. 1 1 1 reen oil. Hard seal 1 (49^ C). Ill I N'aphtha, 3rd run light oil, Intermediate, Washed with 2 per cent, acid, "750." "806." "860-865." 170° T. Washed with 2 per cent, acid, 170° T. Washed with 2 per cent, soda, 4° T. Burninc oil. " 805." Washed with 1^ per cent. soda. 72° T. Distilled with 1 per cent. soda. I 850" oil. [Distilled]. Washed with 2i per cent, acid, 170° T. Washed with 3 per cent, soda, 7° T. " Blue oil." I Cooled to 8° C. Filtered and pressed. Scaled blue oil. I Washed with 3 per cent, acid, 170° T. Washed with 4 per cent, soda, 7° T. Soft Scale (38° C). Lubricant, "888.' 46 MANUALETTE OF DESTRUCTIVE DISTILLATION. Paraffin is a mixture of neutral, non-oxygenated bodies, and contains about 85 per cent, of carbon to 15 per cent, of hydrogen. Its constituents are the " fatty hydrides" of which mention has aheady been made. This point was first conchisively proved by Gill and Meusel, who found that when excess of paraffin is heated with bromine in sunlight for some time, half the bromine is converted into hydric bromide. aH,„+, + Br, = C.H,.H. ,Br + HBr. This reaction is characteristic of hydrides. The same chemists found paraffin to yield cerotate (C27H5^02) when oxidised with chromic mixture. Their sample, then, which melted at 5Q°, consisted chiefly of cerotylic hydride C27H5f.. The softer and more fusible paraffins — melting at 9°, 16°, and upwards — are doubtless mainly composed of lower hydrides. Galletly isolated a shale paraffin melting at 80°. He has found the solubihty of paraffins to be inversely as their melting-point, and the specific gravity to be directly as their melting-point.) Crude paraffin has been recently placed under investiga- tion by F. Krafft {Deut. Ch. G, xxi., 2,256). He submitted samples of crude paraffin melting at 30° to 35° to a series of fractional distillations in a vacuum (H = 15 mm.), and succeeded in isolating saturated hydrocarbons, ranging between Cj^ and C23. Alcohol was employed as the medium of crystallisation. Krafft also obtained the principal physical constants for these bodies; they are shown in the following table : — PARAFFIN INDUSTRY. 47 — — Melting point. Boiling-point. H = 15 mm. Density at the melting- point. Heptadecane CirHgg 22-5 170 0-7767 Octodecane ^isHss 28-0 181-5 -7768 Nonadecane C19S40 32-0 193-0 0-7774 Eicosane . . ^20^42 36-7 205 -0 -7779 Heneicosane C21IT44 40-4 215 -7783 Docosane . . C22H46 44-4 224-5 -7782 Tricosane . . C24H48 47-7 234-0 -7785 Paraffin and similar oils may be converted into jellies or faii'ly hard solids by mixing with them 5 — 10 per cent, of fatty acid and 1 — 2 per cent, of caustic alkali. Accord- ing to Messrs. Chenall, 650 parts of petroleum, 250 parts of soda, and 90 parts of rosin, furnish, with the aid of heat, a design that can be moulded. (Patent 4,446, 1891.) In one of the large Scottish refineries, a yield of over a million pounds of paraffin wax was distributed as follows with respect to meltmg-point : — Percentage. 10.17 18-02 42-33 29-48 100-00 M.P. (F.) 110° 115° 120° 125° According to Thorpe and Young, solid paraffin is gradually changed into liquid kinds and defines by re- peated distillation, ^ntl2n+2 ~ ^n-p^2(n-p)+2 "I" ^P ^2p' Paraffin. Paraffin. define. little or no gas being evolved. This operation, which, 48 MANUALETTE OF DESTRUCTIVE DISTILLATION. when carried out by one continuous heating in a single stiJl, is termed " cracking," is frequently applied to heavy petroleum oils, with or without the aid of superheated steam. On the other hand, it is quite possible for defines to yield paraffins : — Olefine. Carbon. Paraffin. This reaction probably occurs in the manufacture of oil-gas from paraffin oils. D. T. Day has, in fact, shown that pure ethylene (which at 344° undergoes no change) slowly suffers con- traction at 350° — 355°, with formation of a condensation product ; but at 400° — 408° it contracts to half its volume, and contains about 40 per cent, ethane, with nearly as much methane ; and at 450° a little carbon is deposited, while the gas contains about 70 per cent, ethane, and less than 1 per cent, methane. In neither case is hydrogen formed. The reactions are, perhaps : Condensed olefine. Paraffin. Paraffin. when n = 1, 2, &c., the right-hand term is CH^, C^H^q, &c. [Riebech has applied the cracking process, under pres- sure, to the production of light oils. The best results are obtained with brown coal-tar at 3-6 atmospheres, with petroleum and its " residues " at 2-4 atmospheres, and with oil-gas tar at 4-6 atmospheres.] For the following very valuable tables (I and II) the author has to express his indebtedness to the manager of one of the leading Scottish paraffin oil companies : — PARAFFIN INDUSTRY. 49 2 S 8 1 i g 8 i "• ^I^? 1 ^^^ s? g ^ i CO 8 CO O CD rH i ^ cot.^ : : ^ :o -"g co" J (jq o o o a oi . . T' ^ o X '"' q-J o ■IS O -« CD O CO o 8 -5 i 6 xo c O Tfi iCi o o rH a «^ M rH Tf( 1 1—1 " . CO O 8^ Cf^ 1 00 A- O tn »o ^ o -Q d 05 O CO a CO CO Oi O lO i '~' ^ Q Tfl 00 (N p -i o o 1 00 (M ^ rH (N 1 "^ § ^^^'^ 1 (7q 0} 00 (M o 1 1 CO CO .H 00 CD CO 9 I— 1 et-I ^ O t- rH •- q (M CO iO X O' ^ CD lO _ 2 :* ^„ ^„ - 2i : : : : § CO T}( CD r-l X O O lO CD S ^ rH-O^c^*- , n IXNOOO OSOOi . 00 VO «^ CO (>1 (N I— 1 1 V CO CO 8 8 5q Tft J> »0 tH CO ^ 9 : ::::•••-• ai 1 lO Tfi CD 00 \fi O TTi -"T I— 1 l>^ -^ iH rH ^ ^ ^ (N CO t^ I ! o ! c^ •"^ CD*^ to CO ; ; ; ; ; ; ; ; : : ^ s o ■ S £ cq.2^ S g V c ^ Q, .S C 3 g " O . . . . g • • • • ' S^^a^l =5 : : : : : : : : . . ■^ O ^ ^ f U ® 8 : O t. 3 ^ ^ 3 • as O is ^'>- o r "c3 ® •g 03 ^ •'-'^ cr 3 2 03 ^ c3 o |0m kWfiOO J» O PLH 1 " k O OccPm 60 MANUALETTE OF DESTRUCTIVE DISTILLATION. II. Analytical Results from Good Average Shale, Specific gravity Moisture at 104' Volatile matter Fixed carbon. . Ash . . •.: }»-{,. Composition of A sJi. 99-96 Soluble in water 8-27* Silica . . 55-60 Ferric oxide . 12-23 Alumina . 22-14 Lime . . 1-55 Magnesia . . Trace Sulphur 0-94 100-73 Total sulphur in shale 1-80 ash 1-31 Composition of Organic Constituents. Carbon 25-27 Hydrogen 3-67 Oxygen 5-65 Nitrogen 1-14 Sulphur 0-49 36-22 * Coiitiiins -92 sul] huric oxide (SO3). PARAFFIN INDUSTRY. 51 Composition of Organic Constituents, exclusive of Sulphur, Nitrogen, and Ash. Carbon 73-05 Hydrogen , . . . . . . . 10-62 Oxygen 16-33 100-00 The subjoined comparison shows that this organic portion corresponds to a definite chemical relation : — Carbon . , Hydrogen Oxygen ., Found CgHioO 73-05 73-47 10-62 10-20 16-33 16-33 100-00 100-00 The decomposition which this organic matter under- goes at a low heat has been found by the author to be in the proportion 7Cefl,„0 = 0,,H,„Oj = 18C + C^fie,'^, + 4H,0 Fixed Gas and Water. V carbon. oil. which agrees with the experimental ratio on page 49 : — Fixed carbon Gas and oil. . Organic water 100-0 100-0 P 2 Found Calc. 31-2 31-5 58-3 58-0 10-5 10-5 52 MANUALETTE OF DESTEUCTIVE DISTILLATION. Similarly, at a high heat, 70,H.„0 = C,,H,„0, = 60 + C,,-H,fi, + 4H,0 Fixed Gas and Oil. Water carbon. Found. Cale. Fixed carbon . . . 12-8 10-5 Gas and oil . 7(3-0 79-0 Organic water • • • 11-2 10-5 100-0 100-0 The results for Boghead coal are as follows : At a low temperature — (Calc.) 100 (Found) ~ Fixed carbon. . . 33-3 .. 33-3 Gas and oiL 63-3 64-1 + Organic water. 3-3 2-6 At a high temperature — 3C„H,„0 = 60 + C3„H,,0, Fixed carbon. Gas and tar. (Calc.) 100 .. 13-3 . 83-3 (Found) — .. 12-8 .. 84-6 + H,0 Organic water. 3-3 2-6 Cellulose, from which the organic matter in question must at one time have been derived, has also an nC^ formula, and the same characteristic feature reappears in many of the constituents, both of natural and artificial petroleum. Hence it follows that any theory of destruc- tive distillation, as here, considered, must deal mainly with the migrations of an nC^ group. [See COAL Tar.] The organic matter of shales, so far as hitherto analysed, corresponds to a mixture of bodies lying between the fourth and fifth cumulates of cellulose (CgHgO — Cg) with more or less H in excess. PAKAFFIN INDUSTRY. 53 It is Avortliy of remark that the "aromatic" hydrides CnH2n-6) occur oiily in very minute quantities in any one of the low-temperature industries. The following special table contains the melting-points and boiling-points of the normal primary paraffins over an adequate technical range. The numbers have been cal- culated by the author (^Philosophical Magazine, March, 1884) from equations in which all the results of observation have been combined. Where experimental values (marked with an asterisk) are known, they in nearly every case lie close to the calculated ones, which may be regarded as cor- rected determinations. The symbol n is the coefficient of C in the general formula CJl^n+i for paraffins; and the symbol x indicates a melting-point or boiling-point which cannot possibly be exceeded in the odd or even series respectively of n. Normal Para ffins. N. Melting Point. Boiling Point. 4 — + 2-35* 5 11_ 39-13* 6 — 70-68* 7 — 98-66* 8 — 124-00* i) -52-35* . 145-81 10 31-24* 166-76 11 25-79* 184-09* 12 11-38* 201-80* 13 5-85* 215-79 14 + 4-37* 231-06 15 9-67* 242-47 16 n-16* 255-84 17 22-09* • 265-22 18 27-75* 277-11 54 MANUALETTE OF DESTRUCTIVE DISTILLATION. N. Melting-Point. Boiling-Point 19 32-26* 284-87 20 36-67* 295-57 21 40-73* 302-01 22 44-28* 311-70 2a 47-91* 317-08 24 50-86* 325-99 2^ 54-06 330-43 26 57-24 338-68 27 59-39* 342-36 2S .62-40 350-04 29 64-06 353-08 30 66-99 360-27 ai 68-18* 362-75 32 71-09 369-54 33 71-84 371-52 34 74-78 377-96 35 7542* 379-53 oc (odd) 134-18 552-58 oc (eveD ) 140-56 555-67 COAL TAIi I. Coal-tar is formed by a destructive distillation of coal at a high temperature, usually a bright red-heat, or beyond. Although it contains fatty hydrides, they are chiefly liquid ones, and not paraffin. Among its constituents are aromatic hydrides (of which traces only are found in natural or artificial petroleums), their alcohols (occurring in very small quantities in petroleums), and naphthalin (absent from petroleums). Chrysene occurs both in the low and high-temperature oils. COAL TAR. 55 If the general formulae of fatty be compared with those of aromatic compounds, as in the following examples — — Fatty. Aromatic. Hydrides Alcohola ,. defines CnH2n+2 CnH2n+20 C„H2„ CnH2n-6 CaH2n-60 C.H2n-8 we observe that aromatic bodies contain Hg less than the corresponding fatty bodies. Thus is the high-temperature industry, to the extent that it is specially characterised by arornatic compounds, a dehydrogenising process. Coal, moreover, is less hydro genised than cannel and similar shales ordinarily worked for oil. Thus the average composition of British coal used for gas-making may be taken (exclusive of ash) as — carbon, 86; hydrogen, 6; oxygen, 5J; sulphur, 1; nitrogen, 1-^ per cent.; ash, 2^; pit water, 3J per cent. Cannel contains — carbon, 85 ; hydrogen, 7 J ; oxygen, 5| ; sulphur, 1 ; nitrogen, 1| per cent. ; ash, large, very variable ; pit water 2-3 per cent. Tidy has given percentages of nitrogen in coal, ranging from -91 to 1*44 per ceut. ; E. Ronalds, 1-2 to 1*69 percent.; Beilby, from 1-45 to 2*2 per cent. Small percentages of resinoid extract can be obtained from coal by treatment with alcohol, or chloroform. The former has approximately the composition CgH qO ; the latter O^^^^o^ (Siepmann). The caking power is not, however, due to these bodies. The organic matter of coal has a composition inter- mediate between CgH20 and Cg — i.e., the fourth and fifth cumulates of cellulose. It was formerly the custom to prepare coal-tar in 56 MANUALETTE OF DESTEUCTIVE DISTILLATION. horizontal iron retorts, at 940°. This method admitted of a comparatively small consumption of fuel under the retorts, which, however, wore out very rapidly — on the average, in about ten months. Hence horizontal clay retorts are now almost universally employed. These, on the other hand, require an increased amount of fuel to heat themT— and are always worked hotter than iron retorts ; moreover, they produce an undesirably large amount of naphthalin, and consequently a diminished quantity of benzol.'" Never- theless, it is said that a gas-work exists in which, despite the clay retorts, no appreciable amount of naphthalin is formed. If this be correct, we must attribute the gene- ration of naphthalin not so much to temperature as to impurities (perhaps organic sulphur and oxygen) present in the coal distilled. A clay retort is semicircular in section, having a diameter of 18 inches, a length of 9 feet, and a thickness of 2^ inches. It is flanged in front, so as to receive an iron door, which is tightened with wet clay, and pressed on by a screw (or, more frequently, pressed on by a lever, and spontaneously luted by pitch). Five of such retorts can be conveniently heated together ; the best working temperature being about 1,150°. The charge is sufficient to fill them to about three-fourths of their capacity. [Kunath has pointed out that a diminished gas space in the retort must necessarily lead to the formation of a thinner tar.] The residual coke is drawn and quenched every three hours (a minimum) to eight hours. By means of an exhausting apparatus, the distillation is kept in pro- cess at an average internal pressure of about half-an- inch of water. Some graphitic carbon is always formed, and remains strongly adhering to the inside of the retort. ? The products of destructive distillation leave the retort COAL TAR. 57 at about 480°, and after travelling rather more than 20 feet, cool down to about 100°. Heniy's and Wright's experiments show that, as the distillation proceeds, carbonic dioxide, marsh gas, and other hydrocarbides are evolved in diminishing quantity ; hydro- gen, and perhaps carbonic oxide, in increasing quantity. Schulze considers that phenols and phenoids precede aromatic hydrocarbides, and perhaps give rise to them. Cyanogen compounds occur, under the influence of the highest temperature, towards the close of the distillation. L. T. Wright distilled 2 cwt. of a Yorkshire-Derby- shire coal in clay retorts at guch (high) temperatures as to require variable times for complete generation of gas. The results as regards tar and fixed carbon were as follows : — Duration of heat. Gas per foot super of Eetort. Specific gravity. Tar. Percentage fixed Carbon in tar. 8 Cubic feet. 50 1-084 8-69 7 62 1-103 11-92 6 91 1-149 15-53 5 133 1-204 24-67 Tars, obtained similarly, were analysed with the sub- joined results, including also the yield of gas in c. ft. per ton: — Specific gravity. . 1-086 1-102 1-140 1-154 l-20( Liquor . . 1-20 1-03 1-04 1 05 •38 Crude Naphtha. . 9-17 9-05 3-73 3-45 100 Light Oil 10-50 7-46 4-47 2-59 -57 Kreasote 26-45 25-83 27-29 27-33 19-44 Anthracine Oil. . 20-32 15-57 18-13 13-77 12-28 Pitch . . 28-89 36-80 41-80 47-67 64 08 Gas 6.600 7,200 8,900 10,Gl: 11,700 58 MAXUALETTE OF DESTEUCTIVE DISTILLATION. Naphthalin made its appearance prominently in the 1*154 tar: most anthracene was found in the 1-140 tar. Increased temperature was found to destroy preferably the light oils between crude naphtha and kreasote. Thus, a tar of sp. gr. 1-23 yielded — Liquor , . 4-39 Crude naphtha .. 4-11 Light oil , . absent Kreasote .. 18-99 Anthracene oil .. 12-14 Pitch .. 59-14 98-77 Sometimes the retorts are heated by "producer" gas, for making which the red-hot coke, even when of very poor quality, is extremeiy handy. When the coke is of fair quality, one part of it, converted into producer gas, is sufficient to carbonise 10 parts of coal, provided a regene- rative arrangement be used. All the products of distillation, after leaving the retort, pass into a " hydraulic main " ; here the liquid products are deposited, and thereby separated from the gaseous ones. The bent pipe from the retort dips slightly under the hquid in the main, into which no air consequently passes when the retort is open. The illuminating property is due, probably, chiefly to acetylene and other degraded hydrocarbides formed at the moment of combustion. Obviously, also, all the constituents of tar which have any sensible vapour-tension at the ordinary temperature must to some extent be present ; and many of them have, in fact, been traced by Davis. When coal-gas is passed through a scmbber containing COAL TAR. 59 natural or artificial oils of high boiling-point, it gives np (as in the low-temperature industry) a notable quantity of light oils, containing paraffins and benzol. This process was patented by Caro, Clemms, and Engelhorn in 1869. Davis (1882) aids the absorption by refrigerating the gases, and thus obtains a total of 1 j — 3| gallons of 90 per cent, benzol per ton of coal. According to another estimate, 17-candle gas should yield about 1^ gallons of 90 per cent, benzol. The scrubbed gas is a very valuable fuel. In the case of " 17-candle " gas, Wright estimates that l-J gallons, on the average, of 90 per cent, benzol could be extracted from the gas from a ton of coal by scrubbing with oils. Davis states the amount in one case (TliornclifFe coal) as 4'4 gallons, the temperature of the scrubber being kept very low (4-4° C). According to Deville, Paris coal-gas contains constantly 1 per cent, by volume of pure benzene. The yield of tar in very large English works is about 5*3 per cent. ; ammoniacal liquor, 14*1 per cent. ; sulphate, •87 per cent.; gas (10,198 cubic feet), 16*6 per cent. Specific gravity of gas, -48 ; illuminating power, 17 candles. The treatment which the crude tar undergoes is re- markably similar to that to which crude paraffin oil is submitted. The liquor is separated from it and treated for ammonia exactly as in the low-temperature industry ; its specific gravity being about 1*02 (4° Tw.), and the percentage of ammonia about 2. It is observed that an increase of heat in the retorts leads to an increased amount of cyanide and sulphocyamde in the liquor. Coal yields from 6 — 15 per cent, of liquor, from 3 — 6 per cent, of tar (cannel sometimes as much as 9 per cent.), and about 50 — 70 per cent, of coke (containing 2^ per 60 MANUALETTE OF DESTEUCTIVE DISTILLATION. cent, of ash) ; the remainder represents the yield of gas, and the working loss (about 10 per cent.). It is usual to distil coal, or such a mixture of coals, as shall yield about 10,000 cubic feet of gas (sp. gr. 0-5—0-6) per ton, or about 20 per cent. In a given product of coal-gas the middle portions contain most, the latest portions least ammonia. Foster found the nitrogen (1-73 per cent.) in a Durham gas-coal to be distributed as follows during distillation : — Evolved as ammonia „ as cyanogen . . „ uncombined . . Remaining in coke . . 14-50 1-56 .. 35-26 . . 48-68 100-00 Here the ammonic, uncombined, and residual nitrogen are in the ratio N2 : N^ : N^. The distribution seems to depend somewhat on the proportion of ash, such coals as contain little ash giving but little ammonia in the distil- late. This relation is intelligible when we remember that coal-ash is an alkaline substance. It was observed by Knoblauch that 2^ per cent, of lime added to the coal increased the yield of gas 5 per cent., and diminished the illuminating power 5 per cent. There was some increase in the ammonia. Leyboid found about -2 per cent, (by volume) hydric cyanide in the gas of the hydraulic main, and about -02 per cent, in the gas of the holders. The impurity is now under extraction. L. T. Wright found the grains (G), of sulphur per 100 cubic feet other than hydric sulphide to depend on the gam made per ton : — COAL TAR. ■ ». " Cubic feet per ton. a 11,620 .. 44-17 10,772 . . 36-93 9,431 . . 26-75 8,370 .. 19-16 6,896 . . 13-91 61 The above results refer to bituminous coal ; but similar ones were obtained with cannel. As regards the distribution in the tar, Watson Smith obtained the following numbers with a tar containing 1-67 per cent, of nitrogen : — Coke. Nitrogen per cent. Crude benzene . . . . . . 2*33 Light oil 2-19 Kreasote oil . . . . . . 2*01 Ked oil filtered from crude anthra- cene 2-19 Pitch 1-60 And, according to the same authority, the residual nitrogen per cent, is found to be, in the cokes indicated — Coke. Nitrogen per cent. Gas retort (Lancashii-e ?) ., 1*38 Beehive oven .. .. .. 0*51 Simon-Carves oven . . . . 0-38 or inversely proportional to the temperature. Modern tar is heavier than the liquor ; this must neces- sarily be the case where naphthalin and phenols are pro- duced in quantity. The sp. gr. of Enghsh tars is about 1-1 to 1*15 ; of Scotch tars, which are derived from cannel coal, about 1-1. Cannel tars are poorer in useful aromatic compounds than are bituminous tars. Tar is treated with steam (or distilled with one-fifth of its volume of water, or distilled by the heat of a steam- 62 MANUALETTE OF DESTRUCTIVE DISTILLATION. coil) to remove light naphtha, or crude " benzol." The stills hold from 500 to 4,000 gallons, and are horizontal cylinders. The steam brings over about 5 — 10 per cent, at most of hght naphtha (sp. gr. 0*78 — 0*88*) — according as the coal is bituminous or cannel — and some ammoniacal water, which is treated like the other "liquor." The residue of the distillation is heated by fire to about 200°, when most of the heavy oil comes over, and afterwards to over 300°. The residual pitch, which amounts to 30 — 50 — 70 per cent, of the tar, is after several hours' cooling (either in the still or a separate tank), run off into moulds. It is generally utilised for '' asphalt," by mixture with about four times its weight of sand, chalk, or other inert material; or for "patent fuel," by moulding with four parts of coal dust or similar material. The hght naphtha is run off the " liquor " beneath it, and churned with 5—12 per cent, of oil of vitriol, and afterwards with about 2 per cent, of caustic soda (in aqueous solution, of sp. gr. 1*4). Lime may be ads^anta- geously used instead of soda, if great care be taken to avoid excess. The percentage of loss is about the same as that of the added vitriol. Sometimes the naphtha is distilled between the acid and alkaline treatment ; on the other hand, the lime and acid treatment may be performed, if desired, in the same tank. Mixtures of lime and caustic soda are also used ; and this is probably the preferable course. It is also undoubtedly advisable to re-distil the crude naphtha before submitting it to this chemical treat- ment. The residues of this second distillation, when mixed with lime {see RosiN Oil), yield a lubricating " grease," as is the case with several genera of unsaturated hydrocarbides. Finally, the purified naphtha is distilled by steam. About half of it consists of " 50 per cent. * Formerly this distillate was allowed to reacli the sp. gr. -95. COAL TAR. 63 benzol" (to 140° C.) and the remainder (to 170° C.) con- stitutes " solvent " benzol, the later fractions yielding some " burning naphtha." " 90 per cent, benzol " boils at and below 100°. Various fractions can be obtained of a character intermediate to these. The heavy or " dead " oil may be used, as such, for preserving or "kreasoting" timber; for which purpose portions boiling above 310° are better adapted than the more volatile phenols. Kreasoted timber owes its preser- vation, according to WilHams, chiefly to pyridine and quinoline bases, which it retains even after a lapse of thirty years ; in a less degree to naphthalin and phenols, neither of which is found in old kreasoted timber. Some part of its durability may also be due to acridine. The oil is more commonly distilled. The earlier portions of the distillate (150°— 200°) contain impure phenol; the follow- ing portions (200°— 212°) are rich in naphthalin ; the next fi-action (212° — 270°) contains kreasols; and the last (to 360°) yields crystals of anthracene on cooling. Naphthalin is not at present utilised on the large scale ; but anthracene is the source of artificial alizarin. Tar yields less than 1 per cent, of crude anthracene. The mother-liquid of the anthracene, after further concentration by distillation, and a second deposition of crystals, is chiefly valuable for illuminating, and more especially for lubricating purposes. The treatment of the phenol fraction is the object of a special industry, that of carbolic acid. Instead of passing steam through the retort in the first distillation of coal-tar, direct heat alone is very frequently apphed (as in the crude paraffin oil still), the water naturally suspended in the tar providing for some time the necessary steam. In this method the gases at first extricated are sometimes passed through a purifier, and afterwards burned. The " first runnings " from the still are very 64 MANUALETTE OF DESTRUCTIVE DISTILLATIOX. light oils, almost free from phenols, and accompanied olP course by ammoniacal water. As soon as the latter has completely passed over, a considerable access of heat is necessarily required to volatilise, unaided, any further portion of the tar ; so that this period of the distillation is usually very well marked. Light oils of the naphtha class are distilled up to 170° at least; impure phenol (carbolic acid) and naphthalin to a point exceeding 220^ ; kreasols to 270°; and anthracene oil to 360°. The residue is pitch. As in the case of paraffin stills, the worm must be kept hot at the end of the distillation. Not unfrequently, super- heated steam at various temperatures is employed in the last, or last two, stages. Stills of the largest size are re- charged about every two days. Cannel coal-tars yield little, if any, " 90 per cent, benzol," but a large proportion of xylol. Of phenols, cannel-tar yields the largest total bulk, but least phenol proper ; Newcastle tar containing least " total phenols," furnishes the largest proportion of phenol proper. Lanca- shire gas-tar yields about 5 per cent, of crude phenols, containing 65 per cent, of crystalKsable phenol (W. Smith.) The following percentages, taken from Crace-Calvert, may still (the author is assured by a distinguished practical authority) be taken as fairly correct, viz. : — — Light Oils. Phenols. Heavy Oils. Naphthalin. Wigan cannel 9 14 40 15 Newcastle . . 