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    10 views5 pages

    Eb11 CLTR

    Uploaded by

    singhgirendra20001523

    Copyright:

    © All Rights Reserved
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    COAL-TAR COAL-TAR, the black, vigcous, sometimes semi-solid, uid of peculiar smell, which is condensed together with aqueous “ gas iquor ” when the volatile products of the destructive distillation. ‘of coal are cooled down. It is also called “ gai-tar,” because it was formerly exclusively, and even now is mostly, obtained as a by-product in the manufacture of coal-gas, but the tar obtained from the modern coke-ovens, although not entirely identical with gas-tar, resembles it to such an extent that itis ‘worked up with the latter, without making any distinction in practice between the two kinds. Some descriptions of gas-tar Indeed differ very much more than coke-oven tar from pure coal-tar, viz. those which are formed when bituminous shale or other materials, considerably deviating in their nature from coal, are mixed with the latter for the purpose of obtaining gas of higher illuminating power. Tt may be generally said that for the purpose of tar-distllers the tar all the more valuable the less other materials than real coal have been used by the gas-maker. AMI these materials— bog-head shale, bituminous lignite and so forth—by destructive distillation yield more or less paraffinoid oils, which render the purification of the benzols very dificult and sometimes nearly impossible for the purposes of the manufacturer of coal-tar colours. ‘Neither too high nor too low a temperature should have been observed in gas-making in order to obtain a good quality of tar Since in recent times most gas retorts have been provided with heating arrangements based on the production of gaseous fuel from coke, which produce higher temperatures than direct fring and have proved a great economy in the process of gas-making itself, the tar has become of decidedly inferior quality for the purposes of the tar-distllers, and in particular yields much less benzol than formerly, Entirely different from gas-tar is the tar obtained as a by- product from those (Scottish) blast furnaces which are worked ‘with splint-coal. This tar contains very little aromatic hydro- carbons, and the phenols are of quite a different character from those obtained in the working of gas-tar. The same holds good of oil-gas tars and similar substances. These should not be worked up like gas-tars. ‘The ordinary yield of tar in the manufacture of coal-gas is between ¢ and 5% of the weight of the coal. Rather mote is obtained ‘when passing the gas through the apparatus of E. Pelouze and P. Audouin, where itis exposed to several shocks against solid surfaces, or by carrying on the process at the lowest possible temperature, as proposed by H. J. Davis, but this *carbonizing process ” can only pay under special circumstances, and is probably no longer in practical use. All coal-tars have a specific gravity above that of water, in ‘most cases between 4-12 and 1-20, but exceptionally up to 1°25, ‘The heavier tars contain less benzol than the lighter tars, and more “ fixed carbon,” which remains behind when the tars are ‘exhausted of benzol and is a decidedly objectionable constituent. AA tars also mechanically retain a certain quantity of water (or rather gasliquor), say, 4% on the average, which is very ‘obnoxious during the process of distillation, asitleads to bump- "and therefore ought to be previously removed by prolonged settling, preferably at a slightly elevated temperature, which rakes the tar more fuid. The water then rises to the top, and. is removed in the ordinary way or by special separators.” ‘The tar itself is a mixture of exceedingly complex character. ‘great bulk ofits constituents belongs to the class of aro- matic" hydrocarbons, of very diferent composition and degrees 595 of volatility, beginning with the simplest and most volatile, benzene (CyHf), and ending with an entirely indistinguishable mass of non-volatile bodies, which compose the pitch left behind in the tar-stills. The hydrocarbons mostly belong tothe benzene series C,H, the naphthalene series CyHa1e, and the an thracene’ and phenanthrene series CyHms. Small quantities of “fatty” (“aliphatic”) hydrocarbons are never absent, even, jn pure