2 5 12 23 Staffordshire 5 9 35 29 It is difficult to reconcile the numerous confficting statements made on the subject of coal-tar distillation, but COAL TAR. 65 the following may be taken as an average of recent results : — First runnings Light oils Kreasote oils, naphthalin and phenol Anthracene oil Pitch 2-5 5-0 27-5 10-0 55-0 100-0 7-5 The relation of pitch to tar is thus about the same as that of coke to coal ; and the kreasote oils, &c., generally weigh half as much as the pitch. Sometimes as much as 75 per cent, is taken as pitch, the quality of which is then, of course, soft. Good hard pitch of sp. gr. 1*28 melts at about 200°, and has been found to have the composition CeHsO. The following data have been given by Schultz on the authority of Riitgers — Composition of Londo Benzol of 50 per cent. Solvent naphtha Burning naphtha Kreasote oil . . 30 per cent, anthracene Pitch Loss Berlin Gas- Tar. Benzol and toluol for anilines Bright (solvent) oil . , Crvstalhsed carbolic acid Gas- Tar. 1-1 1-0 1-4 33.2 1-0 58-6 3-7 100-0 0-8 0-6 0-2 6^ MANUALETTE OF DESTRUCTIVE DISTILLATION. Kreasol (disinfectiug quality) 0-3 Naphthalin 3-7 Anthracene (pure) 0-2 Heavy oil (for pickling timber) . 24-0 Pitch 55-0 Water and loss 15-2 ( V. supra^ pp. 57, 58.) 100-0 According also to the same authority the yield of anthracene very seldom exceeds 0*5 per cent., and the maximum of crude naphthalin is 8 per cent. ; the tar at Berlin constitutes 4-8 per cent, of the coal. Anthracene from cannel tar generally contains paraffin, a troublesome impurity, best removed by w^ashing with carbonic disulphide. The portion of coal-tar and pitch which is insoluble in ordinary solvents, is known by the name of " free carbon," an expression obviously very erroneous. Schulze states that the neutral tar-oils boiling at 170°— 210° consist of about 50 per cent, resinifiable matter, 15 per cent, trimethylbenzenes, 15 — 20 per cent. tetrame*:hyl- benzenes, and 15 — 20 per cent, of naphthalin. The three kreasols occur in about the proportion metakreasol 40, orthokreasol 35, and parakreasol 25. There can be little doubt that the future economical treatment of dead oil, and in general of crude oils of high boihng-point, will in the main turn upon some method of distillation in vacuo. The following complete analyses of London and average cannel gas-tar (Scotch) have been made in the author's laboratory : — ( :OAL TAR. ( London. Scotch Cannel *Carbon .. 77-53 85-33 ^Hydrogen 6-33 7-33 ^Nitrogen 1-03 -85 Sulphur •61 -43 Oxygen . . 14-50 6-06 100-00 67 100-00 If we deduct nitrogen and sulphur, we shall obtain the following results : — London. C21H02O3. Scotch. C18H20O Carbon 78-82 78-26 86-44 85-71 Hydrogen . . 6-44 6-83 7-42 7-94 Oxygen , . 14-71 14-91 6-14 6-35 100-00 100-00 100-00 100-00 The ubiquitous C3 unit again appears in the mean com- position of the tars ; it must, therefore, be common to both kinds of gas. A conspectus of operations and quantities in the ti eat- ment of coal-tar is given on the next page. * Mean of two determinations. QS MANUALETTE OF DESTRUCTIVE DISTILLATION. < D Q o < O a; o aH v o a~ n — lO ,c "^ ,sl II 1 O CO ;:: to — -o q -s-?- -w t/2x: g J2 o 1 Ph fil ^ ft - = — S o'"'^ I ~ J .h" ~ 1 ■ 2 -cis -a^ iS S & != ^ — O 2 M — s §9 . 1 ^og* COAL TAR. 69 Annexed is a table of the products of destructive dis- tillation of coal. The formula, boiling-points, and melting-points are added, so far as known. Destructive Distillation of Coal. Name. Eormula. B.P. M.P. Hydrogen Ha Metliylic hydride CH4 Hexvlic CeHn 68° Octylic „ CsHis 119 Deeylic C10H22 171 Paraffin . . C„H2„ + 2 Ethylene C2H4 -102-5 Tritylene CaHe Tetryleue C4H8 -5 Pentylene C5H10 31 Hexylene CeHjs 71 Heptylene C7H14 97 Acetylene C2H2 Crotonylene C4H6 25 Terene . . C5H8 Hexoylene CeHio 80 Styrolene CsHg 145 Indene . . C9H8 Thiophene C4H4S 84 Thiotoluene CsHeS 113 Thioxene CfiHsS 137 Benzene . . CfiHe 80 5* ir Parabenzene* . CeHe 97 Toluene . . C^Hg 111 Orthoxylene CsHio 143 Paraxylene CsHio 137 Metaxylene Cgiiio 137 Cumene . . C9H12 1G6 Ethylbenzene . CsHio 133 Pseudocumene . C9H12 165 Hemellithene . C9H12 175 Mesitylene C9H,2 163 Cymene . . C10H14 166 Durene . . C10H14 196 80 •5 Terpene . . C10H16 171 , Naphthalin C,oH8 218 80 Methylnaphthalin CiiHio 242 -x8 Naphthalin liydride . . CioHio 210 Naphtols, — o & CioHsO 279, 288 94, 33 Phenyl CiJI,o 254 70 Acenaphthene . . CioUio 285 100 * ? Dipropargyl. 70 MANUALETTE OF DESTRUCTIVE DISTILLATION. Destructive Distillation of Coal — (continued). Name. Formula. P.P. M.P. riuorene C13H10 295 113 Phenanthracene CuHie 340 99 Anthracene C14H10 360 213 riuoranthrene . . C'lsHio 109 Pyrene CieHio 148 Anthracene hydride . C14H12 305 106 Methy lanthracene ^15Hl2 , . 200 Chrysene CisHis , . 249" Retene CrsHis 350° 99 Picene . . C22H14 519 338 Water .. H2O 100 Hydric sulphide H2S -85 „ cyacide . . HCN 26 -18 „ sulphocyanide . HCNS Carbonic oxide . . CO -193 , , „ dioxide CO2 --78 . , „ disulphide . CS2 47 -110 Sulphuric dioxide SO2 -10 Hydric acetate . . C2H4O0 120 15 Acetonitril C2H3N" 77 Ethylic alcohol (?) CsHgO 78 -130-5 Phenol CgHfiO 182 42 Hydric benzoate C7H6O2 250 120 Kreasols, — o, m p. C^HgO 118, 201, 199 31, (?),36 Pyrokreasols, — a, )8, 7 . C28 1^2602 104,124,195 Phlorol CsH^oO 219 , , Cumarone CgHeO 170 Ammonia NH3 -33 -70(?) Butylamine C^HnN 75-5 Aniline . . CgH^N 182 -8 Cespitine C5H13N 96 Pyridine.. C6H5N 115 ')-Pieoline CgH.N 144 a-a-Lutidine C7H9N 142 j8-Lutidine C7H9N a y-Lutidine C7H9N 157 Collidine CsHiiN 170 Parvoline C9H13N 188 Coridine . . C10H15N 211 Rubidine CnHi;N 230 Viridine C12H19N 251 Acridine . . C13H9N 360 107 Carbazol C10H9N 355 238 P aeny Inaphtylcarbazol Cj.HhN .. 330 Leucoline Cgd^N 220, 238 Lepidine. . C10H9N 254, 268 Iridoline. . Cryptidine CnH„lV 272 Tetracoline C12H13N 292 COAL TAR. 71 Destructive Distillation of Coal — (continued). iXame. Peiitacoline Hexacoline Heptacoline Octacoline Pyrrhol . . Carbon (hydrogenated) Sulphur . . Nitrogen. . Formula. Ci3Hi,N 312 ChHi7N 327 C15H19N 347 CieHoiN 362 C4H5N 133 Cn .« S2 400 N2 -193 P.P. M.P. 115 213 (?) The following are the specific gravities of some of the more important of the coal-tar compounds : — Compound. Sp. gr. AtO^ At 15° At 18°. Benzene .. Toluene .. _ Xylene (mixed isomers) . . Naphthalin Carbonic disulphide Phenol Aniline , . •8991 •8841 •877 1-036 •8846 •8702 1 -272 I'-iss 1-065 Action of Heat on the Organic Matter in Coal. Professor W. Foster {Proc. Inst C.E., April, 1884) has completely analysed, and distilled at a high temperature, two samples of Yorkshire and one of Durham coal. His mean results, apart from sulphur, nitrogen, pit- water, and ash, correspond to the following relations : — 33C + 2C,,H,30 = Organic matter in coal. (Calc.) 100 (Found) — Fixed carbon. Gl-5 ., Gl-5 . C,5H3.0 Gas and tar. 35-7 . H^O Organic water. 2'^ 38-5 12 MAXUALETTE OF DESTRUCTIVE DISTILLATIOX. Foster has also similarly examined a Scotch cannel. His data may in Hke manner be reduced as follows : — 2C12H12O = 12c + Cj^H^^O + H2O (Calc.) — .. 41-9 .. 52-9 .. 5*2 (Found) — . . 41-3 . . 58-7 The Heywood cannel gas-coal, which may be taken as representing an average Scotch cannel, has (page 49) been analysed and distilled. The reactions are — at a low temperature — ^Q^YL^^O = 270 + C^'R.e^s + H2O Fixed carbon. Gas and tar. Organic water. (Calc.) 100 .. 59-6 .. 37-1 3-3 (Found) — .„ 584 .. 38*3 .. 3-6 and at a high temperature — 4CgH„0 = 24C + C„H,e03 + H^O Fixed carbon. Gas and tar. Organic water. (Calc.) 100 .. 52-9 .. 43-8 .. 3-3 (Found) — .. 52*5 .. 43-9 .. 3-9 Mills and McMillan {Journ. Soc. Chem. Tnd., 1891) distilled a Scotch bituminous coal w^ith the following results : — At a low temperature — 28Cj3H,,0 = C\,,H„3 + C3„H,,09 + C3„H,„,03 4 16H,0 Coke. Tar. Gas. At a high temperature — 30C.,H„O = C,,„H,, + (J3oH,„0, + 2C3„H,3„03 + 16H,0 Coke. Tar. Gas. It is evident that the high temperature volatilises in gas twice as much carbon as the low temperature does. COAL TAR. 73 The following results are known as regards the com- position of the organic matter in coal : — Yorkshire and Durham . Balquhatstone Boghead . . Average cannel Heywood gas cannel Good average Scotch sha . . C12H12O .. C,H,20 It may now be regarded as proved that this organic matter breaks up when heated in multiples of C3. Average Composition of Coal- Gas. P. Frankland {Journ. Soc. Chem. Ind., iii,273) has given the composition of fifteen samples of purified coal-gas pre- sumably bituminous). The mean percentage and variations are as follows : — Ethylene and its equivalents. Hydrogen. Carbonic Oxide. Marsh Gras. 6-69 1-45 Variation. 47-39 3-47 Variation. 4-05 0,;69 Variation. 38-83 1-57 Variation. These ratios correspond to 3C2H4 : 24H2 : 2C0 : 20CH, : 200^ ( = 102 vols.; the last being added to fulfil the condition of unpuritied gas). Summing the above formulae, we have the collocation CgoHj^gOg, which may otherwise be ex- pressed as 30CH^ : HH^O : 4H2. Having regard to variation, we shall be correct in regarding average unpurified coal- gas as consisting of redistributed marsh-gas and Avater. Here also the C3 unit recurs. 74 MANUALETTE OF DESTRUCTIVE DISTILLATION. The same author (loc. cit.) gives the composition of three samples of gas from Scotch cannels. His figures show that this gas tends to consist of redistributed methyl and water ; but the data are too few, and their variation too great, to allow of any very exact inference. The output of the United Kingdom in each twelve months since 1857 is given below : — 1858 1859 1860 1861 1862 1863 1864 1865 1866 1867 1868 1869 1870 1871 1872 1873 1874 Tons. 66,109,603 71,979,765 84,042,698 86,407,941 81,638,338 86,292,215 92,787,873 98,150,587 101,754,294 104,500,380 103,141,057 107,427,457 110,431,192 117,352,028 123,497,316 127,016,747 125,067,916 1875 1876 1877 1878 1879 1880 1881 1882 1883 1884 1885 1886 1887 1888 1889 1890 1891 Tons. 131,867,105 133,344,766 134,610,763 132,607,866 134,008,228 146,818,522 154,184,300 156,499,977 163,737,327 160,757,781 159,351,418 157,518,482 162,119,812 169,935,219 176,916,724 181,614,288 185,479,126 (Average present price, 8s. per ton at the pithead.) The American (U.S.) bituminous coal of all kinds raised in 1888 was 91,106,998 tons of 2,240 lbs., having a value of 122,497,341 dollars. Mr. L. T. Wright has compiled the following very interesting table showing the percentage value of each product to the total revenue of the Companies indicated : — Company. Gas. Coke. Tar. Ammonia. Sundries. Nottingham, 1881 and 1882,, S. Metropolitan, 1883 G-ashght and Coke Cos., 1883 Cie. Parisienae, 1881 75-06 72-05 78-47 70-70 8-29 15-18 11-43 18-00 8-21 5-34 2-98 3-48 3-27 7 '04 6-86 1-91 5-17 •39 •26 6-00 Id 1889 there were 578 gas undertakings in the United COAL TAR. 75 Kingdom, with an authorised capital of 76,593,724/. The amount of coal carbonised was 9,633,011 tons: and the amount of gas produced 98,081,319 cubic feet. In 1889 the Paris Gas Company sent out 11,013 milKons cubic feet. There are 971 gas companies in the United States, and 47 in Canada. 592 companies in the United States manu- facture their gas from coal, and 296 under various patents and processes. In Canada 24 companies manufacture from coal and 16 from other processes. One company manufacturing gas from coal with an output of 11,000,000 cubic feet received 75c. per 1,000 feet, 26 companies, with an output of 1,879,900,000 cubic feet of coal-manu- factured gas, received 1-50 dols. ; 6 companies manufactur- ing by other processes, with an output of 900,000,000 cubic feet, receive 1*50 dols., and 45 companies, manu- facturing from coal, with an output of 468,000,000 cubic feet, receive 2*25 dols. per 1,000 feet. The output of 495 coal-gas companies is 17,502,305,000 cubic feet, the income from which is 30,452,710 dols.; 188 companies manufacturing by other processes have an income of 10,291,000 dols. from an output of 5,554,000,000 cubic feet. The average price of coal-gas is 1-73^^0 ^ols. ; of gas manufactured by other processes, 1*81 -^^ dols. In the matter of pubhc lamps, 1,056 receive gas at a cost of Ic. per hour, 100 at IJc, 142 at Ij'-^c, and 100 at l^c. ; 6,000 lamps range from Ic. to 4-7c. per hour ; 104,000 lamps realise 3,319,287 dols., an average of 30*17 dols. per lamp. The output of gas by 517 companies manufacturing from coal requires 1,908,611 tons of coal. The output of 206 companies using water and other processes require 178,563 tons of anthracite coal. The capital required for all the gas interests amounts to 261,000,000 dols., the income from which is about 50,000,000 dols. [1890.] 76 :maxualette of desteuctive distillation. Appendix to Coal-Tar. In the maimfacture of iron by the blast farnace method, tar and ammonia are naturally among the products when coal is employed. Both of thepe products admit of collec- tion. [For drawings of various kinds of condensing and scrubbing plant for this purpose, see Journ. Soc. Chem. Ind., 1885, p. 217.] The volume of the gases from which they are separated is about 130,000 cubic feet per ton. The percentage composition by volume of these gases is, according to W. Jones, carbonic oxide, 25 — 30 ; carbonic dioxide, 3 — 8 ; hydrogen, 5 — 7 ; marsh gas, 2 — 4; nitrogen, b2 — 60. The yield of ammonic sulphate is probably about 16 pounds per ton; of tar, or, more correctly, tar-emul- sion, 20 gallons. The tar, Avhich is intermediate in its nature between shale and ordinary tar, contains a great amount of gas bubbles in suspension, and intumesces very much when heated : it is of rather " dry " quality. It contains no considerable amount of true phenol, benzol, or anthracene. The following results were obtained in the author's laboratory : — Sp. gr. of tar 1*00005^ After steaming (100"^) . . . . I'OOOloj Volatile in steam (100^) . ., 7-34 per cent. Sp. gr. of portion volatile in steam -90800 COAL TAE. 77 Examination of Portion Volatile in Steam. Percentage. Bciling-Poiut. Sp. gr. Per cent, of phenols and phenoids in fraction. 1-70 9 12 12-53 32-80 43-85 100 152 175 200 Above 200 •86936 -87014 •88546 •90631 •92241 6*25 9-38 17-50 Watson Smith examined another sample of sp. gr. -954, and obtained the following (volume) percentage results :— Water (ammoniacal) . . Naphtha and oil to 230° Oil to 300° 300° to sohd distillate . . Solidifying distillate . . 30-6 2-9 7-0 13-0 16-8 The coke amounted to 21-5 per cent, by weight; loss 5-5 per cent. Hard paraffin was esthnated at -54 per cent. The amount of coke is extremely large. Blast furnace tar contains 17-5 per cent, by volume of phenols. Amongst these W. Smith has found meta- kreasol, metaxylenol, pseudo-cumenol, and naphtols. Allen found in Gartsherrie tar (1887), carbon, 83*64 ; hydrogen, 10-59, and sulphur, -09 per cent. A specimen of average Scotch cannel gas-tar gave the subjoined numbers ; — Sp. gr. of tar After steaming . . Yolatile in steam Sp. gr. of portion volatile in steam . . . . . . • • '93334 1-09430^ M2830) 10''33 per cent. MANUALETTE OF DESTRUCTIVE DISTILLATION. Examination of Portion Volatile in Bteam. Percentage. Boiling-Point. Sp. gr. Per cent, of phenols in fraction. 9-85 18-19 26-00 22-85 23-11 o 100 155 175 200 Above 200 •86926 -88255 •91426 •94763 5-00 10-00 14-38 Products from Cohe Ovens. Mr. Jamieson, of Newcastle, has (1882) proposed the following simple process for collecting products from ordinary coke ovens. The oven is lighted at the top ; and the products of combustion, drawn downwards by means of an exhauster, cause destructive distillation of the coal beneath. Paraffiniferous tar and combustible gas reach the base of the oven, whence they are carried through perforated iron pipes to a main. The exhauster produces an inward pressure of 1 inch (water), and effects the combustion of 2 cwt. of coke per ton of coal. There is a yield of from 5' 6 to 8 gallons of crude (low-tempera- ture) oil, and 3 — 10 pounds of amnionic sulphate per ton. Sp. gr. of the oil about -97. The gas amounts to 200 •cubic feet per hour per ton. Analysis of the Oil Lubricant • • . • . . 39-5 Illuminant . . .. 37-7 Scale . . . . . . 13-5 Tar and loss, Siii. .. 9^3 100-0 COAL TAR. 79 Average Analysis of the Gas. Carbonic dioxide . . 4-22 „ oxide . . 23-88 Hydrogen . . 26-67 Oxygen . . 3-29 Nitrogen .. 41-93 100-00 Hydrocarbides do not seem to have been determined in the gas. The tar contains no benzol, but very small quantities of toluol and rather more xylol; the greater part of it boils at 250° — 350°, the distillates up to the latter temperatui'e yielding no deposit on cooling. Above 350°, paraffin melting at 58° passes over. There is only a trace of phenol, and rather more kreasol: these are fol- lowed, on fractionating, by obscure resinous phenoids. Phenols and phenoids together amount to about 5 per cent. Anthracene is not present. The whole distillate is remarkable for the entire absence of fluorescence. It should be borne in mind that the composition of this tar depends very much on that of the coal from which it has been obtained. Thus Watson Smith found from 5^ to 9 per cent, of scale in samples of different origin. Pitch or coke on rectification is, of course, low in this tar. Watson Smith has examined a sample of tar from the Simon-Carves coke ovens. These are worked at an ex- tremely high temperature, and the tar consequently contrasts strongly with that from the Jamieson process. Sp. gr. 1-106.. The (volume) percentages on distillation Avere as follows : — 80 MAN U ALETTE OF DESTRUCTIVE DISTILLATION, Water . . 6-2 Naphtha to 120° 1-6 Below 210° 2-9 ^^ 220° 1-3 j> 230° 0-5 300° 186 Above 300° 34-2 Half-coked pitch 30-4 Loss (by diff.) 4-3 V Mostly Naphthalin. Naphthalin and anthracene. Mostly anthracene. 100-0 Very little " red " or " anthracene " oil was present. Available anthracene, -73 per cent. *' Gas-Producer'^ Tar. The tar from a Sutherland gas-producer has been fractionated by Watson Smith. In general character it occupies a position between the Jamieson and Simon- Carves tars, but near the former. Sp. gr. 1-08. The (volume) percentages are — Below 230° (excluding water) . . 5*4 230°— 300° 10-0 300° to solidification of distillate . . 14*5 Oils, solidifying . . . . . . 10*4 Coke, 30 per cent, by weight ; loss and water, 32 per cent. Naphthalin and anthracene could not be detected ; paraffin amounted to 6*7 per cent, on the weight of the tar. The enormous residue of coke is very noteworthy. Hydrocldoric Tar. An important modification in the conditions of formation of coal-tar has been studied by E. Heusser (Ger. Pat. 24758, 1883). When a mixtnre of chlorine with hydric chloride is passed through an ordinary charged gas retort, it acts as a hydrogenating or dissociating agent, producing a tar WOOD TAR. 81 very rich in benzol, and having the following average composition : — Water 10 Benzol 18 Boihng at 60^—180° Chloro-compounds, heavy hydro carbides, naphtha- lin, anthracene. , . . . 20 Pitch 52 100 18 per cent, of the crude benzol was reduced to 10 per cent, by purification and distilhng to 150°. On the other hand, zinc chloride, in presence of hydric chloride, greatly increases the yield of heavy hydro- carbides from coal, and can even convert some of the lighter constituents of tar, when distilled theremth, into heavy ones. WOOD TAR. Wood consists essentially of cellulose (nC^H^fi.) and 13 per cent, of an isomeric gum, together with 20 — 25 per cent, of water, and a little mineral matter. When heat is applied to it in closed vessels, it decomposes, giving ofi*, among other products, a quantity of steam;* at firsts there- fore, the process is necessarily under *' low-temperature " conditions. As cumula ive resolution continues, less water relatively is given off, and the heat can exert its full effect; the second stage of the distillation is, therefore, under " high-temperature " conditions. * Furfurol can be obtained at about 200^, or even lower. F 82 MANUALETTE OF DESTRUCTIVE DISTILLATION. Cellulose is stable at 150°. The first effect of lieat is at first to dehydrate it. By interpolation among Violette's well-known results on the heating of wood (Ann. Ch. Phys. [3], xxxii. 304), it appears that nQfi^O^ corresponds to a temperature of about 185°, and nQ^fi^ to about 220°, in the absence of pressure ; in presence of pressure, the latter temperature corresponds to nQ^fi^. At a point some- what below 430°, and without pressure, the residue has the composition, nCgHgO. The final stage TzCg is probably not attained under ordinary experimental conditions. Wood thus yields both aromatic and fatty bodies ; and these are specially characterised by being to a great extent oxy-compounds, as is natural in a series of cellulose deriva- tives. It is very interesting to note, as a further consequence of the mixed conditions of this distillation, that naphthalin and parafiin are both present among the products. \_See Cellulose.] The heat is allowed to reach bright redness ; charcoal is left in the retort, illuminating gas is evolved, and the tar is separated and condensed in a very wide copper worm. Sulphur-compounds and ammonia are not given off. AVood may yield approximately — Charcoal . . . . 20 — 30 per cent. Acid water . . . 28 — 50 „ Oily (light or heavy) tar 7 — 10 „ Gas and loss . . . . 20 — 37 „ Morgan has found the following results (1885) with coppice oak: — Liquid distillate (tar, acid, &c.) . . . . . . 50 — 60 per cent. Glacial acid . . . , 3*44 „ Naphtha (-8263) . . . 1-03 Charcoal , , . . . . 31*25 „ WOOD TAR. Tims, dry wood is not unfi •eqiiently split up in the p rtion — CeH.oO, = 30 + 4PI^0 -^ C3H,0 Wood. Carbon. Water. Gas and tar. 100 22-2 44-5 33-3. 83 though this equation must not be taken as indicating the mode of decomposition (page 7). The general met hylic character of the products is strongly marked ; and in the case of different woods, at the same temperature, the total methyl in the distillate is — if Stolze's observations be correct — a constant quantity. The retort is nearly always made of thick boiler-plate, and either horizontal or vertical ; the former position is the better of the two. [Pierce uses a brick still, capable of holding 56 cords (100 tons) of wood; he distils during six days and cools during six days. The products are — char- coal, 30 per cent. ; 5 gals, pyroligneous acid and 175 cubic feet gases per 100 lbs.] When the object of the distiller is to obtain the maximum quantity of acid, the retort should- not be heated beyond 350°— 400°. He, then, probably derives his products, and their collaterals, from the residues /iC^HgOj — wC^HjO of cellulose. When wood is heated for the purpose of making gas, the retort is followed by a heated empty chamber or " generator," in which takes place what is virtually a second destructive distillation. According to Jakowlew — Acetic acid. 100 parts wood } ield— I. II. Linden 10-24 10-17 Birch 9.52 0.29 Aspen 8-0«) 8-37 Oak.. 7-92 8.24 Pine. . b'^b 6-12 8i MANUALETTE OF DESTRUCTIVE DISTILLATION-. Aceti c Acid. 100 parts wood yield — Fir I. 5-24 II. 5-09 Birch bark . . 2-20 2-38 Cellulose from bircli 6-21 • • Cellulose from pine 5-07 The wood should, in any case, be dry. When worked for gas, the charge is about 50 — 60 kilos., yielding about 16 cubic metres of gas in 1*5 hours. When worked for tar, the charge amounts to one or two hundredweight or more, which are distilled in 12—14 houi-s, the initial heat being low ; in this case the gas is burned under the retort. Much decomposition ensues under 150° C. ; but the more carbonaceous products pass over abov^e that temperature. As is usual in destructive distillation, the tar becomes thicker and darker as the process advances, and the rapid application of a high temperature leads to loss of valuable products with increase of gas. The writer has seen in use round cast-iron retorts 1^ inch thick, 7 feet long, and 3^ feet in diameter ; when worn underneath, these could be re-set bottom upwards, and had been known to last from three to ten years. Charge, about six hundredweight. When the gas is utilised, a ton of wood requires about 7 — lOJ hundredweight of coal for its distillation, the latter being demanded by oak wood. In the South United States the destructive distillation of wood is carried on (according to Clark) in cast or wrought iron or steel retorts, the two latter being especially used for large retorts, and the former for small ones. They are generally cyhndrical; 3 — 9 feet in diameter, and 5 — 30 feet long. The furnace gases are first brought under a protecting brick arch below the retort, and afterwards reversed above it. The most resinous pines, preferably with a deep red section, are selected, the old tapped WOOD TAE. 85 trees giving the most abundant yield. The fuel is mainly the gas given off by the distillation itself The tempera- ture for the first 12 hours is 290°, afterwards increasing to 450°. The following are average results from 3.6 charges: — Wood, 4,573 lbs.; light oil, -875 — -95 sp. gr., 13-8 gals.; pine oil, -950 — 1*040 sp. gr, 73*5 gals.; pyro- ligneous acid, 1-02 sp. gr., 185 gals.; charcoal of poor quality, 1*511 lbs. The distillates are allowed to settle when the oil floats on the acid. It is distilled down to four-fifths, and used for kreasoting purposes. Retoi-ts in which the wood is urged forward by a chain, or leaves armed with scrapers, are in use for the distillation of wood. Crude wood-gas contains about 40 per cent, of carbonic oxide, 26 per cent, of dioxide, and 11 per cent, of marsh- gas. The earlier portions contain a good deal of carbonic dioxide with hydrogen and marsh-gas: next follow imperfect hydrocarbides and carbonic oxide. The last portions are very rich in this oxide. The purified gas contains about 3 vols, of hydrogen, -25 vol. marsh-gas, •08 vol. hydrocarbides, and -3 voL carbonic oxide. It is 1*2 times heavier than coal-gas, which it considerably exceeds in illuminating power, and requires very open burners for its proper combustion. The watery portion of the distillate from a ton of wood amounts to about 100 — 130 gallons, containing 4 — 8 per cent, of the weight of the wood in " glacial acetic acid " (hydric acetate), and having the sp. gr. 1-03 — 1*04. This is termed "pyrohgneous acid." It is allowed to rest 24 hours, and then drawn ofi" from below the tar proper (wliich, however, is frequently beneath it), and may be used at once for making iron mordant, which is a solution of scrap iron in aqueous hydric acetate, and contains ferrous, ^vith some ferric acetate. It is also treated witli «b MANUALETTE OF DESTEUCTIYE DISTILLATION. litharge, in order to prepare plumbic acetate (" sugar of lead"). A better product is, however, obtained by re- distilling the crude pyroligneous acid, an operation which is conducted in copper stills, heated by hot gases or an internal steam coil (at 25 lbs. pressure). Cast-iron stills can be used, but are less satisfactory. Tar deposited here must be drawn off hot. The first portion, or 20 per cent, of the distillate, consists of dilute crude ivood spirit or methylic alcohol (CH^O) ; this is used in preparing "methylated spirit" or "finish," a mixture of impure methylic with ordinary alcohol. As the methylic alcohol leaves the still, a quantity of tar which it held in solution separates out. The subsequent acetic distillate has a brownish-yellow colour. It is purified by conversion into sodic or calcic acetate, by saturation with the correspond- ing carbonate. The resulting solution is evaporated to dryness and roasted to a point just short of decomposition (240° in the case of sodic acetate) ; this treatment destroys all tarry matter. The residue can now be distilled with hydiic sulphate or chloride, either with or without a previous crystallisation from water; the operation is performed in horizontal retorts of cast-iron. If sodic acetate be the salt chosen for treatment with hydric sulphate, the residue in the retort is sodic sulphate, which can be sold to the soda manufacturer. The amount of hydiic sulphate or chloride used must depend on the amount of acetate present ; but this latter is always kept slightly in excess when hydric chloride is used, so as to avoid the presence of chlorine in the distillate. Calcic acetate requires rather less than an equal weight of aqueous hydi^ic chloride of sp. gr. 1-16. When hydric sulphate is employed, it is difficult to avoid contaminating tlie product with sulphurous oxide, more especially when imperfectly roasted acetate is used ; in this case, there WOOD TAR. 87 must be fresh rectification over some oxidiser, potassic dichromate for instance. Many distillers rectify their crude " naphtha " (with or without the acetic distillate added) with hme. This keeps back tarry matters, and converts methylic acetate into alcohol. The high specific gravity of the acetate renders this operation important. Cofiey's stills are in use for the further rectification of the naphtha. Naphtha can be made " miscible " with water by diluting till perfect precipitation ensues, agitating warm with melted parafiin, cooling with sustained agitation until the paraffin sets, filtering and redistilling. The paraffin can be steamed and used again several times. Hydric acetate, even in the glacial condition, can also be prepared by a process contrived by Melsens. This consists in half-saturating the aqueous solution with potassic carbonate, evaporating to dryness, and heating to incipient fusion. The residue, which consists of hydi'O- potassic acetate [KH. (0211302)2], is transferred to a retort, and distilled below 300°. The distillate is at first somewhat aqueous, but soon increases in strength, and then solidifies on cooling. The residue in the retort is neutral acetate, which can be evaporated again and distilled with a fresh portion of hydric acetate. In preparing acetic distillates, the spouts of the retorts and worms must be made of copper. Worms have also been constructed of tin, and even silver ; earthenware is not so advantageous. Little, if any, glacial acetate is now made in this country. Among the constituents of crude wood spirit, the fol- lowing have been traced : acetone (at least 3*4 per cent.) and higher ketones; aldehyde, dimethylacetal, and allyl alcohol, propyl aldehyde, and dimethylfurfuran ; methylic 88 MANUALETTE OF DESTRUCTIVE DISTILLATION. formate and acetate, formic, crotonic, and angelic acids ; pyroxanthin, CjgHjgOg ; traces of ammonia and methyl- amines. The tar proper is seldom utilised, at any rate, in Great Britain; and mnch of the Russian wood-tar is adulterated with brown British naphtha. [Genuine Russian tar, from the roots of conifers, has the sp. gr. 1*06.] On distillation, it yields (at 70°— 250°) a hght oil of sp. gr. -841— -877. This contains, successively, oxy-products, including syl- vane, CgHgO, and benzol to 100° ; chiefly aromatic hydrides to 150° ; more aromatic hydrides and phenol, kreasol, &c., together with o^z/-phenol {G^fi^, a characteristic product) to 200°; then naphthalin and paraffin. The paraffin contains lignocerate, ^24)^Afi2^ ^^^ retene. Some pitch remains behind. The 150° — 200° fraction is known as " wood kreasote ;" it contains kreasol and phlorol. The acid tar (180° — 300°) holds phenol, parakreasol, a-metaxy> leuol, guiacol, kreasol, casrulignol, and the dimethylic ethers of pyrogallol, methylpyrogallol, dimethylpropyl- pyrogallol (" picamar "), and propylpyrogallol. The inter- mediate fatty hydrides seem to he absent ; but they are represented, certainly as far as Cjq, by the corresponding fatty ketates (acids), ethylic aldehyde, and methylic alcohol. Valerolactone {C^B.^q02) has also been found in crude pyroligneous acid. The more volatile portion of Swedish pine-wood tar yields, after treatment with potash, two terpenes — australene, boiling at 158°, and (-I-) sylvestrene, boiling at 175°, the two together constituting about 80 per cent, of the oil. According to Hager, pure beech kreasote is not soluble in twice its bulk of anhydrous glycerin, as is the case with other kreasotes. Most woods are available for acetate making; those being (according to Payen} the best which are " hard," or WOOD TAR. 89 whose cells contain most " matiere incrustante " (oxy- cellulose?). Hence tlie trunks are better than the branches. Pine-wood yields most tar (14 per cent, from dried stems, 18 per cent, from roots) ; beech most liquor (45 per cent.) Sawdust can also be used ; bat it requires to be forced through the retort by means of an endless screw. Peat yields similar products. In Russia the outer bark of the birch, after stacking, is made to furnish a gi'een tar or " dagget," exceptionally rich^ in pyrocatechin ; this is used in the treatment of leather, to which it imparts a peculiar smell. The kreasoting of wood with wood-tar was known to Glauber (1648) ; and the preparation of pyroligneous acid is at least as ancient. Apple Tar. In certain cyder districts, presumably French, the marc of apples is destructively distilled. It yields very luminous gas and a yellow tar ; the latter turns black on exposure to the air, and is thick, but becomes fluid at 80^. The product from 100 parts of tar are — "Water . . 30-5 "Benzol" .. . . 15-0 61-5-< Phenol . * 8-0 Kreasote . . 3-0 ^Undetermined carbides, &c. 5-0 f Paraffin oil. . 4-5 ! Paraffin . . ^ Carbon 11-0 21-0 Loss 2-0 90 MA NU ALETTE OF DESTRUCTIVE DISTILLATION. Cork Tar. Cork furnislies illuminating gas and a liquid distillate. The latter consists of a lighter aqueous and a lower tarry portion. The aqueous layer contains hydric acetate and higher homologues, ammonia, some methylamine, hydric cyanide, and methylic alcohol. The tar, which is very fluid, yields 27 per cent, boiling below 210° (naphthahn, benzene, 4 per cent, of the tar ; toluene, 3 per cent, of the tar). The oil boiling above or below this contains very little of a phenolic nature. Much anthracene occurs in the portions of highest boiling-point. Jute. The analyses hitherto made of jute by Cross and Bevan point to a mean composition Cj2HjgOg = 2CgHjQ05 — HgO. It has been found by the present writer to break up on destructive distillation in a different manner from wood, viz. : — C'lsHlsOg = 5C + SH^G + C^HgO, Fixed carbon. Water. G-as and tar. Calc. 100 . . 19-6 .. 29-4 51-0 Found — .. 17-0 . . 3M 51-9 The results are calculated to dry original substance, the substance distilled having contained 9*3 per cent, of moisture. The "water" in the above statement con- tained hydric acetate equal to 3*0 per cent, on the dry substance. The following experiment on the destructive distil- lation of jute was performed in the author's laboratory, as in the case of cellulose. The sample contained 10'65 per cent, of water, and EOSIN OIL. 91 yielded 1*29 per cent, of ash. The results, reduced as before, are iu accordance with the relation : — C„H„0, = 70 + C^H^O, + SH^O Fixed carbon. Gas and tar. Organic water. Calc. 100 .. 27-5 .. 43-1 . . 29-4 Found — .. 27-5 .. 41-3 31-2 The formula for jute is calculated from the analysis of Cross and Bevan {Trans. Chem, Soc. 1882, 100—101), Avho regard it as having the constitution of an aromatic cellulide. This may account for the unusual relations between the co-efficients of C on the right-hand side of the equation. Jute furnishes 3*0 per cent, of acetate when distilled as above described. The amount of tar from 100 grammes exceeded Ice. (a little having been lost). The gas may have been 38-8 per cent. Jute is somewhat " aromatic " in character. This may be the reason for its behaving, when distilled, in a different manner from wood. ROSIN OIL. Ordinary pine resin or rosin — a French or South American product— is essentially a mixture of hydric pinate with sylvate, both of which bodies have the formula ^20-^30^2' ^^^^ ^^ ^^ probable that the corresponding anhydrides are often present. These bodies are perhaps oxidation-products of turpentine or turpentines: — 40,„H„ + 3i), = 2C,„H3„0, + 211,0 Rosin is stable at 150°. AVhen distilled with about 92 MANUALETTE OF DESTRUCTIVE DISTILLATION. ten parts of zinc dust, it yields toluene (meta)etliym ethyl- benzene, naphthalln, and some metliylnaphthalin. In the now obsolete manufacture of rosin gas, 100 pounds of rosin furnished 1,300 cubic feet of illuminating gas of high quality, containing about 8 per cent, of carbonic dioxide, 8 — 9 per cent, of olefines, and having the sp. gr. -58. The tar, in this case, vv^as very fluid, and contained benzol, toluol, xylol, cuniol, cymol. The destructive distillation of rosin much resembles that of wood; but it is wholly a low-temperature industry, and can be carried out below 350°, though this tempera- ture is often exceeded. The retort consists of a vertical cylinder, about two diameters high, and having a spherical top and bottom, or it may be less preferably pan-shaped. Ordinarily the helm is short, but in some cases attains a heiglit of 5 — 8 feet. It is charged to within a few inches of the top with rosin ; an ordinary charge consisting of about 70 barrels, holding about 25 gallons (solid after melting) each.* Direct heat is applied to the bottom of the still ; and the entire operation lasts about 16 hours. Water passes over throughout the entire operation. The products are — 60—70 gallons "spirit." 1,600 „ " oil," for grease-making (if fired slow). 6 — 7 cwt. coke. 40 — 50 gallons weakly acetic water. These numbers may be restated in average per- centages : — The sp. gr. of solid rosin is about 1'075. EOSIX OIL. Spirit 3-1 Oil , . 85-1 Coke . . 3-9 Water . . 2-5 Gas and loss . . 5-4 93 100-0 There is very little gas ; but it is heavy, and power- fully anaesthetic, containining carbonic oxides, ethylene, butylene, and pentine. The layer of coke, containing a good deal of gravel and other mineral impurity from the rosin, is about 6 inches thick ; sometimes, however, it is preferred to work for pitch. It is probable that chemically pure rosin would leave no fixed carbon on distillation. Furck applies direct heat to the bottom of the retort, drives superheated steam through an upper central coil therein, in order to maintain the temperature, and passes steam through the whole mass of rosin. The following are the products : — Acetic water . . . . under 165° Spirit (15 per cent.*) . . ?» Oil {25 per cent.) „ 290° „ (25 per cent.) „ 315° „ (12^ per cent.) „ 350° The residue in the still is liquid, and is run off through a cock, as pitch. Distillation without steam is ordinarily preferred. Oil is, moreover, difficult to separate from the water of steam distillates. The finest products are produced from pale rosins, distilled at the lowest available tern- Keckoned on the volume of the rosin. 94 MANUALETTE OF DESTRUCTIVE DISTILLATION. peratures. For particulars of an examination of the entire course of a distillation, see page 14. The nature of the distillate is partially known. Benzol and toluol have been found in minute propor- tions in the products of the steam process ; but the characteristic feature is a series of C^^^ bodies, directly related to turpentine and to the original rosin, just as the hexyUc hydride (CgH^^) of petroleum is related to its present cellulose (nCgH^QO^). Rapidly distilled oil may contain as much as 10 per cent, unaltered rosin. Even good quahties have been alleged to contain as much as 4 per cent. The "bloom" or fluorescence can be more or less removed by sun-bleaching, or addition of hydric peroxide, nitro-benzol, dinitro-benzol, nitro-toluol, liquid dinitro- toluol, dinitro-naphthalin, carbonic disulphide, or by heating with sulphur. It is probable also that the bloom may be removed by all these reagents from parafiin oils. Kosin oil turns the plane of polarisation of light 30° — 33° to the right — a property which enables it to be easily detected and determined. It can be fraction- ally dissolved in aqueous potash, and wholly in glacial acetic acid. Sp. gr. about '99. At the request of the late Prof. Anderson, a partial investigation of rosin oil was made by the author. A fraction from the "spirit," boihng pretty constantly at 154o_156°, had the sp. gr. -853 at 14*4°, and almost exactly the composition of turpinol {Q-^^R^^^fi. The turpinol of Wiggers and List is said to have the sp. gr. •852, and to boil at 168°. Their product gives a crystal- line hydrochloride CjQlIjg2HCl, but rosin turpinol does not appear to do so, and is certainly not identical with ordi- nary turpinol. When rosin turpinol is treated with strong oil of vitrei, it yields a liquid having the odour of EOSIN OIL. 95 terebene. When treated with bromine, it famishes an oily product, containing from 81 — 43 per cent, of the reagent ; chlorine is similarly taken up to the extent of 50 per cent.; hydric chloride, to the extent of 18 — 19 per cent. Another fraction, boihng at 188^ — 193°, and dried over sodium, agreed in composition very closely with turpentine, but it could not be made to yield a solid hydrochloride. From these experiments it would appear that the order of this destructive distillation is (1) acetate, (2) turpinol, (3) terpenes. The spirit, how- ever, contained a remarkable fraction of constant low boiling-point, consisting of a highly hydrogenised com- pound ; when this is distilled with aqueous hydric iodide, it produces a polymerised turpentine, and another compound not yet examined. The following Table, chiefly due to Renard, contains a list of the known constituents of rosin oil : — Hydrocarhide!^. Name. Formula. Boiling-Point. Amylene QHio 35°-40° C. Hexylene ^&S.\2 67-70 Pentane . . C5H,2 35-38 Hexane . . CeHii 64-66 Toluene hexahydride . . C7H14 95-98 „ tetrahydride . . C7H12 103-105 Toluene CjHs 111 Xylene hexahydride CgHig 120-123 „ tetrahydride . . C8H14 128-130 Xylene . . CgHio 136 Cumene hexahydride . . C^gHis 147-150 „ tetrahydride . . C9H16 155 (?) Cumene . . C9H12 151 Terebenthene (1) . . CioHie 154-157 (2) C10H16 171-173 Cymene hexahydride . . C'loHjo 171-173 Metiso-cymene . . C10H14 175-178 Metapropylethyl benzene C11H16 193-195 Dioctene . . ^16-^28 260 Diterebentyl C20H30 343-346 Diterebentylene . . C2oH,8 — Didecene. . C20H36 332° 96 MANUALETTE OF DESTRUCTIVE DISTILLATION. Aldehydes, Formate . . CH„0.2 A cetate . . an^Os Propionate CsHgO^ Butyrate Isobutvrate C4HSO2 C4HSO2 Valerate . . C5H10O2 Metliylpropylacetate . CfiHioO^ Oenantliylate C7H14O2 Nonylate. . C9S18O2 Undecylate C11H22O; Name. Formula. Boiling-Point. Isolutyl aldehyde Valeraldehyde . . C4H8O C5H10O 60-62 96-98 Ketates. 101 118 146 164 153-155 173-175 Alcoliols, Metliylic alcohol AllyHc CH4O CsHeO 67 103 Kenard considers that about 80 per cent, of rosin oil consists of diterebentyl, 10 per cent, of diterebentylene, and 10 per cent, of didecene. The hexahydrides are isomeric with the define series, and boil at about the same temperature as the defines. When treated with hjdric nitrate or sulphate, they do not form nitro-compounds or sulphonates ; strong nitrate, in fact, converts them into oxalate. The terebenthenes are IcEvorotatory. The methyhc alcohol amounts to '03 per cent, on the rosin ; it is found in the aqueous distillate. The long white crystals which separate from undried rosin oil, especially the fraction 100° — 105°, on long standing, have received various formulae. Recent evi- EOSIN OIL. 97 dence is in favour of the expression CyHj4 02.H2 0. According, however, to later researches by Renard, the formula is C^H-^^-^H^O, corresponding to a derivative ot toluene tetrahydride. Rosin ^' spirit " has been used as a substitute for turpentine in painting, varnish-making, and currying. Both rosin " spirit " and " oil " have the property of combining with alkaline and other hydrates to form peculiar greasy bodies ; which again can hold together, in the form of a buttery mass, an enormous excess of hydro carbide. This phenomenon is mainly owing to the " unsaturated ^' character of the turpentines, one of their oldest recognised chemical properties. Synthetical ex- periments carried out in the author's laboratory show that the following turpentme mixtures — C10H16 + 2CaH202 C10H16 + NaHO C,oH,, + KHO furnish what are probably real chemical compounds of these. The first solidifies in a few minutes ; the second in a few days; the third after a longer period. The minimum ratio in the "rosin grease" of commerce is about 13(CiQHjg) : CaH202; so that the original calcic compound is capable of converting at least eighteen times its weight of liquid hydrocarbide into " grease." The various rosin greases are all, when destructively distilled, decomposed into rosin oil and hydrate. In the actual preparation of rosin grease, a small portion is rapidly stirred with about three-fourths of its weight of slaked hme made to a cream with water. The oil and hydrate quickly unite, extruding the superfluous water, which is at once run off; the solid compound is then diluted with more oil, and the solution stirred into a G y» MAXUALETTE OF DESTRUCTIVE DISTILLATION. further final quantity, nntil the total dilution already mentioned is attained. The whole operation takes about half-an-hour. Rosin grease is used as a lubricant for iron bearings, and especially for the axles of pit waggons, which are much exposed to moisture. On account of the rapidity with which it acetifies under the influence of heat and friction, it is not adapted to brass bearings. As ordinarily sold, it nearly always contains a kindred grease, made from the unsaturated coal-tar hydrocarbides which are left when crude benzol is rectified ; baric sulphate, china clay, and plumbago are also frequently added. A siccatiye rosin oil is prepared by passing an air current through a mixture of rosin oil with litharge or red lead. The preparation dries in twenty-four hours. The purification of rosin oil can be to a great extent eff'ected by treatment with hme-water to remove acetate, and re-distillation with or without a ciu-rent of steam. Open steaming removes almost every trace of odorous matter, and the fluorescence of the heavier oil is some- times concealed by adding nitro-benzol. It has been proposed to lighten the colour and remove the odour by stirring with 1 per cent, of water, 8 per cent, of hydro- chloric acid (to be diluted Avith 1^ times its weight of water), 1 per cent, of red lead, and a further 5 per cent, of the dilute hydrochloric acid. After some days the oil is removed, washed free from acid, and exposed to sun- light. Great care is requisite with processes of this kind, inasmuch as oils, if chlorinated, are unsuitable for lubricants. Good results would be obtained by steaming at ordinary pressures, followed by distillation over an alkali {e.g., 3 per cent, of caustic soda), an alkahne reducing agent, or zinc dust. Rosin oil, more or less refined, is used as a lubricant EObIN OIL. 99 for batching jute, and for the adulteration offish, colza, and other oils. It can only be made into a grease Avith great difficulty. It should be kept in tin vessels. The exports of rosin from New York amounted, in 1881, to 920,943 barrels; in 1882, to 906,882 barrels; in 1883, to 960,870 barrels. Appendix to Rosin Oil. Dyagoiis Blood. — When this resin is distilled with zinc dust to complete decomposition, a light-coloured oil is pro- duced, which is completely volatile in high pressure steam. The fraction 100° — 150° of this oil contains toluene, ethyl- benzene, and styrolene (which is of course partly con- verted into metastyrolene, and constitutes Q>^ per cent, of the total distillate). The 200°— 300° fraction consists in part of a phenolic oil O^^^^o^^, boiling at 236° — 240°; and of two oils not soluble in alkali, whose formula? are CnHjgO (fragrant, boiling at 214°— 215°) and C,^Yl.,^fi (less fragrant, boihng at 256°— 260°). Guaiacum. — The chief product of distillation over zinc dust is kreasol (about 50 per cent.), which is accompanied by toluene, xylene, and paraxylene (about 30 per cent.), small quantities of pseudocumene, and a solid hydrocarbido guaiene, 0^^^^. Elemi. — In a similar manner, elemi yields toluol, meta- and para-methylethylbenzene, and ethylnapthalin. A^nmoniacum. — This resin furnishes, with zinc dust, a characteristic hydrocarbide C13H20, belonging to the ben- zene series. Amber. — A fossil pine-resin. Its constituents are an organic sulphur compound, pyrites, a fragrant oil, a bitumen Cj^H^gO, hydric succinate, 3 — 8 per cent., 10 — 20 per cent, of two resins soluble in potash or alcohol, and 70 — 80 per cent, (not taken up by these solvents) havhig g2 100 MANUALETTE OF DESTRUCTIVE DISTILLATIOX. the formula C20H30O2. When distilled it melts at 350° — 400°, swells up, gives off carbonic dioxide and inflammable gas, succinate, acetate, an oiJy body, and chrjsene. The sulphur, which may amount on the whole to '48 per cent., is from one-half to three-fourths in organic combination. Ash, -08 — '12 per cent. Caoutchouc. — When caoutchouc O^OjQHjg) is submitted to a temperature of about 316° in a close vessel, it yields a very light volatile distillate, and a residual mass which furnishes a good varnish when dissolved in oil. The dis- tillate consists of isoprene or pentine (CgHg), together with caoutchin (C^oH^g), and other polymers of the terpene group : rectification is performed with the aid of steam. It soon turns brown in contact with air, especially if water be present. It is said to have the peculiar property of dissolving copal without the aid of heat, and readily takes up many resins and oils. PETROLEUM. Petroleum is a natural mixture, chiefly of fatty hydrides, and proceeds from an unknown source. Petro- leum springs generally occur near the base of mountain chains. The main points to be considered in respect to the geological conditions under which petroleum and gas occur in quantity seem to be as follows : — 1. They occur in rocks 'of all geological ages, from Silurian upwards. The most productive areas are palasozoic in North America, miocene in the Caucasus. 