tars, and are found in considerable quantities when shales and similar matters have been mixed with the coal in the gas-retorts. They belong mostly to the paraffins Cys, and the olefines C,H. The “asphalt ” or soluble part ofthe pitch i also a mixture of hydrocarbons, of the formula C4Hay; even the “carbon,” left behind after treating the piteh with all possible solvents is never pure carbon, but contains a certain quantity of hydrogen, although less than any of the volatile and Soluble constituents of the tar. Besides the hydrocarbons, coal-tar contains about 2% of the simpler phenols C4Hay-,OH, the best known and most valuable ‘of which is the first of the Series, carbolic acid (@-.) CsH,OH, besides another interesting oxygenized substance, cumarone GH. ‘The-phenols, especially the carbolie acid, are among ‘the more valuable constituents of coal-tar. Numerous sulphur compounds also occur in coal-tar, some of which impart to it their peculiar nauseous smell, but they are of no technical importance or value. Still more numerous are the nitrogenated compounds contained in coal-tar, . Most of these are of a basic character, and belong to the pyridine and the quinoline series. Among these we find a somewhat considerable quantity of aniline, which, however, is never obtained from the tar for commercial purposes, as isolation in the pure state is too dificult. The pyridines are now mostly recovered from coal-tar, but only in the shape of a ‘mixture ofall members ofthe series which is principally employed for denaturing alcohol. Some of these nitrogenated compounds possess considerable antiseptic properties, but on the whole they are only considered as a contamination of the t Applications of Coal-Tar in the Crude State. ‘of coal-tar are employed for various purposes without submitting it to the process of distil Tt is mostly advisable to de- hydrate the taras much as possible for any one of its applications, and in some cases itis previously boiled in order to remove ‘more volatile constituents, ‘No preparation whatever is needed if the tar is to be used as fuel, either for heating the gxs-retorts or for other purposes. Tts heating-value is equal to the same weight of best coal, but it is very difficult to burn it completely without producing a ‘great deal of evil-smelling smoke. This drawback has been ‘overcome by employing the same means as have been found Suitable for the combustion of the heavy petroleum resides, called “ masut,” viz. converting the tar intoa fine spray by means ‘of steam or compressed air. When the gat-maker cannot con- ‘veniently or profitably dispose of his tar for other purposes, he burns it by the above means under his retorts Several processes have also been patented for producing ‘tuminating gas from tar, the most notable of which is the Dinsmore process. This process has been adversely criticized by very competent gas-makers, and no great success can be expected in this line. Coal-tar is very much employed for painting wood, iron, brick ‘work, or stone, aga preventive against the influence of weather ‘or the far more potent action of corrosive chemicals. This, of course, can be done only where appearance is no object, for instance in chemical works, where all kinds of erections and ‘apparatus are protected by this ¢heap kind of paint. Coal-tar should not be used for tarring the woodwork and ropes of ships, 1 purpose for which only wood:-tar has been found suitable. ‘One of the most considerable outlets for crude tar is in the manufacture of rogfing-fell.. This industry was introduced in Germany upwards of a hundred years ago, even before coal-tar ‘was available, and has reached a very large extension both in that country and in the United States, where most of the gas-tar seems to be devoted to this purpose. In the United Kingdom 596 it is much less extensive. For this manufacture a special fabric is made from pure woollen fibre, on rolls of about 3 ft. width and of considerable length. The'tar must be previously deby- dated, and is preferably deprived of its more volatile portio by heating in a still, It is heated in an iron pan to about oo ‘of 200" C.; the fabric is drawn through it by means of rollers which at the sume time squeeze out the excess of tar; on coming ‘out of these, the tarred felt is covered with a layer of sand on both sides by means of a