2. There is no necessary relation to volcanic action. PETEOLF.U:\r. 101 3. The most productive areas for oil in great quantity are where the strata are comparatively mi disturb eel. Oil, but in less abundance, frequently occurs when the strata are highly disturbed and contorted, but gas is rarely so found. 4. The main requisites for a productive oil or gas field are a porous reservoir (sandstone or limestone) and an impervious cover. 5. Both in comparatively undisturbed and in highly disturbed areas, an anticlinal structure often favours the accumulation of oil and gas in the domes of the arches. 6. Brine is an almost universal accompaniment of oil and gas. According to McGee : "Every richly-productive gas field, at least in the Eastern States and Canada, is a dome or inverted trough formed by flexure of the rocky strata ; and in every such dome or inverted trough there is a porous stratum (sandstone in Pennsylvania, and coarse-grained magnesian sandstone in Ohio and Indiana) overlain by impervious shales. These domes or arches vary in dimensions, from a few square miles in some of the Pennsylvanian areas, to 2,600 square miles in the great Indiana field. Within each gas-charged dome there are found three or more substances arranged in the order of their weight ; gas at the top, naphtha (if it exists in the field) and petroleum below, and finally w^ater, which is generally salt, and sometimes a strong and peculiar bitter. This order is invariable throughout each field, w^hatever its area, although in Indiana, at least, the oils are found most abundantly about the springing of each arch, while towards its crown gas immediately overlies brine ; and the absolute altitude of the summit-level ot each substance is generally uniform whatever the depth 102 MAXU ALETTE OF DESTRUCTIVE DISTILL ATIOX. beneath the surface. Since the vohmie of gas or oil accnmulated in any fiekl evidently depends on the area and height of the dome in which it is confined, and upon the porosity and thickness of rock in which it is contained, the productiveness of a given find may be definitely pre- dicted after the structure and texture of the rocks have been ascertained. " In all productive bitumen fields the gas and oil are confined under greater or less pressure. When a gas well is closed, it is commonly found that the pressure at the well-head gradually increases, through a period varying from a few seconds in the largest wells to several minutes, or even hours, in wells of feeble flow ; and that afterwards the pressure-guage becomes stationary. This is the ' con- fined pressure,' 'closed pressure,' or 'rock pressure' of the prospector; or, more properly, the 'static pressure.' When a well is open, and the gas escapes freely into the air, it is found that if the stem of a mercurial or steam gauge is introduced, a certain constant pressure is indi- cated. This is the ' open pressure ' or ' flow pressure ' of the gas expert, and the capacity of the well may be determined from it. The static pressure varies in diff'erent fields. In Indiana it ranges from 300 to 350 pounds per square inch, in the Findlay field it is from 450 to 500 pounds, and in the Pennsylvania field it varies from 500 to 1)00 pounds. " The cause of this enormous pressure is readily seen in Indiana. The Cincinnati arch (in which the gas of the great Indiana field is accumulated) is substantially a dome, about fifty miles across, rising in the centre of a strati- graphic basin fully 500 miles in average diameter. Tliroughout this immense basin the waters fafling on the surface are in part absorbed into the rocks, and conveyed towards its centre, where a strong artesian flow of water PETROLEUM. 103 would prevail were the difference in altitude greater ; and the hght hydrocarbons floating upon the surface of this ground water are driven into the dome, and there sub- jected to hydrostatic pressure, equal to the weight of a colamn of water whose height is the difference in altitude between the water surface within the dome and the land surface of the catchment area about the rim of the enclosing basin. Accordingly, the static pressure is independent of the absolute altitude of the gas rock and of its depth beneath the surface, except in so far as these are involved in the relative altitudes of the gas rock and a catchment area perhaps scores or even hundreds of miles distant. Gas pressure and oil pressure may, therefore, be estimated in any given case as readily and reliably as artesian water pressure ; bnt while the water pressm^e is measured approximately by the difference in altitude between catchment area and well-head, that of gas is measured approximately by the difference in altitude between catchment area and gas rock, and tliat of oil is measured by the same difference, minus the weight of a column of oil equal to the depth of the well. It follows that the static pressure of gas (as indicated at the surface) is always greater than that of oil, particularly in deep wells. It follows also that the pressure, whether of gas or oil, is not only constant throughout each field, but diminishes but slightly, if at all, on the tapping of the reservoir, until the supply is exhausted ; and hence that pressure is no indication of either abundance or per- manence of supply." The comparatively simple structure of the petroleum region here described does not obtain all over the world. Often the strata in which oil occurs dip at high angles, or they may have been sharply folded and broken, the denuded edges of the petroleum-bearing bed being 104 MANUALETTE OF DESTEUCTIYE DISTILLATION. exposed at the surface. In such cases the yield of wells is comparatively small, there being httle or no artesian pressure to force up the oil. Such regions rarely now contain much gas. Although there is much variety of geological structure in petroleum- bearing regions, there is frequently an anti- chnal arrangement of the strata, the oil coming up along the arch. There is no uniformity in the geological ages of the strata which yield petroleum. Even in North America the age ranges from lower silurian to tertiary; both gas and oil also occur in the drifts. Rocks of secondary age, however, with the exception of the cretaceous, are not oil-bearing in North America. In Europe, only small quantities occur in palasozoic rocks. In Hanover it ranges from trias to cretaceous. In Eastern Europe it is mainly tertiary, and wholly so in the Caucasus. In other parts of the world the petroleum-bearing beds are, so far as is known, rarely of older date than upper secondary. Volcanic rocks occasionally contain petroleum, but there is good reason to believe that these cases are generally the result of impregnations into porous reservoirs of volcanic rocks from neighbouring sedimentary strata. The oil and gas fields of Pennsylvania and New York have a very simple geological structure. The rocks he comparatively undisturbed, being only gently folded into a series of anticlinals and synclinals parallel with, and along the north-west side of the main axes of the Alleghanies. These folds have themselves a gentle inchnation towards the south-west. In the Alleghanies, and to the south-east of the range, where the rocks are greatly distru'bed, neither oil nor gas is found. Some of the larger gas wells are on or near the summits of anti- PETROLEUM. 105 clinals, but many are not so placed. In the Trenton limestone fields of Oliio and Indiana, the productive areas are mainly over anticlinals, gas occurring at the crown of the arch, oil on the slopes. The essential conditions for a largely productive field of gas or oil are — a porous reservoir (generally sandstone or limestone) in which the hydrocarbons can be stored, and an impervious cover of shale retaining them in the reservoir. But over large areas the limestone has been dolomitized, and so transformed into a cavernous and porous rock in which gas and oil are stored. The enormous quantities of gas and oil given out from beds of limestone and sandstone can be fully accounted for when their porous nature, thickness, and extent are taken into consideration. Some of these rocks can contain from one-tenth to one-eighth of their bulk of oil. The high pressure under which gas and oil flow from deep borings is in most cases of an artesian character. In Kansas, gas occurs mainly in the lower coal measures. In Kentucky and Tennessee, oil is found in the Ohio shales (Upper Devonian), in Colorado in shales of cretaceous age. In California it is found in tertiary strata, mostly much disturbed. In Mexico, the West Indies, and parts of South America, tertiary strata seem to be the chief source of oil. The age of the petroleum-bearing unfossiliferous sands, &c., of the Argentine Republic (province of Jujuy) is not certainly known; they have been referred by diff"erent writers to various ages from silurian to tertiary ; they are probably sub-cretaceous. In Europe and Asia the petroleum-bearing beds are of secondary or tertiary age, the paleozoic rocks yielding only an insignificant supply. 106 MANUALETTE OF DESTRUCTIVE DISTILLATION. In North-West Germany we find petrolenm in the Kenper beds, and more or less in other strata up to and including the Gault. As we pass to the south and south- east from this district we find, as a general rule, that oil occurs in newer strata. The various productive horizons of different districts are as follows : — North-West Germany . . Keuper to Gault. Rhone Vallev 1 t •^ L . . Jurassic. Savoy J ^•^ . I ., .. Neocomian and Cretaceous. Sj)ain J la-aryJ Oligocene. Lower Tertiary (Flysch). Eocene. Neocomian to Miocene. Elsass . . Bavaria. . Italy . . Galicia North-East Hu Poland -^ Koumania r . . . . Miocene. Caucasus J The important districts of Baku occur on plains over anticlinals of miocene beds. The petroleum-bearing sands are interstratified with impervious clays, separating the strata into distinct pro- ductive horizons. In Algeria oil occurs in lower tertiary beds. Tlie Egyptian petroleum comes from miocene strata. Petroleum seems to be unknown in peninsular India ; but it occurs in many places along the flanks of the Himalayan range, and also in Lower Burma, generally in lower tertiary strata. In Upper Burma and Japan, the oil-bearing rocks are probably newer tertiary. In all these areas the beds are greatly disturbed, and the same is the case with the great Carpathian field; but it fre- PETE OLEUM. 107 quently happens that the most productive regions are along antichnal hnes. In New Zealand, oil occurs in cretaceous and tertiary strata. Gas occurs in the jet-rock of the upper lias in East Yorkshire, along with some heavy hquid bitumen. The gas sometimes finds its way down into the ironstone mines worked in the middle lias. Mr. G. Barrow states that one blower burnt for over twenty years in the Crag Hall ironstone mine, a few miles south-east of Salt- burn. The jet rock of the upper lias in Yorkshire often has hquid bitumen in the beds and inside the fossils, especially in the ammonites. Bitumen, in various forms, and in small quantities, is not uncommon in the fossiliferous palseozoic rocks of England. Petroleum occurred in the Deep Main Pit at Biddings Colhery, Alfreton, Derbyshire; and in larger quanticies in Southgate Colliery, near Chesterfield, from the roof of the "top hard" coal. Petroleum, in small quantities, has frequently been found in the Derbyshire lead mines, which are worked in the carboniferous lime- stone; gas also occurs in these mines, which has some- times caused explosions. The Mineral Statistics of the United Kingdom give the following as the production of petroleum in Derbyshire :— 1886, 43 tons; 1887, 66 tons; 1888, 35 tons; 188i», 30 tons; 181)0, 35 tons; the whole of this being from the Southgate Colliery. Petroleum is found in the sandstone beds in the coal measures of Shropshire: some of it was sold years ago under the name, " Betton's British Oil." From the very frequent occurrence of sahne water in most petroleum-bearing beds, we might occasionally expect to find that petroleum or gas occurs with rock salt ; but this seems to be seldom the case. Marsh gas 108 MAXUALETTE OF DESTRUCTIVE DISTILLATION. has been noticed, although rarely, in rock-salt mines at Northwich (where petroleum also occurs), and Winsford, but only in small quantities. In North- West Germany, and also in Roumania, rock salt and petroleum occur in closely associated strata, but not together. Gas was found in the early borings for salt at Middles- brough ; and at the Seaton Carew boring some oil Avas obtained. In both cases the source probably was the upper beds of magnesian limestone. United States. The earliest notice dates from 1(52 7, where some oil springs near Lake Erie were \asited by Daillon, a French missionary. In 1789 it is recorded that the Indians sold the oil to the white people at four guineas a quart. There is good reason to believe the petroleum of Pennsylvania w^as knoAvn to races who preceded the Indians, as here and there shallow wells or holes abound, evidently made for petroleum, the history and uses of which were unknown to the Indians. Some of these ancient pits still remain in the wilder parts of Warren Co., but elsewhere they have disappeared. The early petroleum Avells were very shallow, only a few feet deep, in which water and petroleum collected, and the latter, floating on the top, Avas taken up by blankets. Petroleum and gas in deep wells and borings seem to have been discovered accidentally in 1814, in Ohio, Avhen boring for salt and brine. In 1829, a rather remarkable event occurred near Burkesville, Cumberland Co., in Kentucky. In boring for salt-water, oil Avas struck, Avhich discharged many barrels at interA^als of from two to five minutes. After spouting in this Avay for three or four PETROLEUM. 109 weeks, the flow became constant at several thousand gallons per day. The oil flowed into the Cumberland river, and when set on fire it burned on the surface of the water for more than forty miles below the well. Although the impoi-tance of boring for oil should have been apparent from the success of the accidental trial in Kentucky, and from others in Alleghany, no systematic attempt to drill for oil was made till 1859, when Mr. Drake, the superintendent of the Seneca Oil Company, put down the famous " Drake Well " at Titusville. This was bored only 69-| feet to an oil-bearing bed; the oil rose to within 10 feet of the surface. The well pro- duced, at first, 25 barrels a day by pumping ; but after- wards the yield fell to 15 barrels. Numerous wells were drilled in the following year (1860), and in 1681 the first " flowing well " was obtained on Oil Creek. At once many other wells were bored, some flowing at the rate of from 2,000 to 2,500 barrels per day. Wells were quickly bored in other areas, and the oil industry rapidly developed. The first pipe for the transport of oil was laid in 1865. In accounts of the earlier explorations for petroleum, we read little of natural gas; the gas had probably escaped into the air, and it was only met with in quantity and under pressure where deep borings were carried out. As far back, however, as 1821, natural gas was used in a small Avay for lighting houses at Fredonia, Chatuaqua Co., New York. In 1845 it was observed near Utah. No further development of this industry seems to have taken place till 1870, when gas engines were run by natural gas at Pine Grove, in Venango Co. In 1872 gas was dis- covered at Newton, and was laid on in pipes to consumers for fuel and light. Gas was used in iron-making at Leechburg in 1874. 110 MAXUALETTE OF DESTRUCriYE DISTILLATIOX. Pennsylvania^ New York, Ohio, and Indiana. — The quotatiou given on p. 101 sufficiently illustrates the general character of this important region. Its amazing productivity is well known, and statistics of the various districts are readily available. To emphasise some points of chief geological interest is all that can here be attempted. The geological position of the gas and oil-bearing rocks range from lov/er silurian (Trenton limestone) to lower carboniferous. Until the gi'eat stores of the Trenton limestone were discovered, the Devonian and lower car- boniferous strata were the most important sources. The oil-sands of Venango Co., Pennsylvania, are often in lenticular beds, the longer axes of the beds ranging from north-east to south-west. In thickness they range from a thin band up to 100 feet. Their width may be only one or two miles, their length sometimes 20 miles. Some of the strata die out before reaching the outcrop, and consequently are known only by borings. AVhen two or more such beds occur in vertical succes- sion, the lowest usually contains most oil or gas. The lenticular nature of the sand may explain how in some cases neighbouring wells affect each other, whilst else- where they may not do so. The early borings were mainly along valleys. When explorations were carried on over high ground, the beds discovered were called " mountain sands." These he some hundreds of feet above the true Venango sands; they occasionally contain some oil and gas. Beneath the Venango group, other gas or oil-bearing sands were subsequently discovered, the most important of which are the Warren sands of Warren Co., and the Bradford sands of McKean Co. The Berea grit is the most important source of oil in Eastern Ohio. PFTKOLEUM. Ill Tn all cases these productive sands are underlain and overlain by shales. The underlying shale is the source of the petroleum or gas ; the sand is the porous reservoir in which they are stored ; the overlying shale is an imper- vious cover Avhich retains them in the reservoir. When gas and oil are found stored in limestone, they may sometimes have been produced in the limestone itself, but the impervious cover of shale is still required to retain them. The Trenton limestone, the chief source of gas and oil -in Indiana, and an important source now in Western Ohio, is the upper member of a series of lime- stones which have been proved to a depth of 1,'S()0 feet. The true Trenton limestone itself is several hundred feet thick. All this thickness of limestone may have produced the hydrocarbons, although they are stored mainly in the upper part of the Trenton. But not always so : it is only when the Trenton limestone occurs in the cavernous con- dition that it is highly productive. This condition is due to some of the lime having been removed, its place being taken by magnesia. The storage capacity of the porous sandstone and lime- stone is very great, and sufficiently accounts for the great yield of the wells. The Waterlime bed, at 500 feet in thickness, and ^vith a capacity of only 0*1 per cent., would contain 2,500,000 barrels of oil per square mile. One hundred square miles of such rock would yield the entire production of New York and Pennsylvania up to January, 1883. But the capacity for storage is often much more than the figures taken here. Carll has shown that some rocks can contain from one-tenth to one-eighth of their bulk in oil. As already described, the most productive areas of the Trenton limestone are mainly over anticlinal lines, in the arches of which the gas and oil are stored. Sometimes 112 MANUALETTE OF DESTKUCTIYE DISTILLATION. these anticlinal areas are closed at one or both ends, by the compactness and impermeability of the rock. Kvipufj pmo^o 5 B'^ limestone, shale, limestone. Eiver sha shale, harle. 1 CO cy iagara iagara [in ton udson edina tica S 3 ;z; ;z; O W ^ h:> H o w o o o o X H O H O K 02 t- O kO The anticlinal structure seems to be of more import- ance with gas than with oil, the gas collecting in the PETROLEUM. 113 crest of the arch. But complete anticlinals are not always formed ; often there is merely a lessening of the dip, the gas colleoting on the terrace. In Eastern Ohio man;y of the gas and oil-fields have this terrace-hke structm-e. The village of Murraysville (Co. Westmoreland), north- east of Pittsburg, is the centre of the principal gas area, which is about half-a-mile wide by 6 miles long. It con- tained (1884) nine wells, one of which is 1,320 feet deep. Tarentum. Washington (Penn.), and Canonsburgh are other centres. The (computed) value of natural gas used in the United States was 475,000 dollars in 1883, and 1,460,000 dollars in 1881. The depth of the petroleum wells in the United States increased from 436 feet in 1861, to 1,606 feet or more in 1878. There has been a further increase in depth since the latter year, especially in certain localities. Thus the comparatively recently drilled Gordon well in Washington Co. has a depth of 2,400 feet. The cost of this well is stated to have been 7,500 — 8,000 dollars. The surface diameter generally averages about 10 inches, and the bottom diameter 5f inches. The distribution of petroleum from the oil districts, and the mode of conveyance, are certainly among the most striking features of the industry. Pumping-stations convey the oil from something like 21,000 isolated oil wells of Northern Pennsylvania, and carry it to Philadel- phia, New York, Baltimore, &c. It is pumped from valleys over the hills, the highest elevation being in any one place above 1,500 feet. The pumping-stations are distant from 20 to 25 miles, and the oil is pumped in from the 20-mile station in advance into enormous reservoirs of 100 feet in diameter, and 40 feet to 50 feet in height ; it H lU MANUALETTE OF DESTRUCTIVE DISTILLATION. is again pumped out for another 25 miles, and so on to Baltmiore and Philadelphia. Petroleum is apparently produced by the long-con- tinued application of a gentle heat to some derived form of cellulose ; for if the temperature were a high one gas must be evolved from the soil in more places, and in far greater volume than is ever found to be the case. An exceptional well (the " Delameter '') in Butler Co. is said to evolve 1,000,000 cubic feet per hour (about 300 tons per day), at a pressure of iOO lbs. per square inch. This gas has an illuminating power of T-J candles, and contains about 82 per cent, marsh gas, 10 ethylene, and 7^ hydrogen. Ford has given the following analyses of gases from the " gas wells " of Pennsylvania : — Carbonic dioxide . . 0-00 •61 •81 „ oxide •40 •61 •81 Oxygen . 2-60 •40 •61 Ethylene •80 •61 •81 Hydrogen . . 3-51 29-75 2^94 Marsh gas . . . 88 -40 68 01 94 02 Nitrogen . 4-29 0-00 0-00 100^00 100-00 100-00 100 00 •67 40 3-12 61 2-90 61 2-45 67 31 ^52 72 39-97 00 19-35 00 100 -00 A good well yields about 15,000,000 cubic feet m 24 hours, at a pressure of under 200 lbs. per square inch. Carnegie's results (Pittsburg, 1884) are as foUows : — Carbonic dioxide •8 •6 .. •4 .. •3 „ oxide .. 1^0 •8 •58 •4 1-0 •6 Oxygen .. 1^1 •8 •78 •8 2-10 1-2 Ethylene . . •7 •8 •98 -6 •80 •6 Etbylic hydride . . 3-6 5-5 7-92 12-30 5-20 4-8 Marsh gas 72-18 65^25 60^70 49-58 57-85 75-16 Hydrogen 20-02 26^16 29-03 35 -92 9-64 14-45 Nitrogen . . •• -• •• 23-41 2-89 100-00 100-00 100-00 100-00 100 00 100-00 PETROLEUM. 115 Petroleum contains in solution both hydrogen and tlie fatty hydrides C — C^, which are gases or vapours nnder ordinary conditions; these latter were detected by Ronalds and Fouque. The Hquid terms C^ — C^^ were isolated by Pelouze and Cahonrs, and by Schorlenimer : solid paraffins C25 — C3Q are also present, in amonnt increasing with the density. The last chemist found traces of benzol and its homologues (aromatic hydi'ides). In the portion of Penn- sylvanian petroleum boihng at 170° — 190° Engler found •2 per cent of pseudocumene and mesitylene. (Baku oil contains about '1 per cent., and small quantities occur in the oils of Alsace, Galicia and Italy.) Warren has detected the olefines C^^ — C^g ; gaseous defines also occur. Of the above constituents, hexylic hydride, CgH^^, a substance closely related to cellulose, nCQH.^QO^, is the most charac- teristic; this was also found by Greville Williams in boghead cannel oil. The highest known hydi-ocarbide in American petroleum is unsaturated, melts at 260°, shows a strong blue fluorescence, and has the formula (CqE.^)?i, n being probably 4. The oil of high boiling-point also contains anthracene, chrysene, pyrene, fluoranthrene (C.H,) n, &c. Native petroleum is always more or less coloured, and requires refining with caustic soda and vitriol, just as is the case with artificial petroleum. Sp. gr. -73 — -97, the lighter gravities predominating : sp. gr. of Peunsylvanian oil, '79 — '83. American petroleum is distilled prior to export, in order to remove the dissolved gaseous hydro- carbides, which, if allowed to escape into the air, would furnish a readily inflammable and explosive mixture. Such distiUation may be performed under reduced pressure at first, and the evolved vapours liquefied by compression. The processes of purification present no peculiar features. h2 116 MAXUALETTE OF DESTRUCTIVE DISTILLATION. The distillates from average petroleum of sp. gr. -79 have been stated as follows: — Per cent. Sp. gr Gasohne . . 1—1-5 'Q6 "C Naphtha" 10 •70 "B Naphtha" 2-5 •72 "A Naphtha" . . 2—2-5 •74 16-5 lUuminant . . . „ 50—54 •81 Lubricant . . 17-5 Wax 2 Loss .. •• 10 100-0 After the illuminating oil has been removed, the stills are sometimes fired more slowly, thus causing their con- tents to undergo partial destructive distillation. The heavy oil is thus " cracked " into marsh gas and hydrogen, naphthas, illuminant, and a thick " residuum '* (lubricant). Ohio petroleum of sp. gr. -791 has furnished: — 16 per cent. Naphtha, 70° Baume. 68 „ Burning oil. 6 „ Paraffin oil. 10 „ Residuum. Maybery and Smith found a sample of it (sp. gr. '925) to contain 11'97 per cent, of sulphur. In the census year 1879-80, the total amount of crude petroleum treated was 731,533,127 gallons, at the follow- ing cost (Peckham) : — PETROLEUM. 117 Fuel Acid Alkali Bone-black Packages . . Bmigs, paint lioops, ;lue, &c. Dollars. 1,319,008 1,206,200 105,770 62,815 15,319,215 645,412 The value of the crude oil is estimated at 16,340,581 dollars. The 12 refineries at Pittsburg employ (1886) 9(^0 hands, whose wages amount to say 490,000 dollars. The capacity of these refineries is 77,008 barrels crade a week. The yield of refined oil is about 75 per cent, of the crude, which, if the refineries were all running to their capacity, is equal to about 3,500,000 barrels refined oil a year. Petroleum and its waste products are themselves de- structively distilled in the United States for gas. Petroleums vary very much. The best and safes guide to their composition and usefulness is a knowledg of their specific gravity and the percentage of bromin they absorb in dry solutions. The follo^ving table shows the amount of petroleur raised in the United States, and exported : — Years. Barrels. Production. Export. 1859 1860 1861 1862 1863 .. 1864 1865 1866 1867 5,000 520,000 2,113,600 3,056,000 2,610,000 2,130,000 2,721,000 3,732,600 3,583,000 26,000 259,000 672,OCO 759,000 709,000 1,605,000 1,596,000 118 MANUALETTE OF DESTRUCTIVE DISTILLATION". 1868 1869 1870 1871 1872 1873 1874 1875 1876 1877 1878 1879 1880 1881 1882 1883 1884 1885 1886 1887 1888 1889 1890 1891 Years. Barrels. Production. 3,716,000 4,351,000 5,371,000 5,531,000 6,357.000 9,932,000 10,883,000 8,801,000 9,015,000 13,043,000 15,367,000 19,827,000 26,048,000 29.638,000 30,460,000 24,000,000 24,089,758 21,600,651 26,803,400 28,249,597 27,615,929 35,163,513 45,000,000 50,150,000 Export. 2,313,000 2,446,000 3,316,000 3,800,000 3,722,000 5,800,000 5,492,000 5,533,000 6,080,000 8,315,000 7,914,000 9,944,000 9,961,000 14,804,000 14,574,000 15,628,000 15,892,259 16,431,300 29,051,067 27,336,254 33,809,573 34,452,131 33,119,256 The subjoined table shows the fluctuations in the price ■V barrel of petroleum in America : — Per Barrel. Per Barrel Year. Dollars. Year. Dollars. 1859 . 19-77 1875 1-33 1860 9-77 1876 2-61 1861 0-52 1877 2-37 1862 1-00 1878 ] 17 1863 3 11 1879 0-88 1864 7-85 1880 94 1865 6-65 1881 0-85 1866 3-76 1882 0-76 1867 2-40 1883 0-74 1868 3-57 1884 0-85 1869 5 -64 1885 0-88 1870 3-86 1886 . ; 0-81 1871 4 -42 1887 0-67 1872 3-68 1888 0-90 1873 1-84 1889 0-77 1874 117 1890 0-77 PETROLEUM. 119 Kentucky and Tennessee, — As petroleum fields, these are not of great importance. But there are some other peculiarities which render Kentucky interesting and instructive, as a source of gas, which here occurs in the Ohio shale. Elsewhere the incursion of salt water into a gas well is the sure precursor of failure, showing that the reservoir is becoming exhausted ; but here salt water and high-pressure gas occur together. Some of the wells here, also, have been long productive; one, at Moreman, has been producing gas and brine since 1863. Salt has been manufactured here from brine since 1872. Professor Orton estimates that the gas from this well has had a total value of 200,000 dollars. Colorado. — Professor Newbery describes the oil here as occurring in the middle cretaceous beds— the Colorado shales. Borings have been made to a considerable depth at Florence, near Canon city; the deepest (in 1888) was 3,047 feet. The wells give a steady stream of oil, of from 20 — 100 barrels per day, the average being about 50 barrels. Some of the wells are said to increase in flow. There are oil spiings in Western Colorado, but these have not yet been developed. The production in 1887 was 76,295 barrels, and in 1888 was 297,612. The total yield of the district in 1890 was about 1,200 barrels per day, but the wells could yield 2,000 barrels per day of 31° Baume oil. Out of 300,000 barrels of crude oil, 100,000 barrels of illuminating and 5,000 barrels of lubricating oil have been manufactured. Wyoming. — Petroleum has long been known to occur here, but it has not been largely worked. The best known district is in Carbon Co., where wells to a depth of 800 feet were put down. Oil came at first under con- siderable pressure, but soon fell to a steady flow of from 600 — 1,000 barrels per day. The oil is of low quality, the 120 MANUALETTE OF DESTRUCTIVE DISTILLATION. luminant averaging only about 25 per cent. It is said that oil of a better quality, in some cases yielding 61 per cent., exists further to the north-east. California, — Petroleum is chiefly found in the southern counties. It occurs mainly in sandstone of tertiary age. The beds are generally inclined from 30° — 85°, and, con- sequently, with outcropping edges. High-pressure wells are naturally rare, and the oil is obtained by pumping. An exception occurred at Adam's caiion, Ventura Co., where a boring 720 feet deep met with oil, which rose 75 feet into the au% and flowed at the rate of 800 baiTels per day. The yield is comparatively small, but the wells give a steady production for a longer time than most gushing wells. Some wells are now 1,000 feet deep ; one is 2,330 feet ; but most are less than 1,000. There is not much natural gas in California ; it occurs near Los Angeles, flowing at a low pressure. The cost of wells is stated in the official reports to be about three times what it is in Pennsylvania, partly on account of the steep inclination of the beds. (The Los Angeles wells yield about 160,000 barrels of heaA'y quahty per annum.) The statistics of the production of oil in California for the past eight years are reported as follows : — 1879, 568,606 gallons; 1880, 1,763,215; 1881, 4,194,102; 1882, 5,402,671; 1883, 6,000,000; 1884, 6,000,000; 1885, 8,760,000; 1886,10,950,000; 1887, 28,500,000. Through- out the southern portion of the State there has been a great development in the production, and several com- panies have been foniied to work it. Russian Petroleum. Petroleum is found in abundance on the shores of the Caspian Sea, more especially in the neighbourhood of PETROLEUM. 121 Apsclieron and Baku ; and tliere are also solid deposits of naphthagil or neft-gil, which resembles bitumen, and has been worked for hght oil and paraffin. Neft-gil yields about 15 per cent, of crude paraffin, and 40 per cent, of illuminating oil ; but the yield sometimes amounts to 40 per cent of paraffin. The naphtha region of the Apsclieron peninsula has an area of 4*3 square miles, and may be divided into two parts — Balakhany, which has yielded naphtha since the earliest times, and Sabountchi, which was explored in 1872-3. The district (as Abich long ago pointed out) lies over the crown of a low anticlinal, which is probably the easterly con- tinuation of the great Caucasus anticlinal. Another, and an increasingly important, productive area is on the shores of the Caspian at Bibi-Eibat, south of Baku, and about ten miles from Balakhany. The surface is occupied by loose sand, the rocks below being of late tertiary date ; beneath these probably he the cretaceous and Jurassic strata, which form the main mass of the Caucasus, but it is doubtful if any borings have touched these rocks. The most important area of the Caucasus, after Baku, in some respects, is that of Kouban. This lies at the north-western end of the range. The wells here are usually of smaller depth, and are less productive than at Baku, although one well — as far back as 1879 — is said to have been bored to a depth of 1,020 feet ; and, in 1860, several thousand barrels of oil per day were given by one well for a considerable time. Here, as at Baku, tlie heaviest oil sometimes comes from the highest beds. The third productive area is near Kertch, in the Crimea. The wells here are not deep, and, compared with the two other districts, are not highly productive. One well, however, has been carried to a depth of 940 feet, and 122 MAXUALETTE OF DESTRUCTIVE DISTILLATIOX. produced about 30 barrels per day for a time, its total production being about 3,500 barrels. Around the Caucasus there are several other petroleum fields, which will rise in value when the highly productive district of Baku declines. Attempts have recently been made to work those near Batoum. The construction of the new line of railway from Vladikavkas to Petrovsk, which is now being commenced, will open up a new and hitherto almost unknown petroleum field, situated in Terskoioblasti, near the town of Groznii. There are comparatively few petroleum areas in the interior of Russia ; but oil has been noticed in the govern- ments of Samara, Simbirsk, Kazan, and elsewhere ; it is also recorded from Petchora, in Archangel. Since 1876 above 300 wells have been added, and the yearly production of crude oil has increased from 6,000,000 to 115,000,000 poods, or from 30,000,000 to 575,000,000 gallons ; and this remarkable increase has been effected on the same old territories that were known centuries ago — viz., Bibi-Eibat, Balakhany, and Sabountchi, and Surak- hane, at a distance respectively of from three to nine miles from Baku, and of a total area not exceeding 1,200 acres. The average cost of a well, including labour, derrick, boring tools, pipes for casing, boiler, engine, &c., is reckoned to amount to 20,000 roubles, or about 2,000/. There are 136 refineries, of which the twelve largest are furnished with 216 stills, of a capacity of 750,000 gallons, and producing yearly 125,000,000 gallons of kerosene ; and the 124 small refineries, having 325 stills, of a capacity of 475,000 gallons, produce yearly about 15,000,000 gallons of kerosene. Owing to low prices, forty of the above-mentioned small refineries have entirely PETROLEUM. 123 stopped operations, and at many others, not except- ing large ones, work has now for the same reason been partly suspended. It is estimated that by using the actual working capacity, taking 300 working days, the twelve large refineries are prepared to turn out yearly 200,000,000 gallons, and the 124 small refineries 125,000,000 gallons of kerosene. The number of labourers employed on the different works has greatly diminished during the last few years, owing to a variety of mechanical improvements econo- mising mechanical labour, but partly owing also to temporary suspension of operations on account of bad business. Wages have not much altered, and are as low as Is. per day for unskilled, and from 2s. to 4s. for sldlled labourers. With regard to the future prospects of the actually- worked territory near Baku, the level of the subterranean petroleum deposits of that territory is steadily lowering at the rate of about 50 feet for every 500,000,000 gallons of crude oil extracted. The average depth of productive wells some ten years ago was 200 feet ; it is now about 500 feet. The number of Avells in working has now increased to 335 at Balakhano-Sabountchi, to 13 at Romany, and at Bibi-Eibat they have remained unchanged at 14. The average depth of the bored wells in working is 96 sagenes (sagene = 7 feet) at Balakhano-Sabountchi, 120 at Bibi-Eibat, and 103 at Romany. As regards the average production of naphtha every 24 hours, only including the ordinary bored wells and not the springs, it reaches 2,803 poods at Balakhano-Sabountchi, 4,007 poods at Romany, and 5,616 poods at Bibi-Eibat. The highest price of crude oil at the wells is at present 1 copeck per pood, or less than a farthing for five gallons, 124 MANUALETTE OF DESTRUCTIVE DISTILLATION. and it is estimated that even at such a low figure the cost of production is, in the average, safely covered. The cost of producing refined oil is more amenable to cal- culation. The production of 1 pood of kerosene requires, in the average, 3^ poods of crude oil, at 2 copecks per pood, dehvered at the refinery, G J copecks ; sulphuric acid, IJ copecks ; caustic soda, ^ copeck ; labour, 4 copecks ; total, 12 i copecks. The above quantity of crude oil, upon having been refined, leaves 1^ poods of residue, which, as liquid fuel, may be realising at 2 copecks per pood, giving fully 3 copecks, which have to be deducted from 12^ copecks. The cost of producing 1 pood of kerosene is thus made out to amount only to 9^ copecks, or of 5 gallons to about 2d. and a very small fraction. The cost of heating is not taken into account, as the given quantity of 3J poods of crude oil still leaves J-pood partly used up for heating, partly destroyed by the very process of refining. For storing petroleum in tanks for a period of from three to twelve months respectively, from 1 to 3 copecks per pood, or from about \d. to |d per 5 gallons, is charged. For conveying crude oil from the wells to the refineries by pipe on a distance of about 8 miles, the rate is \d. per 5 gallons, and it was formerly |d The freight on the same quantity from Baku to Tsaritsin has been reduced from 20 to 13 copecks, or from about bd. to '6ld. The railway rate from Baku to Batoum has been reduced to 16 copecks per pood, or M. per 5 gallons. Through transports to the different markets of Russia and Europe at fixed rates are available, but to a very limited number of traders. The costs of transports from Baku to the more distant markets are as follows : — To St. Peters- burg, per 5 gallons, Is.; Warsaw, ditto, lOtZ. ; Odessa, ditto, Id. ; Vienna, ditto. Is. M. ; Berlin, ditto, Is. M. ; Constantinople, ditto, Id.-, Marseilles, ditto, 8iLigbt oils. 20J 31\ Heavy oils containini 2 1 J mucb paraffin. 3 Pitch. 4 Coke. 100 Warren and Storer's very careful researches (1867) yielded the numbers detailed below : — [Melting-point Sp. gr. 38°_40° 875] Educts. Decylene Undecylene. Duodecylene Naphthalin . Tridecylene B.P. 175-8 187-4 195-9 208-3—219-5 232-75 The fractions below 175° were small in amount, and consisted chiefly of heptyhc and octylic hydrides (con- taminated Avith defines and perhaps also toluene), xylene, nonylic hydiide, nonylene, and cumene successively. The following numbers represent much more recent (1883) results (Sp. gr. -885) :— 144 MAXUALETTE OF DESTRUCTIVE DISTILLATION. Refined Products. Per cent. Burning oil (sp. gr. -832) . . .. 30-38 Lubricating oil (sp. gr. -901) . . 51*24 Scale (melting at 51-4°) . . . . 10-74 Bottoms 1-40 93-76 Setting-point, 7*2^ The only otlier locality in Upper Burmali where petro- leum has been actually collected in notable quantity is Pagan-Kyet, about 10 miles above Pagan, or about 50 above Yenangyoung, on the opposite or west bank of the River Irrawaddy. Here there are 14 wells which about a year ago were officially stated to yield about 8,000 viss of oil per month. For some time past Messrs. Finlay Fleming and Co. have refined the produce of these wells together with the Yenangyoung oil at Rangoon, but the yield of the Pagan wells has been steadily diminishing, and is now very small. The firm in question have, how- ever, obtained a concession, and are about to commence drilling in the Pagan oil-field. The oil from this locality has a sp. gr. of -837, a setting-point of 60° F., and a vis- cosity of 5-91 at 90° F. (rape oil at 60° F. = 100). It is, therefore, of considerably less density than the Yenang- young oil, and it yields a larger percentage of kerosene, but a very much smaller percentage of paraffin. In the Ferghana district of Turkestan there were (in 1883) 200 valley wells, in two chief ranges, 27 and Qh miles long respectively, and situated in the limestones and slates of the local *' chalk " formation. Sp. gr. of the oil, 0-95. Persian petroleum yields 87 per cent, of burning oil. The pitch lake of T7inidad is well known. The PETROLEUM. 145 bituminous matter comes from the " Newer Parian " formation of G. P. Wall, which is probably upper miocene. Petroleum is recorded from Cuba and from St. Domingo. In Columhia, the existence of petroleum in some quantities has been reported at Tubara, twelve miles from Barranquilla, near the mouth of the River Magdalena. Mexico. — Petroleum occurs in tertiary beds on the east coast, in the State of Vera Cruz, between the Panuco and Tuxtan Rivers. The wells so far sunk are mostly near the coast. Around Lake Culco there are said to be forty oil-springs. Algeria. — Petroleum springs were discovered about ten years back in Algeria, in the eastern part of the province of Oran, at Ain Zeft, nearly midway between Cassaigne and Renault. Here the beds are of lower tertiary age ; they dip at a high angle from N.N.W. to S.S.E. The petroleum, with salt water, comes out of grey and blue marls with g^^sum and sulphur. Very little has yet been done to explore these deposits. The importance of any considerable amount of petroleum near the shores of the Western Mediterranean is obvious. As regards local consumption, there is the protection duty on imported petroleum, which may allow workings to be made at a profit. In Poland^ petroleum occurs at Wojeza, in the govern- ment of Kielce ; it is found in sandstone, intercalated with shales, in miocene beds. In south-west Hungary^ Croatia, and Slavonia, Dr. J. Noth describes the petroleum as occurring in folded strata ; sometimes along anticlinals, sometimes where these anticlinals have been bent over to the north-east, so that a boring goes twice through the same bed. £ 146 MANUALETTE OF DESTRUCTIVE DISTILLATION. Further south, petroleura is known in Bostiia. Bitu- minous matter also occurs in phocene gravels of Selenitza in Albania. No petroleum is yet known in Bulgaria or Servia (cf. p. 159) ; but in the latter country the eocene strata are rich in bituminous schists, and contain thin beds of salt. The whole geology of this country is said by Dr. A. B. Griffiths to resemble that of the Galician area. In North-Eastern Hungary, along the southern flanks of the Northern Carpathians, petroleum occurs in neocomian, middle eocene, upper oligocene, and in more recent strata. Exceptions to the general rule as to the occurrence of petroleum in ordinary cretaceous or tertiary beds are said by Noth to occur in parts of this district. To the south- east of Nagy-banya, in the Szatmar country, petroleum is found in dolomitic limestone, underlying mica-schist. In the Nagy-banya basin, and also in the Matra Range, it occurs, impregnating trachytic tuffs of miocene age. Germany. — Attention has hitherto principally been directed to the Liinberger Heide district, known as the Oelheim Belt, three miles north of Peine, on the Hanover and Brunswick Railway. At the eastern part of Oelheim the oil is stored in the gault. There seems, also, to be some in the wealden beds, and in the upper Jurassic strata. To the west there are triassic beds ; but these seem to be mostly barren of oil, although Piedboeuf believes that the fossiliferous middle trias {Musehelkalk) is the true source of the petro- leum, which has been stored in the overlying beds. At Horst, petroleum was first found in the gault; recent borings passed into lower strata — probably wealden — and then obtained oil in larger quantities. Here, as is frequently the case, the lighter oil came from the lower bed. Petroleum idso occurs at Wietze and Steinfiirder, near the River Aller, some miles ncirth of Hanover: here I'ETROLEUM. 147 it lies in the keuper beds, in the immediate neighbourhood of rock salt. This belt comprises about 25,000 acres, but the borings are at present confined to about 20 acres. In 1881, there were twelve pumping wells in operation here, yielding 1,250 barrels per Aveek. At present there are in this district 14 pumping wells in operation, with an aggre- gate production of 60 to TO barrels of crude oil per day ; and 9 wells are in process of boring. Dr. Kramer states, that at a recent date the production of the Oelheim district had fallen to 50 barrels per day, but had since been slightly increased. Petroleum has also been found in Alsace, on the Lower Ehine, at Schwabweiler, Pechelbronn, and at Lobsan; also near Carlsruhe, in the Grand Duchy of Baden. At the beginning of the year 1888 there were two borings only at Hiinigsen that had been made for the purpose of obtaining raw petroleum, and during the course of the year eight more borings were undertaken. Of these ten oil-wells, six yielded petroleum, three had to be given up as useless, and one was still being experi- mented upon. The output of the two older wells at Hiinigsen has not appreciably diminished. At the beginning of 1888 there were twelve wells being pumped at Oelheim ; of these, four had to be given up, while six became more productive during the course of the year. At the commencement of 1889 there were no less than 14 wells being pumped from. The following figures exhibit a comparison between the outputs for the years 1887 and 1888 : — f2 148 MANUALETTE OF DESTRUCTIVE DISTILLATIOX. Hanigsen 54,342 Oelheini 982,092 Total (1888) .. .. 1,036,435 Kgs. Total (1887) .. .. 1,003,023 In the refinery at Peine tlie amount of raw oil Avorked up was as follows : — Kgs. 1887 2,323,904 1888 2,968,828 The petroleum of Hanover has been known for a long time. It escapes from the gault and other beds, to which it properly belongs, into the drift sands, and then appears at the surface. Hanoverian petroleum somewhat resembles coal-tar. It contains paraffins, olefines; pseudo-cumol, mesitylene, and other aromatic hydrocarbides, in not inconsiderable quantities; resins, and sulphur compounds, and their hydrides. The lubricating fraction is thin. Bavarian petroleum is found comparatively near the surface. Colour, greenish-brown; sp. gr. -811. On dis- tillation, it yields at 180° 14 per cent, of light naphtha (sp. gr. -731) ; at 320°, 39 per cent, of a yellow illuminant (sp. gr. -786) ; and thereafter, 16 per cent, of a reddish- yellow lubricant (sp. gr. '834), and 25 per cent, of lubricant rich in paraffin. Oelheim and Wietzer crude petroleum yield nothing below 150°. In Bavaria, petroleum occurs to the south of Munich, on the shores of the Tegernsee. Borings have been made to the depth of nearly 650 feet. The quantity of oil is PETROLEUM. 