self-acting apparatus; and is ultimately ‘wound round wooden rolls, in which state it is sent out into the trade, This roofing-fet is used asa cheap covering, bothby itself and asa grounding for tiles or slates. In the former case it must bbe kept in repair by repainting with tar from time to time, a top covering of sand of small gravel being put on after every coat of paint. Coal-tar is also empioyed for the manufacture of lamp-black, ‘This is done by burning the tar in ovens, connected with brick chambers in which the large quantity of soot, formed in this process, deposits before the gases escape through the chimney. ‘Numerous patents have been taken out for more efficiently collecting this soot. Most of it is employed without further manipulation for the manufacture of electric carbons, printing inks shoe-blacking, patent leather and so forth. A finer quality ‘of lamp-black, fee from oily and empyreumatic parts is obtained by calcining the soot in closed iron pots at a red heat. Distillation of Cool-Tar-—Muclmoreimaportant than all appli- ‘cations of crude coal-tar is the industry of separating its eo stituents from it in a more of less pure form by fractional dis- Aillation, mostly followed by purifyingprocesses, Most naturally this industry took its rise in Great Britain, where coal-gas was invented and made op a large scale before any other nation took it up, and up to this day both the manufacture of coal-gas and the distillation of the tar, obtained as a by-product thereof, are carried out on a march larger scale in that than in any other country. The first attempts in this line were made in 1815 by F.C, Accum, and in 1822 by Dr G. D. Longstaif and Dr Dalston. A‘ first the aim was simply to obtain “naphtha,” used in the manufacture of india-rubber goods, for burning in open lamps and for some descriptions of varnish; the great bulk of the tar remained behind and was used as fuel or burned for the purpose of obtaining lamp-black, tis not quite certain who first discovered in the coal-naphtha, the presence of benzene (g.2.), which had been isolated from cil-gas by M. Faraday as far back as 1825. John Leigh claims to have shown coal-tar benzene and nitro-benzene made from it at the British Association meeting held at Manchester in 1842, but the report of the mecting says nothing about it, and the ‘world in general learned the presence of benzene in coal-tar only from the independent discovery of A. W. Hofmann, published in 184, And it was most assuredly in Hofmann’s London laboratory that Charles Mansfeld worked out that method of fractional distillation of the coal-tar and of isolating the single hydrocarbons which laid the foundation of that industry. His patent, numbered 11,960 and dated November 11th, 1847, is the classical land-mark of it, About the same time, in 1846, Bronner, at Frankfort, brought his grease-remover ” into the trade, which consisted of the most volatile coal-tar oils, of course not separated into the pure hydrocarbons; be also sold water- white “creosote” and heavy taroils for pickling railway timbers, and used the remainder of the tar for the manufacture ‘of roofing-felt. The employment of heavy oils for pickling timber had already been patented in 1838 by John Bethell, and from this time onward the distillation of coal-tar seems to have heen developed in Great Britain on a larger scale, but the utiliza- tion of the light ells in the present manner naturally took place only after Sir W. H. Perkin, in 1856, discovered the first aniline colour which suddenly created a demand for benzene and its homologues. The isolation of carbolic acid from the heavier oils followed soon after; that of naphthalene, which takes place almost automatically, went on simultsneously, although the luses of this hydzocatbon for a long time remained much behind the quantities which are producible from coal-tar, until the COAL-TAR manufacture of synthetic indigo opened out a wide eld for i ‘The lat ofthe great ccoveres a that line was the preparation of alarin fom anthracene by C. Gracbe and C.. Lichermann, 1868, son followed by parens forts practical manufacture by Sir W. H. Perkin in England, and by Graebe, Liebermann thd il. Cao in Germany. "The preseat extension of the industry of coal-tar ditiling can be only very roughly estimate from the quantity of col tok produced in vavious