149 not large ; it occurs in the Flysch (here of lower tertiary- age), a series of hard shales, grits, and impure limestones, which form a zone along the northern flanks of the Bavarian highlands. The beds are sometimes nearly- vertical, or they dip at a high angle to the south, in which case they may be reversed. Beds of asphalt and bituminous schists occur in the district. Dr. V. Giimbel states that these by distillation yield an oil like that of the Tegernsee. He concludes that the petroleum has been thus produced. In Elsass, petroleum occurs at Schwabweiler, impreg- nating beds of sand and sandstone, which are mainly of lower oligocene age, but perhaps partly middle oligocene. Borings have been made to a depth of 950 feet. iVt Hirzbach the oil occurs in dark-coloured clays, in the lower part of the middle oligocene. All the petroleum strata yield brine. Dr. Andrae thinks that the petroleum here was formed in the rocks in which it is now found. Piedboeuf and Strippelmann think that it has impregnated them from underlying strata. Petroleum also occurs at the foot of the Eastern Vosges, from Worms to Basle. The crude oils of the three leading German districts have been compared (by Kraemer and Bottcher) Avith the ordinary standard oils. The results are as follows : — go Jd « Locality. be o ^ ^ i be u i a"' ? o p. s ^ p. O) M w to Ph tc H w. 35-91 «3 -856 « 1. Tegernsee •812 20-04 •726 26^12 •782 14^02 •825 3-07 2. Pechelbram •888 1-.30 •720 16 ^37 •778 17-07 •824 47-88 -893 16-28 3. Oelheim •885 •74 •750 11^05 •805 9-75 •852 73-91 -900 3-92 4. Pennsjlvaaia ... •814 14-34 •725 25^35 •811 13 ^75 •820 40-99 •850 5^57 .=). Galicia •842 14-21 •723 16 -93 •786 12-30 •83 1 47-58 •882 8 -95 6. Baku •880 •63 •762 21 -73 •811 15-55 •853 57-97 •903 4-10 From 1 and 4 (fraction above 250^') 4 per cent, of good 1^ MANUALETTE OF DESTRUCTIVE DISTILLATION. paraffin was obtained; 2 and 5 pelded 1*5 per cent. The percentage of sulphur was in (2j, -14; (3), '08; and (6), '0(>. {See also Engler, Dingl. polyt. J., pp. 207 and 268). Italy. — Petroleum springs are widely distributed along tlie northern flanks of the Apennines, from near Bobbio on the west to near Imola on the east ; oil impregnates the rocks, which are mostly of eocene age, so that wells are frequently contaminated. Petroleum has long been worked at Monte Gibbio. Gas, petroleum, and salt water issue in small mud volcanoes ; the Salsa di Sassuola and the Salsa di Querzola being perhaps the best known. The natural gas of Barigazzo has long been famous ; but gas issues at many otlier points. The foUomng are the most important statistics : — Production. Importation. ■s.s g-^* Year. ** Tons. Value in Lire. II Tons. 1878 . . 4 602 62,000 98 Not given. 1879 .. 4 402 50,000 70 55,660 1880 . . 2 283 88,595 24 57,571 1881 . . 2 172 76,540 24 59,571 1882 . . 4 183 86,844 121 61,500 1883 . . 5 225 58,387 92 67,630 188i . . 6 397 135,452 110 73,603 2,26i 557,818* 375,625 * Equivalent to 22,312^. sterling. In 1887, Italy produced 208 tons of petroleum, and 18,507 tons of asphalt and bitumen. Ancona is the chief oil-producing district; Tocco, in PETROLEUM. 151 Abruzzo (Cliilti Province), being the precise locality of the industry. Year. Mineral Production Value Persons Active. in Tons. in Lire. Employed. 1878 1879 — — — 1880 . . 80 12 000 11 1881 . . 58 8,700 12 1S82 74 27,160 72 1883 . 125 16,650 ]3 1884 • • Totals . . 90 43,900 17 427 108,410 The position of the Tocco Wells is 400 metres above the level of the sea, and belongs to the miocene (superior formation). In 1867 we have the first authentic record that in boring at Tocco the strata consisted of marl and gypsum, until the calcare nummilitico was reached, at a depth of 110 metres. The Societa Francese passed the calcare nummilitico and part of the calcare cretaceo. The dug wells of Montechino, Piacenza, have been worked about 80 years; they have a depth not exceeding 240 feet, and yield 160 — 180 lbs. of a very pure oil per day. Other Itahan locaHties are Vorghera, Piacenza, Parma, Modena, and Caserta. In Sicily, oil has been found in the province of Girgenti. Porro has examined four specimens of Italian petro- leum from Petralio Montanaro (Piacenza), Rivaunazuno (Vorghera), Tocco Casiona, and St. Giovanni Incarico. The first was of sp. gr. '7849, and gave 44*7 per cent, of light oil ; 19-8 at 127°— 150°, 22 at 150°— 203°, 14-4 above 203°, and 6*9 residue. The second had the sp. gr. -9132, and gave 22 per cent, below 220°, 33 at 230°— 270°, 37 152 MANUALETTE OF DESTRUCTIVE DISTILLATION. above 270°, and 7*7 residue. The third and fourth had the sp. grs. -951 and '974 respectively; they furnished severally 63*5 and 69*6 per cent, of oil, 32*2 and 28*3 of pitch, and 12 and 20 of gas. India. — The petroleum of India occurs in middle or lower tertiary rocks along the flanks of the Lov^er Hima- layas, generally where the beds are highly inclined. Frequently it occurs in the neighbourhood of salt deposits, or is associated with saline water. Throughout India petroleum occurs in the tertiary formation, as in Russia and Galicia. The strata in the oil- producing localities are greatly disturbed, and drilling is everywhere in India more or less difficult. Apparently petroleum occurs in the greatest abundance in the Khatan oil-field in Baluchistan, but the oil is not of satisfactory quality, even regarded as liquid fuel ; the locality of production is comparatively inaccessible, and the climate is bad. Undoubtedly the best oil from the point of view of the kerosene refiner is that which is obtained in the Arakan islands (the eastern Baranga and Rami, p. 139). Petroleum seems to be unknown in Peninsular India. The petroleum field of Baluchistan lies in the Mari Hills. At Khatan, in a boring 524 feet deep, oil was obtained on seven horizons. The petroleum of the Punjab, of which great things were once expected, seems to be of small value, and Mr. Medlicott thinks it the least productive of the Indian areas. The petroleum of Assam seems to be of some import- ance. It is generally found in the coahbearing beds of the middle tertiary. At Makum, oil-springs occur, and borings were here made to a depth of nearly 200 feet, when oil rose to within 44 feet of the surface. From one bore-hole 1,500 gallons were drawn in 12 hours, after PETKOLEUM. 153 which the flow varied much, occasionally reaching the original rate. In one hole, 200 feet deep, the oil spurted for a time with a pressure of 30 lbs. to the inch. Punjab. — Accounts of the Punjab oil-springs were published by Mr. A. Fleming in 1848,^ and in 1853 t ; by Mr. Maclagan in 1862 1; and by Mr. A. Fenner in 1866.§ A few years later Mr. Lyman was deputed to examine the deposits, and liis reports were issued collectively in 1871.11 From these it appears that in the Rawalpindi district there are some 16 spots at which indications of petroleum are met with in the tertiary rocks. Baluchistan. — The oil-field of Khatan is situated on the Mari Hills of Baluchistan, about 40 miles in a direct line to the east of Sibi Station on the Quetta branch of the North-Western Railway running fi-om Ruk Junction to Quetta. The oil occurs in the eocene formation, and is found exuding in many places, much of the oil which has thus escaped having been converted by exposure into a hard mass. Borings were first made here on behalf of the Indian Goverment by Mr. R. A. Townsend, Superintendent of Petroleum Explorations, in the cold season of 1884-85, and it was found that immense quantities of petroleum were obtainable at moderate depths. The wells drilled by Mr. Townsend are five in number, and are situated in a valley surrounded by mountains about 4,000 feet high. Their diameter is only 4J inches, and their depth does not much exceed 500 feet. The geological features of the * Journ, Asiat. Soc, Bengal, xvii. f Ibid., xxii. X Supplement to the " Punjab GoAcrnment Gazette." § Proc. Punjab Government Public Works Department. II Reports on the Punjab Oil Lands bj B. S. Lyman, " Government Press," Lalioi'e. 154 MANUALETTE OF DESTRUCTIVE DISTILLATION. locality liave been carefully dealt witli by Mr. Townseud in an official report.* Unfortunately the oil obtained is of remarkably high specific gravity and viscosity. Its density is, accord- ing to Redwood's recent results, practically identical with that of water, and it is in consequence freed with very great difficulty from the water with which it is associated as it comes from the well. Even when the oil is warmed the water does not readily subside. If an attempt be made to distil the oil containing water, the contents of the still froth up and pass over bodily. By prolonged exposure in a capacious vessel to a temperature somewhat above the boihng-point of water, the oil can be sufficiently dehydrated, but a far better system has been suggested, and will probably before long be announced. The oil is black or extremely dark-brown in colour by transmitted Hght, with comparatively little fluorescence, and it possesses very little odour. Its flashing-point is 280° F. (Abel test), and it contains no hydrocarbons available for use as ordinary burning oil. According to the official report of Colonel Conway- Gordon, experiments made by pumping four of the wells (the fifth had not then been drilled) showed that the yield of each well was from 400 to 600 barrels of oil in the 24 hours. " Thus any one of the existing wells is more than competent to deliver the entire supply of 50,000 barrels of oil a year, which is estimated to be the amount required for the Sind-Pishin section of the North-Western Railway." An oil similar to that obtained at Khatan occurs at Shoran, in Kalat, in the province of Kach Gandawa, in * Keport on the Petroleum Explorations at Khntan, by R. A. Townsend Superintendent of Petroleum Explorations in Baluchistan {Records of the Geological Survey of India, vol. xix., Part 4, 18S6). TETROLEUM. 155 Rind Baluch country. Slioran is about 42 miles from the railway at Belpat, and it is a question which of the two fields it w^ould be best to develop for fuel pui'poses. The prospect of an abundance of mineral oil in Assam has been proved. In his description of the coalfields of the Naga Hills, published in 1876, Mallet enumerated the places where oil has been observed in this district. In all cases the oil rises either on or close to the outcrop of the coal-bearing gToup, and usually near the outcrop of one or more seams of coal ; indeed, Mallet records one instance in which he saw the oil oozing out of the coal itself, though he points out that this may have been accidental, the coal being merely the last rock through which the oil passed on its way to the surface. Thick soft sandstone is the rock principally met with in boring, but blue clay also occurs. The strata, which are much disturbed, belong to the tertiary epoch. The most likely sites for productive wells appear to lie within the area of the immense concessions granted to the Assam Railways and Trading Company, and it is well known that this Company has for some time past been drilling at Digboy. Assam crude petroleum is dark-brown in colour, of rather high viscosity (the viscosity of a sample of sp. gr. -940 was 14-2 at 90° F., rape oil at 60° = 100), and has a shght and not unpleasant odour. Its specific gravity appears usually to range from '933 to -940, and its flashing-point is some- times as high as 212° F. (Abel test). It begins to distil freely at 280° F., but considerably less than 20 per cent, volatilises within the range of the mercurial thermometer. The oil contains none of the kerosene hydrocarbides, but it yields by the ordinary process of distillation 89 per cent, by weight of lubricatmg oil distillates. The proportion of 156 MANUALETTE OF DESTRUCTIVE DISTILLATION. solid hydrocarbides is not large ; the carbonaceous residue varies, according to Eedwood's experiments, from between 3 and 4 per cent, to over 8 per cent. Another sample had a specific gravity of -971, and commenced to boil at 460° F. Egypt. — Petroleum occurs in Egypt, in the vicinity of the Red Sea, at Gemsah, and Gebel el Zeit. It doubtless originates in the lowest Devonian sandstone (Mitchell), nowhere more than 300 feet thick, and resting directly on crystalline rocks. Above the sandstone, on the eastern slope of the plateau lying behind the crystalHne coast range, are layers of marl, alternating with fossiliferous breccias belonging to the upper cretaceous formation, about 250 feet thick. These are succeeded by more chalk, followed by upper miocene limestone about 300 feet thick. Oil occurs superficially throughout a district about 40 miles long and 5 — 12 miles wide. The specific gravity of the oil is about -880 ; it has a dark-brown colour, and a disagreeable odour, due to the presence of sulphur com- pounds. The loss on treatment with vitriol is about 50 per cent. It yields no burning oil, but a very large per- centage of lubricant of apparently good quality. Colour, dark-brown, almost opaque ; when diluted with petroleum spirit a green fluorescence was observed. Specific gravity at 17° C. = 0-9352. When cooled to — 15° C, the oil became thicker, but no solid separated out. The speed of flow, measured at 35° C. in Engler's viscosimeter, was 6 min. 40 sec. The extracts obtained by treating the oil with water and alcohol were neither acid nor alkaline in reaction. The ash consisted entirely of iron and lime, and equalled 0-12 per cent. When the oil was distilled, the only gas evolved was sulphuretted hydrogen. PETROLEUM. 157 The amount of hydrocarbides soluble in a mixture of concentrated and faming sulphuric acid in the portion of the oil distilling up to 310° C. was found to be 24 per cent. The residue (76 per cent.) consisted of paraflfins and naphthenes, and gave figures for its refractive power closely agi-eeing with those obtained from Baku petroleum, which consists chiefly of the latter ; the Egyptian oil, however, contained sulphur, even after the treatment with acid. The oil was examined as to it commercial value by distillation from a copper still, superheated steam being- employed when the temperature reached 300° C, as is done at Baku. Per Sp. gr. cent. at 17° C Burning oil .. 11-3 . . 0-841 Intermediate oil . . 25-0 . . 0-880 Machine II „ . . 16-7 . . 0-927 Machine I „ . . 16-7 . . 0-949 Cylinder 17-0 . . 0-955 Coke and loss . . 13-3 . — 100-0 Peru. — Deposits of asphalt have long been known to exist in the north of Peru, near Payta. A tract of land 20 miles long by 12 miles wide, at Talara, near Payta, has now six wells; and the refined product is in extensive demand on the west coast of South America. In the valley of Tucigal, about 4-7 metres from the coast, there are 28 wells, ranging in depth from 45—240 metres, the daily output of which is 1,000—2,000 barrels. The shipments in 1891 from Zairetos amounted to 2,324,219 kilos. crude oil; 1,190,161 illuminant, and 1,115,667 lubricant. 158 MANUALETTE OF DESTRUCTIVE DISTILLATION. Salathe states tliat the crude oil from Zairetos yields — t° c. Per cent. Product. 20°— 30° 2-8 Rhigoline. 30^— 80° 9-0 G-asoline. 80°— 150° 11 1 Benzoline. ] 50°— 230° 18-5 Light kerosene. 230°— 280° 10-0 Heavy kerosene. 12-8 Liglit lubricant. Above 280° 4-8 Heavy lubricant, free from paraffin, buttery at— 30°. 31-0 Pitch. There is a pipe line to the harbour of Paloena, which is 11 kilometres from the wells. Petroleum is known to occur over a tract 120 miles long by 60 miles wide on this coast. In Venezuela^ between the Rivers Zulia and Catutumbo and the Cordilleras, petroleum in considerable quantity is expelled from natural springs, together with boiling water. In Argentina the Jujuy product has been found to yield (from 100 litres) 90 litres of oil sp. gr. -861, and 10 kilos, of coke. On distillation, the 90 htres of oil furnished : — Naphtha, '740 sp. gr. Kerosene, -827 sp. gr. Heavy oils, '900 sp. gr. . . Litres. 6 34 30 70 New Zealand. — Petroleum occurs on the east coast of North Island at Poverty Bay, and at Waiapu, East Cape ; borings to a depth of about 1,000 feet have been made. The rocks of these districts are cretaceous and tertiary. Here the crude product yields 84 per cent, of illuminant. On the west coast of North Island, at Sugar] oaf Point, Taranaki (New Plymouth), a heavy oil, sp. gr. 960—969 PETROLEUM. 159 oozes from cracks in a trachyte-breccia ; wells have here been bored to a depth of many hundred feet, but no con- siderable supply has been obtained. Servian oil shale (from Subotinci) yields on dry distilla- tion, oil, 34 per cent. ; water, 8 ; ash, 29^ ; carbon (in ash), 17-3; gas, 11*5. Purer specimens give as little as 7 per cent, of oil. Japan. — This area has been described by Mr. Lyman. Petroleum occurs in tertiary strata probably pliocene. The oil-bearing rocks are folded, with the axes of the folds running nearly north-east and south-west, the folds being frequently reversed ; where so, the reversed dip is towards the neighbouring seashore — to the north-west in Echigo, and to the south-east in Tootoomi. This structure is further complicated by another series of folds, running nearly north and south. As would be expected in such a disturbed area, none of the wells flow, the oil is raised in buckets. The wells range up to over 700 feet in depth. The production in 1884 was about 4,750 tons; in 1882 it was nearly 3,530 tons. Petroleum has been recorded from Saghalien, the large island north of Japan. Indications of petroleum have also been recorded at Alexandi'etta {Syria), Vannes (Binttany), Miang Fang (Siam) ; in Java, Sumatra, and Borneo, There are bonngs for gas 3,000 feet deep in tlie district of Tsieu-Lum Taing {China). Petroleum occurs on the flanks of the Puy-de-la-Poix, east of Clermont {France), flowing from the calcareous peperino, of Avhich the Pay is composed. Borings, recently made near the village of Lussat, are said to have met with natural gas at a depth of 450 feet. Petroleum is also known near Gavian, in Herault, and near Grenoble. It occurs in numerous places along the nortliern flanks of the Pyrenees, in cretaceous and tertiarv beds. 160 MANU ALETTE OF DESTRUCTIVE DISTILLATION. Petroleum is found near Burgos (Spain), and also in cretaceous beds in Catalonia. ASPHALT. Asphalt is solid at the ordinary temperature. It ap- pears to be formed by the oxidation of the unsaturated hydrocarbides in petroleum. The most remarkable deposits are in Cuba and Trinadad, the asphalt from which islands has been found to yield 1*75 per cent, of paraffin. Other noted localities are the Dead Sea, Seyssel (France), Limmer, the Abruzzo, aud the Yal de Travers. It occurs also, of every degree of consistence, and in immense quantity, along the coast of the Gulf of Mexico, chiefly in the States of Tamaulipas, Vera Cruz, and Tabasco, where not unfrequently it is associated with rock-salt and "salt- petre." Asphalt being, like resin and terpenes, somewhat acid towards lime, is frequently retained in limestone rocks, or contains much lime. Organic sulphur has been found in some American specimens to the extent of 10*85 per cent. It is in gi-eat request for paving purposes. Strippelmann and Engler obtained from Bentheim asphalt (sp. gr. 1*092), when working on the large scale, burning oil, 12*72 ; " gas oil" and lubricant, 9*78 ; paraffin, 1*50; paraffin grease, 0*65; coke, &c., 48*47; loss, 28*88 per cent. The tar was free from phenol and kreasote. Asphaltic rock and bitumen in the form of conglomerate are found in various localities in Italy. In the Abruzzo there are two clearly-defined rocks — grey and black ; these are found in the miocene formation of the tertiary epoch. The calcare madreporico is con- sidered the true horizon of the asphalt. ASPHALT. Yields have been stated as follows : — 16L Ancona. Caltanissetta. Napoli. Eoma. Tons. Value in lire. Tons. Value in lire. Tons. Value in lire. Tons. Value in lire. 1878 6,879 244,581 IVot given. Not given. 100 1,600 1879 6,163 318,574 4,000 140,000 1,9G0 18,800 50 1,000 1880 1,660 115,520 4,000 120,000 150 1,500 450 20.450 1881 3,380 184,850 4,000 120,000 1,500 7.500 50O 22,500 1882 3,662 81,052 2,500 30,000 1,770 8,850 400 16,800 1383 2,156 177,850 2,500 37,500 1,850 9,250 233 11,750 188 i 9,100 345,200 6,000 90,000 2,000 10,000 250 10,000 Totals 33,000 1,467,627 23,000 537,500 9,230 55,900 1,983 84,100 The Abruzzo bitumen yields on distillation : — Per cent. Sp. gr. Flash-point. Burning oil Intermediate Lubricant 15 33 16^ •850 •945 •990 54-5° 121 •r 157 -2° The shipments of asphalt from Trinidad amounted in the first six months of 1889 to 32,460 tons. Turkish asphalt from Albania (about 16 miles from Valona) is free from paraffin. On analysis its four qualities give the following re- sults : — — Volatile. Coke. Ash. Finest , r 66-2 29-0 4^8 A 69-9 10-5 19 •e B 58^7 14-7 26-6 C 63 •! 51 31^8 162 MANUALETTE OF DESTRUCTIVE DISTILLATION. The finest quality is insoluble in alcohol, slightly soluble in ether, but readily soluble in bisulphide of carbon, chloro- form, benzol, and turpentine — melting at 60° C. or 140° F. Neither bleaching agents nor carbon has any effect on the colour. The finest, on being distilled at a low temperature, gives off 50 per cent, of an oily substance, having a sp. gr. 0*905. On redistillation the oil begms to boil at 100° C, rising so on to 200° C, and at 300° C. will boil over. When the remainder of the high boiling-point fraction is frozen, no paraffin separates, whilst that of the lower temperature assumes the semi-solid appearance of vaseline. The following organic analyses of the finest and ordinary, or C kind, may be instructive, as the large amount of oxygen present shows that they do not belong to the ozokerite or paraffin series, but are true asphalts : — Finest. C. Carbon . . 78-8 74-0 Hydrogen . . . . 8-3 7-5 Oxygen 7-5 18-4 Nitrogen . . 0-5 • • Ash . . 4-8 -• 99-9 The better kinds are suitable for the best japans, while the most inferior can be used for inferior articles, such as Brunswick blacks, ironwork, &c. The commonest can be " sweated '^ and purified to be equal to the best. The cheapest can also be utilised for strengthening the rock asphalts, none of which can be used without such addition, the Trinidad bitumen having up to now ousted every other article from the markets of the world for that purpose. In 1888 the United States produced 3,800 tons of asphalt and 50,000 tons of serviceable bituminous rock. OZOKERITE. 163 OZOKERITE. Ozokerite is a name applied to the solid or pasty varieties of petroleum. It occairs in England (Newcastle), Dairy (Scotland); Galicia, Ronmania (near Plojesti and Slavick), Hungary ; Wettin-on-Saal (East Frisia), Derbent (near), Baku, Islands of Tcheleken and Swatoi, Ekater- inoslav, Station of Kalocliinsky, and Truclimenia ; Egypt ; Utah, Texas, Arigona, Oregon, Canada, Manitoulin Island ; in the Kok-Tube Mountain (Namangan), Turkestan ; and elsewhere. The strata in which it occurs are chiefly tertiary and cretaceous. The principal seat of the ozokerite industry is at Boryslau (Moldau), where the ozokerite seems to have found its way into the miocene formation through a fault. The mineral is found in veins ranging in thickness from a quarter of an inch to several feet, over an area of about 1,000 metres by 350 metres. The deposit narrows con- siderably with the depth. The density of ozokerite ranges from -85 — '95, and the melting-point from 58° — 100°. The ordinary Gahcian product melts at 62°. Boryslau ozokerite of sp. gr. -93 furnishes about 26 per cent, of kerosene and 54 per cent, of scale. Baku ozoke- rite of sp. gr. -903 (m.p. 79°) yields 81*8 per cent, of scale; the Persian variety (sp. gr. -925) 53-5D per cent. ; and the Newcastle kind (sp. gr. -890 ; m. p. 60^—70°; 64-95 per cent. There are many refineries of ozokerite and ozokerite oil in Austro-Hungary, where the latter is largely used. The Moldavian oils are mostly sent in tank cars to Itzkany-Suczawa on the Austro-Roumanian frontier ; those of Wallachia, in so far as they are not refined on l2 164 MANUALETTE OF DESTEUCTIVE DISTILLATION. tlie spot, are tanked to Aiistro-RoTimanian refineries at Orsova on the Danube, Fiume, Vienna, Buda-Pestli, and the small refineries in Transylvania. Ozokerite oil is refined m the same manner as native petroleum. Solid brown ozokerite is refined by (1) distillation, usually with superheated steam — at 300° — 320° for parafiins (followed at 380° — 420° by yellow oxidised resinous bodies) ; (2) treatment of the sohd distillate with about 6 per cent, of strong oil of vitriol (about 1 per cent, by volume of soda of 1-2 sp. gr. being used when required) and washing with water ; (3) crystallisations from a low percentage of tlie light oil — or methyhc, ethylic, or amylic alcohol- - follo\^ ed by treatment with charcoal. In the last opera- tion the melted ozokerite may be preferably melted with animal charcoal, in the absence of a solvent, and the use of magnesic silicate has been patented as an efficient substitute for charcoal. The jield amounts to 60 per cent, of white scale. Fuller's earth also gives excellent results ; and aluminised charcoal might probably be very usefully employed. Ceresin is ozokerite bleached without distilla- tion, e.g., by heating to 200° C. with strong oil of \dtriol, washing, and filtering the melted mass through silicates. Another mode of " bleaching " consists in melting at 70°, decanting, melting with 5 — 15 per cent, of sulphur, and distilling in steam. The product is pressed at 35° — 50°, crystalHsed from amylic alcohol, and again similarly pressed. Native ozokerite may yield approximately — Petroleum. . . . . . , , . . 