counties Decidedly atthe head i Crest Britain, where about, yoos tone are produced per annum, Inost of Which probably tndp ts way into the tardies, wht in'Germany and the United States mach les gs-tar i Procliced anda very urge proportion oft is used for rocing-felt End other purposes "We shall now sive an out distlation ofa. Debyirtion~The frst opetion in coal dititing isthe seqerll f the mechantaty’Soted wansr” Some water fe chem Tak egauinee"Si the tases pana Ke, apt ts of cour Sando fo sou by mechoncal means, bat apt of ny da SheSbian' tof a rn cara hs ten ache Toe hae reroute Ver tlc vistus se ae et mined Shirai a and the woke ee eel by sole are shu wk hn! terre lcontnz eo etic ne ‘water nso thetap enamored Becca nc tar che sl Sal anda bevemoved hers Oe hea ed into the tart ig 1. T is Gol as sheet an apt tenght teas ote, i EMR en hong atthe en of the operation bote the fe Hae GO PBL othe aeceete and ses bag ine of the processes used in the —Tar Sul (sectional elevation)! traversed the holes 55 in the annular wall ebuile below the sti ftenace gases are fed around the stil by means ofthe fue whence they. pass to the chimney. Castiron necks are provided in the top for'the outlet of the vaponrs, for a manhole, supply-pipe, ther smometer pipe, Safety valve and fora and sleaniipis reaching ‘own to the boctom aud brsching out into number of distibuting he ilustrations in this article are from Prof. G. Lugge's Coal Tar and Ammonia, by permission of Friedrich Vieweg u. Sohn. COAL-TAR ‘arms. Near the top there is an overflow pipe which comes into ‘etion om ling the sil." in the lowest part of the botcom there i {funning-off valve or tap. In some cases (but only exceptionally) 4 perpendicular shaft ie provided, with horizontal arms, and chains izing down fom thew drag along the bottom forthe purpos of ewping it clean and of faciitating the eacape of the vapours. This arrangeaent is quite unecessary where the removal of the vapours [promoted by the injection of steam, but this steam must be\care~ fy dried belorehand, or, beter, tightly superheated, in order to eat explosions, which might be caused by theentry of tiquid water {ito the tar during the Iter stages of the work, when the tempera tse has arfen farabove the bellingpoine of water. ‘The steam acts th by stirring up the tar and by rapidly carcying off the vapours formed in distillation. he latter beet {t'even more thoroughly attained by’ the application ft vacuum, espetally during the later stage of di fliacon. For this purpose the receivers, in which the Figuids condensed in the cooler are collected, are con nected with an air pump or an ejector, by which a ‘cn of bout na hay atesplre, is made Which lowers the baling provete by about 86° Cur this hot mercly hastens the process, but alco produces an fimprovenient of the quality and yield of the products, ‘Sotaly of the aeraeng a, morgove wens ‘ralzogether prevents the formation of coke on the Su otom: which fotherwie very, rouble. ‘Most manufacturers emply ordinary stills” as described, A few of then have introduced continue fuely acting’ still, of which that constructed by Frederic Letinard fas probably found 2 wider apple on thag any of the oer” They al work oh rinciple of gradually heating the tar in several com Partments, following one ater the other. The fresh {Grieg ar one end and he pitch ro fom the other. ‘The. vapours formed in the. various Compartments are separately carsied away. and con- ‘lensed, yielding at one and the same time those products which are obtained in the ordinary still at {he dicent peri of the dation. “Although in theory this cgntinous process has great advantages over i ndiary esl of working he complica {om of the apparatus and praetieal dificulcics aisin in'the manipulation have deterred most manbiac: fgers rom introducing “Ph arcs are stn brickwork fn uch a manoey that there fs no oveg heating of thelr contents For this purpose the fre-grates placed a «good distance from the bottom er even covered ya brick arch 30 thatthe flame doesnot touch the stilrbottom ata tnd acts only indirectly, but the sides of the stil ate always dizeety face “he free nut note cared, co greter Beat than is necessary to provide againet the overheating of any part of the stl or protected inside by liquid tar, or, at the end of the Speraion, by ad pitch The outlet pe eal. pote Bainet Oveheating at a ays iting tern The cacy of taal ranges fom sf $0 tons hey hold aul about 10 tons, fn whieh case they can be worked ‘during one day. "The vapours coming from the still are condensed in coolers of various shapes; one of Which ie shown in figs 2 and 3. 