25 Lubricating oil Paraffin . . Coke Pitch and loss 21 36 8 10 100 OZOKERITE. 165 At Swatoi Astrow, near Apscheron, ozokerite is distille I in flat-bottomed retorts, holding 1,500 — 2,000 pounds each. The results are, according: to Grabowski — "Benzol" .. Naphtha Paraffin Heavy lubricating oil Coke Per cent. 2—8 15—20 36—50 15—20 10—20 Having regard to the fact that native ozokerite is chiefly worked for the purpose of obtaining solid paraffinn, distillation in a vacuum might obviously be advantageous ; this would bo, facilitated by the circumstance that Uttle or no gas is given off in the process. Crude ozokerite, as ordinarily distilled, contains chrysene, but not naphthaliu. The still holds about three tons. The purification of ozokerite by oil of vitriol is attended with very appreciable loss, on account of the oxy-com- pounds which the mineral is now known to contain. These, unlike the paraffins, are attacked somewhat ener- getically by oil of vitriol. Ozokerite, after purification for candle-making, melts at 51° — 61°, is quite odourless and colourless, and has a waxy section. The kind prepared by Otto^ of Frankfort- on-the-Oder, is said to melt at 83°, and to be so hard as scarcely to yield to the finger nail. The natural undistilled hydi'ocarbides of ozokerite are of great value for lubricating purposes. The following table gives the quantity and value of ozokerite mined in Austria-Hungary in the years indi- cated ; — 166 MANUALETTE OF DESTRUCTIVE DISTILLATION. Years. Tons. Value per ton. £ 1877 . 8,818 22 1878 10,177 26 1879 . 8,922 22 1880 . 10,360 29 1881 . 10,478 22 1882 . 9,899 22 1883 10,459 24 1884 . 11,751 27 1885 . 12,818 26 1886 . 13,702 22 1887 7,921 20 1888 8,640 21 1889 . 7,439 20 1890 . 6,071 24 In 1890 the United States produced 350,000 lbs. of refined ozokerite, valued at 6,563/. Among the by-products from ozokerite is the residue of the steam distillation. Since 1875, Field and Tailing have employed a vulcanised weld of this hard, black, waxy substance with india-rubber as an electrical insu- lator. Vaseline, paravasehne, and the like, are mixtures of iso-paraffins (e.g., C^g— C20) with lower hydrocarbides, and are taken from petroleum and ozokerite stills after some of the oil has volatilised ; their sohd paraffin is more or less removed, and the residue bleached without dis- tillation. Bleaching is effected by treatment at 30° with 10 per cent, of oil of vitriol, stirring for half-an-hour, and separating the carbonised layer. The clear portion is treated ^vith aqueous potassic dichromate, washed, heated to 80° with granular spodium (bone-black), and filtered hot. Another method consists in passing the oil through thirty charcoal filters (as constructed for sugar-refimng). After the bituminous matters have been removed, there is OZOKERITE. 1()7 a steaming at 250^, followed by filtrations. Vaseline is white, odourless, and tasteless, and has the sp. gr. 0-848. It is much in request as a lubricant, anti-rust, and basis for ointments and perfumes. The following table, due to Boussingault, shows the composition of a number of combustible substances from South America and other localities : — 1 2 3 4 5 6 7 Carbon . . Hydrogen Oxygen . . Nitrogen 86-82 13-16 0-00 0-02 82-85 13-09 4-06 0-00 85-29 8-24 6-22 0-25 77-84 8-93 11-54 1-70 82-7 10-8 6-5 0-0 71-89 6-51 21-57 03 80-96 5-13 12-50 1-41 — 8 9 ]0 11 12 13 14 Carbon . . Hydrogen Oxygen . . Nitrogen 87-05 5-00 6-56 1-39 87-81 3-88 7-67 0-61. 93 -05 3-35 3-43 0-17 92-25 2-27 4-94 0-54 94-83 1-27 3-16 0-74 97-6 0-7 1-7 97-87 0-37 1-70 0-06 1 and 2 are analyses of hitmnen from the fire-pits of Ho-Tsing, in the province of Szu-Tchuan, China. This bitumen is dark-green by reflected light, brown by tj-ans- mitted light. It is liquid at ordinary temperatures, but cooled deposits a crystalline granular mass of naphtlialin. 1 gives the analysis of the portion remaining liquid 2, the analysis of the semi-solid portion. 3, Egyptian asphalt^ which left an ash consisting of ferric oxide. 4, Bitumen of Judea^ found floating on the Dead Sea. 5, Fossil resin, from the auriferous alluvium at Giron, near Bucaramanga, New Granada, resembling amber in appear- ance. 6, Fossil 7'esin, from the auriferous alluvium of Antioquia, New Granada. 7, Coal from Canoas, plateau of Bogota (height, 2,800 m.). It occurs in grit connected 168 MANUALETTE OF DESTRUCTIVE DISTILLATION. with Neocomian limestone. 8, Fibrous coal from Antioquia. 9, '' Fusain'' from Blanzi. 10, '' Fusain" from Montram- bert, Loii'e. Fusain is a variety of coal resembling wood-charcoal in appearance. Some stalks, the interior of which is composed of fusain, are covered with a bark which has been converted into coal. It is apparently the fossil form of wood which was dried by exposure to air before becoming embedded, and which has not under- gone the same changes as vegetable debris, which decom- poses in swamps. 11, Anthracite from Chih. 12, Anthra- cite from Muso, New Granada. It occurs in masses in the schists in the emerald mines. It is hard, brilhant, and takes on a very high polish; sp. gr. 7*689. 13, Anthra- cite, supposed to come from Brazil. 14, Graphite from Kaison. PEAT. Peat consists of the cumulatively resolved fibrous parts of certain mosses and graminaceae. It gradually darkens from brown to black with increasing age. Judging from Dr. Angus Smith's results, it grows at the rate of about an inch in the year. A pectinous substance and a complex hydrocarbide fichtelite, have been found among its con- stituents. As a fuel it is most economically used at the spot where it is grown. It has been, however, destruc- tively distilled at a low temperature for tar, a branch of industry now scarcely profitable. The process gives a very porous, friable charcoal, possessed of great deco- lorising power; gas rich in carbonic dioxide is also given off. A ton of good peat may yield more than 5,600 cubic feet of gas. The purified gas contains about 11 per cent, of vaporised hydrocarbides, 37 per cent, of marsh BROWN COAL OR LIGNITE. 169 gas, 31 per cent, of hydrogen, and 19 per cent, of car- bonic oxide ; it is thus (as its mode of formation suggests) less oxygenated than wood gas, but more oxygenated than coal gas. The liquor is rich in hydric acetate, which amounts to about '2 per cent, on the peat ; ammonic sulphate, taken similarly, exceeds 1 per cent. Good peat yields about 3 — 6 per cent, of tar proper, which is comparatively easy to purify by the usual method. A specimen in the writer's museum had the sp. gr. -954. According to Vohl, 100 parts of peat tar from six sources fm-nished, on the average, 20-1 per cent, of paraffin oil (sp. gr. -82), 21*8 per cent, lubricating oil (sp. gr. -86), and 3*4 per cent, of paraffin. This last estimate seems doubtful. Wagenmann found as a mean, 2*1 per cent, of paraffin ; Kane and Sullivan about 1 per cent. ; other experimenters have obtained from -75 to '5, and even -1 per cent. Peat yields from 5 to 50 per cent, of ash, one-third of Avhich may consist of ferric oxide. To this source may not improbably be due the occasional ferruginous charac- ter of peaty waters, and the decolorising power of peat charcoal. BROWN COAL OR LIGNITE. Brown coal is intermediate between wood and coal proper, which latter it succeeds in geological time. It sometimes retains the fibrous structure of wood, has a yellow or brown colour, and pasty consistence, and is easily fusible ; at others it is quite black, and closely resembles coal. The better kinds retain much moisture. One of the common constituents of lignite is pyropis- site, a crystalline mineral, more or less soluble in petroleum. 170 MANUALETTE OF DESTRUCTIVE DISTILLATION. ether, and alcohol, melting at 79° — 82°, and closely related to a formula CgHjgO. According to Thomas, the greater part of the gas occluded in lignite consists of carbonic dioxide, with which olefines, oily aromatic compounds, and appreciable quan- tities of carbonic oxide are associated. Lignite coke is in use as a substitute for bone- black. Brown coal has been worked for many years at Weis- senfels, in Saxony, where it has yielded by the ordinary treatment, the ordinary products of the low-temperature process. At these works, according to a report of Dullo (1862 ?), the brown coal fm-nishes 17*8 per cent, of buttery tar, which yields 20 per cent, of paraffin, and 43 per cent, of illuminating oil. The means of Vohl's more recent figures, which refer to 13 sources, are — 18*6 per cent, of paraffin oil (sp. gr. -82), 32*4 per cent, of lubricating oil, and 4*1 per cent, of paraffin — reckoned on the tar, which may be taken at 11 per cent. In gravity and other respects, this tar very closely resembles shale tar. A geocerate, C26H52O2, is among its constituents. It also contains a remarkable hydrocarbide, picene, (^22^u^ melting at 335°, but obtainable in larger quantities by the destructive distillation of the residues of Californian petroleum. The above numbers refer to distillates obtained in horizontal cast-iron retorts. If steam be introduced during the process, the tar yields, it is said, as much as 30 per cent, of paraffin. The product is purified with some difficulty from sulphur and nitrogen. Although brown coal in many respects resembles peat, it much surpasses that substance in the value of its pro- ducts of destructive distillation, furnishing, in fact, about BONE OIL. 171 three times as much iar, and three tunes as mnch paraffin as peat. Such of the brown coals as most closely resemble avoocI contam but little nitrogen, and yield, of course, an acid distillate ; such as are akin to coal give an alkaline distil- late, being more nitrogenous. [According to Albrecht, the brown coal industry yielded in 1871 about 4,921 tons of paraffin, and double that weight of illuminating oil. He also states that a ton of medium quality yields 60 — 65 per cent, of finished pro- ducts, consisting of : — 15 — 17 per cent, paraffin. 29 — 35 „ illummating oil. 10 — 15 „ heavy oil. 2 — 4 „ kreasote. 4_ 6 „ pitch.] For the action of heat upon lignite oils and other oils of high boiling-point, see JowrTiaZ of the German Chemical Society, xi, 723, 1210, 1222, 1431 ; or London Chemical Society s Abstracts, 1878, 1860-63, 961. BONE OIL. Bones consist of about two-thirds mineral ingi-edients, not altered by heat (tricalcic phosphate), and one- third osseine, which is destroyed by heat. The latter substance has the following composition : — Carbon .. .. .. .. 50-4 Hydrogen . . . . . . . . 6*5 Nitrogen .. .. .. .. 16*9 Oxygen .. .. .. .. 26*2 172 MANU ALETTE OF DEbTKUCTlVE DISTILLATION. Thus bones yield about 6 per cent, of nitrogen. When they are soaked for several days in dilute hydric chloride, their calcic salts dissolve, leaving a mass of flexible osseine, which retains the shape of the original bone. Osseine dissolves in boiling water, being thereby trans- formed without change of composition, into an equal Aveighfc of gelatine ; hence it is an isomer or polymer of gelatine. In the destructive distillation of bones it is the osseine alone that furnishes distillate. The manufacture of bone oil is an industry that survives from mediaeval times. The bones are submitted to a preliminary treatment in order to remove fat. This is effected by prolonged contact with hot water, or, much better, by steaming in vertical cyhnders. The cylinders hold about 5 tons of bones, and the operation of steaming lasts about 12 hours. At the end of that time cold water is admitted from below in quantity more than sufficient to cover the bones ; the fat is thus brought to the surface, and is then skimmed off. During the operations of steaming and watering, some gelatine solution is of course formed in the cylinders ; this is removed, concentrated, and sold as " glue substitute." The bones are preferably distilled as thus saturated with moisture ; dry bones furnish a partially solid distillate, which would inevitably choke an exit-pipe of moderate length. The distillation is performed in horizontal cylin- drical retorts made of cast-iron ; a convenient size is 9 feet long by IJ feet in diameter. The retort is completely filled with its charge, and then closed after the fashion of a gas retort ; the addition of an exhauster has also been proposed. It is next heated to the lowest possible degree of redness, during eight hours. The residue in the retort consists of " animal charcoal " or " bone-black ; " this consists approximately of: — BOXE OIL 173 Charcoal . . . . . . . . 10 Calcic phosphate . . . . . . 84 „ carbonate . . . . . . 6 100 According to some authorities, it invariably retains nitrogen in greater proportion as the temperature has been lower. Seven retorts can be heated at one time. Another and less manageable method is applied to the distillation of dried bones. The retorts, preferably five in number, are charged as before, and their distillate con- ducted while gaseous, and through a very short exit-pipe, into rectangular leaden chambers. Here a great deal of the amnionic carbonate solidifies; it is purified by sublimation. Both methods furnish a liquid distillate, containing, as in the case of coal, an aqueous and an oily portion. The aqueous portion is a solution of ammonic carbonate, cyanide and hydrosulphide, together with methylamme and its homologues, pyridine and its homologues (of at least two series), pyrrhol and ethylic alcohol. The oily portion is also charged with these, and contauis in addi- tion, fatty nitriles, C2 — Cg (not, however, when fat is absent), fatty and aromatic hydiides, naphthalin, aromatic dihydro-hydrides, CgH^^ — C^H^g, pyrroline and its first two homologues. The sp. gr. of the oil is -914 — '945 ; it begins to boil at about 80°. This product was formerly known under the name of Oleum animale Dippeli. The aqueous distillate is treated for ammonia in the same manner as the aqueous distillate from coal, excepting that weaker vitriol (sp. gr. 1*2) is used, on account of the richness of the ammoniacal liquor. The resulting sulphate is apt to be coloured with pyrrhol-red. 174 MANU ALETTE OF DESTRUCTIVE DISTILLATION. A ton of bones yields 10 — 12 gallons of oil, and 130 — 140 gallons of liquor of sp. gr. 1*03 — 1*04. Attempts to purify the oil for illuminating purposes have hitherto resulted in faihu'e. The exhausted ammoniacal liquor has been used as a sheep-dip. The oil, when distilled, yields an elastic pitch, in request for vamish-making. In addition to the above products, the destructive dis- tillation of bones furnishes a very decided amount of gas. Unfortunately this gas contains too much sulphur, and in too intimate a state of combination, to admit of economical purification. It is, however, possessed of very consider- able illuminating power, and is therefore somewhat used to light the more open parts of works ; but the greater part of it is burned under the boilers or retorts. Bone oil is easily utilised in the same way. The extent of this industry depends in a great measure upon that of sugar-refining. Some conception of its mag- nitude may be formed from the fact that for every ton of refined sugar more than a ton of animal charcoal is used ; the charcoal is then re-burned and used again, thus under- going a loss of value to the amount of 40 per cent, per annum. Horn^ hair and Uatlier yield a liquid distillate, very similar to that from bones. Weidel and Ciamician distilled gelatine, and found among the products pyrocoll, C,oHgN202 (a crystalline sohd), pyrrhol, homopyrrhol, CgH^N, and dimethylpyrrhol, together with methylamine_, butylamine, and perhaps quinoline. WOOL. 175 WOOL. Tlie following special experiments on the destructive distillation of wool have been made in the author's laboratory. The sample, which consisted of well-scoured yarn, contained 14-93 per cent, of moisture, and yielded -84 per cent, of ash ; 50 grm. of it were distilled during six hours. A suitable tower, containing standard acid, was placed to intercept any ammonia that might pass off with the gas. The first products observed in the course of the distillation were hydric sulphide and water; crystals of ammonic carbonate were observed next, and these were succeeded by a pale yellow oil. The distillate smelled very strongly of members of the pyridine series, and a very pungent body, probably acridine, occurred in the latest stages of the operation. Analyses of wool by Marcker and Schulze, and Scherer, are given in Watts's Gmelin, xvii, 351 [an unfortunate exchange of H for N in this analytical statement led the w^'iter (Trans. Chem. Soc.^ 1883, 142) to an erroneous formula for wool]. Their .percentages agree fairly well with the expression adopted below : — Carbon Marcker and Schulze. (Mean.) 49-54 . . Scherer. 50-65 CagHesNnSO . 50-49 Hydrogen Nitrogen 7-29 . . 15-60 .. 7-03 17-71 . 7-01 . 16-61 Sulphur 3-44 . . .. 3-45 Oxygen 2413 .. •• . 22-44 100-00 100-00 The " fixed carbon " contained a considerable quantity 176 MANUALETTE OF DESTRUCTIVE DISTILLATION. of nitrogen. The following equation corresponds with the determinations so far as made : — ^30^65^11^013 = C21N3 + C10H39 " Fixed carbon." G-as and tar. + 5 (NH3CO2) + 3HCN 4- H2S + 3H2O. Percentages found. Calc. Water . . 5-4 . . 5-8 Residual carbon. . . 24-9 . . 26-1 Nitrogen therewith 4-3 . . 4-5 Ammonia 8-6 .. 9-2 It must, however, be added that the sulphur was not entirely evolved, as '24 per cent, was found in the fixed nitrogenous carbon. Portions, also, of CO2 and HON ought doubtless to be credited to the gas and tar ; but it would have been a matter of extreme difficulty to deter- mine the free cyanide and carbonate. The actual tar amounted to about 2*5 cc. per 50 grm. of wool ; it was lighter than water. FIXED OILS. a. Vegetable. These bodies are mixtures of solid and liquid glyce- rides. They were first destructively distilled, on the industrial scale, by Taylor, in 1815. The retort consisted of a horizontal iron chamber, filled with coke, and heated to low redness, or a little higher. Above this was placed the oil reservoir, by which the gas was washed. From 90 — 96 per cent, of the oil was converted into gas. Sp. gr. '604 — '710; defines, 16 — 32 per cent. Analysis FIXED OILS. 177 showed 37 per cent, marsh gas; carbonic oxide, 14 per cent. ; hydrogen, 21 per cent. Castor Oil is destructively distilled at Jeypore for the production of illuminating gas. The seed, pressed at the works, yields 33 — 40 per cent, of oil, which is distilled without purification. A maund (82 lbs.) of oil yields about 800 cubic feet of purified gas, at an average cost of 35s. IQd. per 1,000 cubic feet. The illuminating power of the gas is such that the burners in use consume only IJ cubic feet per hour, corresponding to 17 — 18 candles. Some tar is formed in the process. p. Animal. These oils, in their general chemical deportment, much resemble the vegetable fixed oils. Warren and Storerhave made a detailed examination of the distillate from the hme soap of Menhaden oil, which is prepared from a kind ot herring {^Alosa menhaden). The oil was saponified with one-fourth of its weight, i.e., an excess of caustic lime, and the dried soap distilled from iron retorts. The brown malodorous distillate was rectified in a steam current, which left a thick residue, containing much crystalline matter. After purification with vitriol and soda, and by distillation in steam, the oil exhibited the general aspect of a petro- leum. The following table gives the relative yield, in a total distillate of 6,400 cc. of the substances indicated — intermediate fractions, in which the boiling-point was not constant, not being taken into consideration : — r cent. Substance. B.P. 0-8 ^'Amylene LAmylic hydride . , 34-5— 35-1) .. 39 3-9 Hexylene .. 65 2-1 Hexylic hydride . . 68-5— 69-5 3-1 Benzene . . 79-9 78 MANUALETTE OF DESTRUCTIVE DISTILLATION. er cent. Substance. B.P. 4-7 . (Enantliylene. . . 95 7-6 . Heptylic hydride . 97-8 6-9 . Toluene . Ill 12-5 . r Octylene LOctyHc hydride . 123-8— 125-2 . 128—129 13-3 . Xylene 7-8 . Nonylene . 153 23-5 . ^Cumene LDecylene . 174 175 10-2 . Undecylene .. . 195-4 3-1 . Duodecylene . . . 212-6 Thus the distillate, while well characterised by the presence of olefines and hydrides of the fatty series, is remarkably rich in aromatic products. The latter are mainly due to the high temperature requisite for the decomposition of the lime soap. SUINT. Suint, the dried sweat of sheep, constitutes about 15 per cent, of the weight of the fleece. It dissolves in the water in which the raw wool is washed. The evaporated residue consists of 50 per cent, organic matter, and yields one-third of its weight of pm-e potassic carbonate, the remainder being sulphate and chloride, very free from sodium. One-third of the potash used in France is derived from this source (6,000,000 kilos, of wool). The distillation of the solid suint gives rise to gaseous hydrocarbides and a good deal of ammonia ; the residual coke is lixiviated for potassic salts. A kilo, of suint furnishes 210 litres of gas of very high illuminating power. BEET-ROOT RESIDUES. 179 BEET-ROOT RESIDUES. The jiiice of the beet is somewhat rich in nitrogenous bodies, among which aspartic salts and betaine (trimethyl- glycocine) are especially noticeable. Potassic salts are also present in considerable quantities. Fermented beet- juice, after removal of the alcohol, is termed *' vinasse " by the French distillers, who evaporate and ignite it, thereby producing about 2,000 tons of potassic carbonate annually. A process devised by Vincent has been now for some time employed, whereby the nitrogenous constituents are also recovered. The spent wash is concentrated until it has the sp. gr. 1-81, run into cast-iron retorts and distilled, each charge taking four hours to work off. The gaseous products are passed through condensers, and then burned under the retorts. The aqueous portion of the distillate contains ammonic sulphide, carbonate, and cyanide ; methylic hydrate, sulphide, and cyanide, abundance of trimethylamine, and many of the fatty acids. The tar, when again distilled, yields more ammonia, series of oils, and pyridines, phenol, solid hydrocarbides, and pitch. The aqueous distillate is neutralised with hydric sulphate and evaporated to crystallisation; the mother liquid retains trimethylamine sulphate, which can be utilised for the manufacture of methylic chloride, and in the production of alkaline carbonates. Vincent has observed that, while the wash is concentrating in the retort, the quantity of ammonia increases, mono- and di-methylamines gradually taking the place of the trimethylamine. Commercial trimethylamine contains, among other bodies, isobutylamine, propylamine, mono- and di-meth}^- amine (sometimes 50 per cent, of the latter) ; the tri- methylamine itself being occasionally as low as 5 — 10 per cent. M 2 180 MANUALETTE OF DESTRUCTIVE DISTILLATION. CELLULOSE. The following experiments on the destructive distilla- tion of cellulose were carried out in the author's laboratory. The still used was a glass flask holding 1,130 cc, and gradually heated to redness during six hours. The material used for distillation was well-scoured "hand- kerchief cloth." It contained 5*99 per cent, of water, and yielded '65 per cent, of a^h. By means of a piece of combustion tubing about 1-3 m. long, the still was con- rected with a two-necked receiver, on the outside of which cold water was constantly playing. The top of the still was covered with sheet asbestos. Heat was applied by means of a Fletcher burner. The distillation lasted six hours, during which a red heat was gradually ttained. The following are the particulars of an experi- ment (substance taken 100 grm.) : — Grammes. Wate?' measured after drawing from receiver 42*5 „ in substance . . . . . . . . 6*0 36-5 Hydric acetate (sp. gr. 1*06) in water . . 2*4 34-5 Acetate : water : : C^B^fi^ : 2H2O . . . . 1*2 35-7 Experimental drainage correction .. .. 1*1 Total water . . 36*8 = 39*4 per cent, on dry organic cotton. CANNOSE. 181 Grrammes. Fixed carbon in retort. . , . . , . , 26*5 Ash correction , , •? 2/)- = 27-6 per cent, on dry organic cotton. Tar (heavier than water), about 2*5 cc. Hydric acetate, 2*040 grm. = 2*20 per cent, on dry organic cotton. The equation is SCeH.oOj = 12C + Fixed carbon, (Calc.) 100 .. 29-fi .. (Found) — . . 27-6 . . Gras and tar. Organic water 29-6 . . 40-8 30-0 . . 39-4 In this case the weight of (gas and tar) is about equal to that of the fixed carbon. The C2 from the acetate, added to the tar, amounts to about 3-6 per cent. Hence the gas, saturated with moisture, must have amounted to about 26*0 per cent. [In this and similar experiments, all the acid in the distillate is reckoned acetic] CANNOSE. The following are the particulars of an experiment carried out by the author on the destructive distillation of cane sugar. The sample contained "15 per cent, of moisture, and yielded -03 per cent, of ash. The same apparatus was used as in the case of cellulose. I'lie operation is extremely liable to fail, owing to intumes- cence. Accordingly, only 25 grammes were distilled, the time taken being eleven hours. The corrected results were as follows : — 182 MANUALETTE OF DESTRUCTIVE DISTILLATION. ^12^22^11 = 9C + C3H2O + lOH^O Fixed carbon. Gas and tar. Organic water. (Calc.) — .. 31-(^ .. 15-8 .. 52-6 (Found) — .. 31-5 .. 17-7 .. 50-8 Sugar furnishes 2*42 per cent, of acetate when thus distilled, and very little tar. The gas probably amounted to about 17 J per cent. W. Foster has found high-temperature cane-sugar coke to contain 95 per cent, of carbon and 1*1 per cent, of hydrogen ; the low-temperature coke contained 94.1 per cent, of carbon and 1*2 per cent, of hydrogen. Fischer and Lay cock found the distillate to contain propylaldehyde and dimethylfurfuran. STARCH. Horvat {Chem, Centr., 1887, pp. 38—39) distilled starch with lime, and found among the products acetone, mesityhc oxide, and isophorone (207°). The fraction 128° — 207° comprised a series of ketones of the formula SUMMARY. 183 SUMMARY. The application of heat to cellulose and kindreii bodies leads to cumulative resolution; and the process is in principle the same, whether performed by nature or by human contrivance. At each stage in such resolution pecuhar products may be given off. At a high tempe- rature the liquid distillate is characteristically " aromatic;" at a low temperature " fatty." In either case the persist- ence of the TiCg group can be freely traced throughout the products of destructive distillation. Inasmuch as a chemical equivalent for much of the " temperature " can be found in " time," petroleum ma}' appear in rocks never actually igneous; and we can understand the occun-ence of degraded hydrides, such as turpentme with other " aromatic '* compounds, in living- trees. APPENDIX A. Shale Ketorts. The accompanying folding plate is intended to illustrate, by typical instances, the development of requirements in the construction of retorts. Old Vertical TyiM. [Fig. A]. — This kind of retort was largely used by Young's Paraffin Company. It was about 10 feet high and 2 feet in diameter.; the section being sometimes circular, sometimes oval. The line of the water seal, and the method of firing, are indicated in the diagram. Hendersons Retort. [Fig. B]. — " The products of dis- tillation pass off at the bottom of the retort by pipe (19) to the condensers. When the shale is exhausted the bottom plate (11) of the retort is removed by a hand lever apparatus (15), which at the same time folds back the little door (13) upon the furnace arch, and this door acts as a shoot to guide the spent shale into the furnace below. The carbonaceous matter left in the shale acts as fuel for the next charge. " Four retorts are built into the one retort oven (2). One of these is discharged into the furnace every four hours, and thus the heat is kept up. The furnace is divided into two by the partition (4). At the bottom of this partition, the non-condensable gases of the distillation are introduced to help the combustion of the spent shale and to increase the temperature. After the spent shale is thoroughly burned the bottom plate (17) of furnace is 186 APPENDIX. relieved of its counterpoise weight, and folds down to dis- charge the burned spent shale into the hutch below, to be passed (through a pond of water requiring evaporation) to the spent shale heap. *' The products of combustion pass from the furnace up through the flue (7), which protects the bottom of the letorts from overheating, into the oven (2). The new hot products displace the previous cooler ones at the top of the arch, and the colder products pass off from the bottom of the oven by the exit-pipes (8), which either (as in drawing) let off the products of combustion direct into the atmosphere, or, as is always done now, into a common flue Avhich passes along the side of the retort bench, and carries the gases to the chimney-stalk. " Superheated steam is carried in by a pipe (18). Very Httle air is required to burn the spent shale. The bottom plate (17) of furnace is solid, and allows air to pass only at its edges, and the suction through the oven from exit, being at the bottom, is only gentle." Young's Retort. [Fig. C]. — Vertical sections of two forms of this retort are given in the figure. Low red-heat distillation takes place in the upper portions. A, B ; the under portions A\ B^ being at a cherry-red heat. D, D^ are outlets for oil vapours and ammonia. A damper d can be slid inwards to form a division between the two portions A, A^ of the left-hand retort. E is a circular chamber furnished with numerous openings e into the retort ; into this steam is introduced through F placed preferably in a coil in the main flue G leading to the chimney-stalk. The heated products of combustion pass from the combustion chambers H through the ports h into the chamber or oven, and around the lower part of the retorts, as shown by the arms ; then through ports h^ in the partition wall C^ into the upper chamber or oven, and APPENDIX. 187 round the upper part of the retorts. A brick damper A'^ regulates the relative temperatures of the upper and lower retorts. The retorts are charged at the top, and dis- charged at the bottom, by means of a trap and shoot, into the combustion chamber. In the right-hand fonii of retort the steam, ammonia, and gases from the lower retort have to pass up through the shale ; in the left-hand form this is not the case. Young and Beilby Retort. [Fig. D], — The left-hand diagram shows the retorts proper; in the right-hand figure a superheater S and gas-producer are combined. The retorts are charged at the top, from which part also oil vapours and ammonia are led away. The upper part A of each retort is of iron, the loAver parts are of fire-clay, and these are subjected to a very high temperature. Steam is introduced internally below at S^, in order to destroy residual nitrogenous compounds and generate " water-gas," and the retorts are heated partly by " pro- ducer " gas, partly by the internal combustion due to the steam. In order to prevent fusing, not quite all the carbon of the shale is burned off. In this retort a very high temperature is employed below, in order to obtain an exhaustive yield of ammonia ; hence the need for a producer. " This gas-producer is a vertical retort, built of brick, closed by a door at the top, and provided with an exit-pipe which connects the retort with a system of mains and condensers. At its lower end the retort terminates in a closed fire-place and ash-pit, Avith regulating doors or dampers. The dross or small coal is introduced by the top door, and, resting on the fire-bars, fills the retort from top to bottom. The upper part of the retort, being surrounded by flues through which fire-gases are led, is kept at a full red lieat. The coal at this part of the retort is distilled, and ISS APPENDIX. parts Avith gases and vapours whicTi pass away by the exit-pipe to be cooled and condensed. As the coke passes down into the retort it is met by a current of steam which is partly decomposed, burning the carbon, and producing ammonia and "water-gas," which pass off along with the other volatile products. When such coke as has escaped the action of the steam reaches the fire- bars, it is burned into carbonic oxide by a regulated admission of air. This red-hot carbonic oxide passes off by ports at the lower end of the retort, and is burned in the flues surrounding the shale retorts. The gases from the upper part of the retort, after having been depiived of their condensable constituents, are also returned." It has been found an advantage to give each retort a separate hopper and valve. Moreover, in recent forms, the superheater S is dispensed with, and the gas-producer is in duphcate ; so that the left portion of Fig. D (2) is now the same as the right. Total yield of gas about 15,000 cubic feet per ton of shale. Couper-Rae Retort. [Fig. E]. — Below each retort A is a chamber B of fire-brick, and having about twice the capacity of the retort. This chamber is built solid — i.e., is not surrounded by flues. A jet of steam at C also injects air — a pecuharity of this retort. The retort A is exter- nally fired and surrounded by flues, as well as heated by the gases from B. The figure shows a pair of retorts. Stanrigg Retort. [Fig. F].— (Neilson, Patent 9783, 1889). The vertical section shoAvs the construction of this very simple form of retort. Upon a core bed lies a charge of about 60 tons of shale, the daily charge being about 12 tons. The retort is of 9-inch brick, in a casing of iron ; and is about 46 feet high by 7^ feet at the top and 11 feet at the bottom. Low-pressure steam (weighing about 100 lbs. per ton of shale) is introduced at G ; air APPENDIX. 189 also leaks in at the discharging door, as required. A Root's blower pulls over all gaseous products at E, where the temperature does not exceed 82°. The oil thus obtained from Stanrigg shale amounts to 40 gallons (ep. gr. -860) per ton; and the sulphate to 30 lbs. per ton (nitrogen in shale = 1*2 per cent.). It is found that a less height than 46 feet fails to give the maximum yield of ammonia. Gas, 60,000 cubic feet per ton. This retort has the disadvantage of producing less benzoline by reason of the large volume of gas which it makes, from which scrubbing cannot completely remove it : half a gallon of benzoline, perhaps, may be taken through in this way. But the cost of construction is so small (say 200/.), the heat is so well kept within it, aixl the manage- ment so extremely simple, that it mil probably be largely adopted in future. 190 APPENDIX. APPENDIX B. Bibliography. [The following list of Memoirs and Works has reference to the leading points in the development of modern Destructive DistiUation. The student consulting it will find it afford a convenient starting-point for the voluminous bibliography of this subject.] a. Memoirs. 1825. Faraday, M. On New Compounds of Carbon and Hydrogen, &c. Philosophical Ti^ansactions, 1825, p. 440. 1826. Unverdorben, 0. Ueber das Verhalten der organ- ischen Korper in hoheren Temperaturen. Poggendorff's Annale?i, viii, 253 and 477. 1830. Reichenbach, C. Beitrag zur nllheren Kentniss der trocknen Destination organischer Korper. Schiveig- gei^'s Journal, lix, 241. 1832. Reichenbach, C. Ueber das Kreosot, &c. Schweig- gers Journal, Ixv, 461. 1834. Runge, F. F. (Jeber einige Produkte der Stein- kohlendestillation. Poggendorff' s Annalen, xxxi, 65, 513, and xxxii, 308. Runge, F. F. Kyanol und Pyi'ol, zwei neue Produkte der trocknen Destination. Oken, Isis, Col. 608. 1835. Dumas, J. B., and Pehgot, E. Sur I'esprit de bois, &c. Annales de Chiniie et de Physique, Iviii, 5. 1836. Klauer, C. Ueber das Oleum animale Dippelii der Alten. Liehig's Annalen xix, 135. APPENDIX. 191 1842. Zinin, N. Beschreibung einigerneiien organischen Basen, dargestellt durcli die Einwirkung des Schwe- felwasserstoiFes auf Verbindungen der Kohlenwasser- stofFe mit Untersalpetersaure. 1843. Hofmann, A. W. Chemische Untersuchung der organischen Basen im Steinkohlentheerol. Liehig's Annalen^ xlvii, 37. — Ueber eine sichere Heaction auf Benzol. TAehig's Annalen, Iv, 200. 1848. Brodie, B. C, An Investigation on the Chemical Nature of Wax. Philosophical Transactions^ 1848, p. 147. 1849. Brodie, B. C. (On the same.) Philosophical Trans- actions^ 1849, p. 91. Anderson, T. On the Products of the Destructive Distillation of Animal Substances. Ed. Philosophical Transactions, xvi. Mansfield, C. B. Researches on Coal Tar. Journal of the Chemical Society, i, 244. Stenhouse, J. On the Nitrogenated Principles of Vegetables as the Sources of Artificial Alkaloids. Philosophical Transactions, 1850. 1851. Violette, Memoire sur les charbons de bois. Ann. Ch. Phys. [3], xxxii, 304. 1854. Bechamp, A. De Taction des protosels de fer sur la nitronaphtaline et la nitrobenzine. Annales de Chimie et de Physique, xlii, 18(5. 1856. Wagenmann, C. Ueber die Destillation des Pho- togens und Paraffinols im Vacumn. Dingier^ s Journal, exxxix, 43. Vohl, H. Ueber die Produkte der trockenen Des- tillation des rheinischen Bliitterschiefers (Schiste bitumineux), &c. Liehig's Annalen, xcvii, 9. 1856 (8), Vohl, H. Ueber die Destillationsprodukte der Braunkohle und des Torfs. Journal filr praktische Chemie, Ixviii, 504; Ixxv, 289. 192 APPENDIX. 1857. Williams, C. G. On some of the Products of the Destructive Distillation of Boghead Coal. Philo- sophical Transactions^ 1857, pp. 447 and 737. 1858. Kekule, A. Ueber die Constitution und die Meta- morphosen der chemischen Verbindungen, und ueber die chemische Natur des Kohlenstofis. Liehig's Annalen, cvi, 129. Hlasivvetz, H. Ueber Buchentheer-Kreosot und die Destillationsprodukte des Guajakharzes. Journal fur Ijraktische Chemie, Ixxv, 1. Pelouze, J., and Cahours, A. Recherches (sur les petroles d'Amerique). Comptes rendus, Hv, 1241 ; Ivi, 505 ; Ivii, 62. 1867. Warren, C. M., and Storer, F. H. Researches on Volatile Hydrocarbons. Memoirs of the American Academy^ ix, 177. 1868. Gill, C. H., and Meusel, E. On Paraffin and the Products of its Oxidation. Journal of the Chemical Society, xxi, 467. 1872. Schorlemmer, C. On the Normal Paraffins. Philo- sophical Transactions, 1872, p. 111. Thorpe, T. E., and Young, J. On the Combined Ac lion of Heat and Pressure upon the Paraffins. Pro- ceedings of the Royal Society, xx, 488. 1877. Mills, E. J. On Cumulative Resolution. Piiiio- sophical Magazine. 1883. Foster, W. The Behaviour of the Nitrogen of Coal during Destructive Distillation. Chem. Soc. Journ. (Trans.), p. 110. Piedboeuf, L. Couches petroliferes d'Europe Meri- dionale. Bcv. Univ. des Mines, xiii, 3. Tervet, R. On the Production of Ammonia from Coke. Journ. Soc. Chem. Industry, p. 445. 1884. Renard, A. Sur les essences et huiles de resine. Ann. Chim. Phys. [6], i, 223. APPENDIX. 193 1885. Beilby, G. The Production of Ammonia from the Nitrogen of Minerals. Journ. Soc. A^^ts. Carnegie. The Gas Wells of Pennsylvania. Mac- millans Magazine. Mills, E. J. Destructive Distillation. Journ. Soc. Ch. Industry, iv, 325. Redwood, B. The Russian Petroleum Industry. Journ, Soc. Ch. Industry^ iv, 70. Fawsitt, T. A. Wood Naphtha. Ibid., p. 319. Morgan, T. On the Treatment of PyroHgneous Distillate. lUd., p. 730. 1886. Armstrong and Miller. The Decomposition and Genesis of Hydrocarbons at High Temperatm-es. Trans. Chem. Soc, 1886, p. 74. 1888. Wright, T. L. Coal Distillation. Journ. Soc. Ch. Industry, p. 59. Ayi'es, A. Compressed Oil Gas and its Applica- tions. Proa. Inst. C. E., xciii. 1889. Steuart, D. R. The Manufacture of Paraffin Oil. Journ. Soc. Ch. Industry, p. 100. 1890. Peacock, D. L. Consular Report (Batoum). Redwood, B. The Oil Fields of India. Journ. Soc. Ch. Industry, p. 359. 1891. Topley, W. The Sources of Petroleum and Natural Gas. Journ. Soc. Arts, p. 421. Mills and McMillan. Destructive Distillation. Journ. Soc. Ch. Industry. 1892. Redwood, B. Galician Petroleum. Journ. Soc. Ch. Industry, 1892, p. 91. /3. Works. 1598. Artis avriferae quam chemiam vocant, volume n primum; pp. 239-240. [Notions on Distillation.] 1658. Glauber, J. R. Miracuh mundi (continuatio), p. 13 194 APPENDIX. [Wood vinegar, with drawing of plant] ; and Furni novi philosophici ; pars prima, p. 26 [Rosin oils]: — pp. 47-52, [Destructive distillation in general.] 1686. Lemery, N. A Course of Chemistry, translated from the 5th French edition, pp. 3-12 [Principles] et seq. [Operations.] 1730. Quincy, J. Lexicon Physico-Medicum, or a New Medical Dictionary. Art. Destination. [Physical theory, by Freind ; also various special distillations.] See also, Freind, J., Chemical Lectures, 2nd edition, Lect. iii (1737). 1764. Macquer, M. Elements of the Theory and Practice of Chemistry, 2nd edition. A Translation. [Oils, Charcoal, &c., from a phlogistic point of view.] 1786. Higgins, B. Experiments and Observations re- lating to Acetous Acid, &c. 1800. Watson, R. Chemical Essays. Vol. iii, Essay i : On Bitumens and Charcoal. 1863. Hofmann, A. W. International Exhibition, 1862 : Report on Chemical Products and Processes. [Nume- rous details on the Principles and Processes of Destruc- tive Distillation.] 1865. Wright, W. The Oil Regions of Pennsylvania, showing where Petroleum is found, how it is obtained, and at what cost, &c. N. Y. 1865—1871. Zincken. Die Braunkohle. 1867. Payen, A. Chimie industrielle, vol. ii (organique). 1868. Wurtz, A. Dictionnaire de Chimie pure et ap- pliquee. [Special articles.] 1872. Wagner, R. A Handbook of Chemical Technology (Translated by Crookes). 1874. Albrecht, M. Das Paraffin und die Mineralole. [A pamphlet containing very numerous manufacturing- details.] APPENDIX. 195 1874-5. Watts, H. A Dictionary of Chemistry, 2nd edition. [Special articles.] 1875. Ure, A. Dictionary of Arts, Manufactures, and Mines, 7th edition. [Special articles.] Wrigley, H. E. Special Report on the Petroleum of Pennsylvania : its Production, Transportation, Manufacture, and Statistics. Maps and illustra- tions. 1877. Hofer, H. Die Petroleum-Industrie Nord Americas. [History, economics, geology, and technology.] 1878. Pechar, T. Coal and Iron in all Countries of the World. [Statistics.] 1878-9. Strippelmann, L. Die Petroleum-Industrie Oester- reich-Deutschlands. [Geology, mining, economics, technology.] 1881. Burgmann, A. Petroleum and Erdwachs. [Pro- cesses, plant, and testing.] Brunton, B. H. The Production of Paraffin and Paraffin Oils. {Proc. Inst, C, E,) [Processes and results of manufacture.] 1882. Schultz, G. Die Chemie des Steinkohlentheers. [Materials, plant, references.] Meade, Richard. The Coal and Iron Industries of the United Kingdom, comprising a description of the Coal Fields and of the principal Seams of Coal, with returns of their produce and its Distribution, and Analyses of special varieties; also an account of the occurrence of Ores in Veins and Seams; Analysis of each variety ; and a history of the Rise and Progi-ess of Pig-Iron Manufacture since the year 1740, exhibit- ing the economies introduced in the blast furnaces for its production and improvement. Lunge, G. A Treatise on the Distillation of Coal Tar and Ammoniacal Liquor, and the separation from 196 APPENDIX. them of Valuable Products. [Also in a German edition.] Reinsch, P. F. Microphotographien lib. die Struc- turverhaltnisse der Steinkohle dem Carbon. 13 plates. 4to. Leipzig, 1883. 1883. Grouven, H. A New Method for the Determina- tion of Nitrogen in all its Combinations. Translation by G. Beilby. 1884. Marvin, C. The Region of the Eternal Fire. [The Petroleum Region of the Caspian in 1883.] Schaedler, C. Die Technologie der Fette u. Oele der Fossilien [Mineralole]. Illustr. Plates. Leipzig. 1885. Peckham, S. F. Report on the Production, Tech- nology, and Uses of Petroleum and its Products (1879-80). [An exhaustive treatise on the subject, with voluminous bibliography.] 1886-7. Schaedler, C. Die Technologie der Fette und Oele der Fossilien [Mineralole], &c. Leipzig. 1887. Crew. — Practical Treatise on Petroleum. Wagner's Jahreshericht. (Annual.) Kerl's Reperto7'ium der technischen Literatur. (Annual.) Hastings's Gas Worhs Statistics. (Annual.) Sto well's Petroleum Reporter. (Monthly.) Journal of Gas Lighting. (Weekly.) The Petroleum World. (Weekly.) Journal of the Society of Chemical Industry. (Monthly.) The Oil and Colourman s Journal. (Monthly.) Neue Wochenschrift fur den Gel und Fettwaarenhandel. (Weekly.) Report of the Geological Survey of Pennsylvania. (Annual. See years 1885-86, for detailed maps and section.) Mineral Resources of the United States. (J. D. Weeks. Annual.) ^ APPENDIX. 197 APPENDIX C. Weights and Measures. Foreign. Centimetre 2*5399 centimetres Metre . . 0-304794 metre . . = 0.914383 „ .. = Litre . . . . • • - 4.543458 litres . . ■- Gramme . . . . - 0-064792 gramme . . : Kilogramme . . . . - 0-453523 kilogramme : 50-802377 kilogi-ammes: 1016*04754 kilogrammes : Kilogramme . . Centner Pood Barrel . . Chaldron (coal) Burmese viss . . ■•{: English. 0-39371 inch. inch. 39-370 inches. 3-2809 feet. 1-0936 yards, foot, yard. 0-220097 gallon, gallon. 15-43235 grains, grain. 2-204621 pounds (lbs.) pound. hundredweight (cwt.). ton. •0009842 ton. 110-231 pounds. 16-25 kilos. 35-82 lbs. Barrel (42 gals. American). 35 gals. Imp. 53 cwt. 3*65 lbs. 198 APPENDIX. Temperature. Deg. C = f (Deg. F. - 32). Specific Gravity. ^ *_ Peg. Twaddell x 5 + 1000 Sp.gr. X 1000-1000 ^ ^^^ ^^^^^^^j^ * Water being taken as 1,000. INDEX Acid, acetic, 87. tar, Eare's treatment, 33. Albama, petroleum in, 146. Algeria, petroleum in, 145. Amber, 99. Ammoniacum, 99. Anthracene, 66. Apple tar, 89. Argentina, petroleum in, 158. Asphalt, 160. Assam, petroleum in, 155. Astatki, 129. Baluchistan, petroleum in, 153. Barangas, petroleum of, 139. Beet-root residues, 179. Bibliography, 190. Bitumen, 160. Blast-furnace tar, 77. Bone, liquor from, 173. oil from, 171. Bosnia, petroleum in, 146. Brown coal, 169. Broxburn, section in, 21. Burmah, petroleum in, 138. California, petroleum in, 120. Canada, petroleum in, 131. Cannose, 181. Caoutchouc, 100. Cellulose, ISO. Ce resin, ] 64. Chenall's process, 47. Coke, Coal, 58, 59, 61. Coal, composition of, 55. • coiirse of distillation of, 57, 60. distilled in varied time, 57. distilled with lime, 60. gas, composition of, 73. organic matter in, heated, 71. output of, 74. yields from, 59. Coal tar, 54, 61. composition of, 65, 67. refining, operations in, 69. treatment of, 61. constituents of, 69. Coke ovens, products from, 78. Colorado, petroleum in, 119. Columbia, petroleum in, 145. Cork-tar, 91. Cracking, 48. Crude oil, 16, 29. Cumulative resolution, 7. Deblooming, 94. Depth and quality of shale, 22. Distillation, destructive, defined, 5. fractional, 11. Dragon's blood, 99. Educt, defined, 5. Egypt, petroleum in, 156. Elemi, 99. Galicia, output of petroleum in, 137. petroleum in, 134. G-as from paraffin oil, 36. Canadian, 75. Gras, Coal, cyanide in, 60. Paris, 75. scrubbed, 59. sulphur in, 61. United States, 75, Gas, natural, 109. natural, analyses of, 114, occluded, 19. oil, 36, 176. in shale distilling, 26. Gas- tar, nitrogen in, 61, Gas, Wood, 85. Gelatine, 174. Germany, petroleum in, 146, Guaiacum, 99. Heats, high and low, 49. Hungary, petroleum in, 145. India, petroleum in, 152. Indiana, petroleum in, 110. Italy, petroleum in, 150. Japan, petroleum in, 159. Jute, distillation of, 90. Kentucky, petroleum in, 119. Lignite, 169. Liquor, parallin, 27. rosin, 93. wood, 85. 200 INDEX. Mexico, petroleum in, 145. Naphtha, wood, 87. New South Wales shale, 16. statistics of, 18. New York, petroleum in, 110. New Zealand, petroleum in, 158. Oils, fixed, distUled, 176. Ohio, Findlay, section through, 112. petroleum in, 110. Ozokerite, 163. output of, 166. Paraffin industry, 16. operations in, 45. statistics of, 38, 41. jelly, 47. nature of, 46. Paraffins, normal, boiling-points of, 53. Paraffins, normal, melting-points of, 53. Paraffin oil, refining, 30. solidified, 47. still, coke, 130. wax, liquefied, 47. refining, 34. Peat, 168. Pennsylvania, petroleum in, 110. Persia, petroleum in, 144. Peru, petroleum in, 157. Petroleum, 100. composition of, 115. Burmese, analysed, 143. Canadian, composition of, 133. production of, 133. Gralician, composition of, 135. heating power of, 129. occurrence of, 100. pipe-lines, United States, 113. E/Ussian, 121. wells, United States, 113. United States, 108, 117. Poland, petroleum in, 145. Products, conditions influencing, 6. Product, defined, 5. Eefining, Russian, 127. Refineries, Russian, 122. Retort, 23. Couper-Rae, 25, 188. Henderson's, 24, 185. Retort, Holmes's, 23. Rolle's, 23. shale, described, 185. Stanrigg, 188. • Taylor's, 37, 176. Young's, 186. Young and Beilby, 25, 187. Rosin, distillation of, 13, 91. oil, 91, 93. oil, composition of, 94. • grease, 97. • refining, 98. oil, siccative, 98. spirit, 93, 97. Roumania, petroleum in, 137. Russian oil, coke, 130. oils, composition of, 129. oil, statistics of, 125. refining, cost of, 124. Scottish shales, geology of, 19. results from, 43. variations in, 42. Servia, oil shale in, 159. Spirit, wood, 88. Starch, 182. Suint, 178. Sulphate, 28. prices of, 40. Sulphur and paraffins, 19. Summary, 183. Tar, gas producer, 80. hydrochloric, 80. wood, 81, 88. Tennessee, petroleum in, 119. Turkestan, petroleum in, 14 i. Trinidad, 144. Vaseline, 166. Yenezuela, petroleum in, 158. Yiscosities, 128. Weights and measures, 197. Wells, Galician, 137. Russian, 123. Wood, distillation of, 85. products from, 82. retorts for, 83, 85. Wool, 175. Wyoming, petroleum in, 119. HABKISON AND SONS, PB1NTEB3 IN OBDINAKr TO HEB MAJESTY, ST. MABTIN'S LANE, LONDON. L "si^BJrcT r "" ' -^ '^"T'-r^^ \