'The eooling: pipes are best made of cast-iron, say ine wide inside and laid 59 fo have a continous fall owards tte bottom, "A steampipe (0) fe provided for heating the cooling water, which ie neceseary durin {ht later pare of the operation to. prevent the stopping up of the pipes Uy the solidification of the distillates. “A cock (@) allows Fic, 2-—Condensing Worm (Plan), scale 2 steam tobe injected into the condensing worm in order to clea any ‘The cooling pipe is at its lower end connected with receivers for the various distillates in auch a manner that by the turning of a coe the How of the distillates into the receivers can be changed at Ina suitable place provision is made for watching the colour, the speriég rave and the generat sppearanes of he dnlatce “At the end ot the tain of apparatus, and behind the vacuum pump for ejector, when one fs provided, there fs sometimes a purifier for the gases’ which ‘remain alter condensation? or these’ gases. are Carried back into the fee, in which case a Water-trap must be inter= Pa Te ot cn ting stlaion of the ar The number of fractions taken during the distillation varies from four to six Sometimes a fist fraction 1s taken as ire runsings,"up toa temperature of 105" Cin the still, 597 and a second fraction as" ight ol,” up to 210° C., but more usually, {hese two are not separated ia the ret disllacion, and the frst oF Eight oil” fraction then embraces everything which come over tun the drops no longer flost on, but show the same spesihe gravity as water, "The specie gravity of this fraction varies from O: oe The exe Faction the © mide ol or cable oof Spetinc gravity t-0n, boiling up to 240" Crit eontains moat of etfboliScid sh paphalee, he next feation othe beavy ll ‘or "creosote oll" of specie gravity tog. Where the nature ofthe ‘coals distilled for gas te such that the tar contains too litte anthra ‘gene to be economically recovered, the creosote~oll fraction i carried ‘ight to the end; but otherwise that is in most case, a last fraction Fic. 3.—Conden made at about ¢ anthracene oil” or" ag st seset the rene ‘During the light-oil period the fring must be performed ve cautiously, especially where the water has not been well rem fo\prevent bumping and boiling over. Te has been observed that, Sar fom theta "howe er incline mon fo ping over which cold'waer must be Rep rung thovgh the ooer. Phe dane once separates into water (gasliquor) and light oil, eating at the top. “Fowards the end of this traction the distillation seems t9 {eset ei of Increasing the fre, and gating nee ard nthe etl "This is eaused by the combined water splitting of from thetate nd phenol desing sight expnony in the tae {AP toon asthe epecitie graviey approaches 1, the supply of cold water to the cooler is atleast patty cut of, so that the temperature Site ate e"up fo 4 Co This neceay bea o rw sapthalene would crying outa pou up the pipet le steam ie injected into the still during this period no sty ‘ofthe pipes need be feared in any’ Ease, but this must Be done eaucioush ‘When the cartolic it has, passed over and, the temperature in the ail has risen to about 240°C {he tae ca ‘he ru fey aways hep the temperature inthe cooler at leat up to.4oe Ce The efeneote ol wich, how comes” over often SSharates # goad deal of “Solid naphthalene on “The lat fraction is,made, ether when the ther, span ges 270 Ce he rc ee iheaace Whae comes over now ig the anthreenea The wing may cease towards the end as the steam (with the vacuum) il Gal che work by itself “The water inthe cooler should now pprosch the bolting: point. he point of finishing the distillation is diferent in various ‘and for various objects Tt depends upon the fact whether Soff or ira plech fs wanted. "The later must be made where (thas t0 be SoU dea dlacance, as soft piteh cannot be casily eared during the ‘warmer ecason in failway trucks and not at all in shipa, where would Trin into 9 single lump. “Hard pitch fe algo always made where as Inch anthracene as posible f fo be abtained. Far hard pitch the

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