INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1950
(238)Thomas, R. M.,and Reynolds, H. C. (to StandardOil Development Co.), U. s. Patent 2,477,018(July26,1949). (239)Thomas, R. M., Young, D. W., and Calfee, J. D. (to Standard Oil Development Co.), Ibid., 2,468,523(April 26,1949). (240)Tong, L. K. J., and Kenyon, W. O., J . Am. Chem. SOC.,71, 1925 (1949). (241) Troyan, J. E., and Tucker, C. M., Zndiu Rubber WmZd, 121, 67 (1949). (242)Vanderbilt, B. N.,and Bascom, F. (to Standard Oil Development Co.), U.8.Patent 2,461,359(Feb. 8, 1949). (243)Walling, C., J. Am. C h . Soc., 71, 1930 (1949). (244)Walling, C.,and Mayo, F. R., Di8c~8siomFaraday SOC.,1947, No. 2,295. (245)Weber, K.H.(to Armstrong Cork Co.), U. S. Patent 2,476,341 (July 19, 1949). (246)Welch, L. M., Nelson, J. F., and Wilson, H. L., IWD.ENG. CHEM., 41,2834 (1949). (247)West, H.J. (to American Cyanamid Co.), U.S. Patent 2,476,127 (July 12,1949). (248)Whetstone, R. R. (to Shell Development Co.), Ibid., 2,476,936 (July 19,1949). (249)Whinfield, J. R.,and Dickson, J. T. (to E. I. du Pont de Nemours & Co.),Ibdd., 2,466,319(March 22,1949). 41,1564(1949). (250)White, L.M.,IND.ENQ.CHEM.,
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(251) Whitehouse, A. A. K., Ann. Rept8. SOC.Chem. Ind. Progreacl Applied Chm., 33,352 (1948). (252) Wiles, Q.T..el al., IND.ENQ.CHEM.,41, 1679 (1949). and Brauer, G. M., J. Polymer Sci,, 3,708(1948). (253) Wiley, R. H., (264) Willie, J. M.,IND.ENQ.CIIEM.,41, 2272 (1949). (256) Winding, C. C.,Ibid., 41,1900(1949). (256) Wolfe, W. D. (to Wingfoot Corp.), U. 9. Patent 2,491,433 (Dec. 13,1949). (267)Wolk, L. I. (to Phillips Petroleum Co.), Ibid., 2,458,456 (Jan. 4, 1949). (268)Young, D. W.,and Sparks, W. J. (to Standard Oil Develop ment Co.), Ibid., 2,462,703(Feb. 22,1949). (269)Ibid., 2,479,450(Aug. 16,1949). (260) Ziegler, K.,Kunstofe, 39,45 (1949). (261)Zinke, A. G.,Harms, F., and Pichelmayer, H., M m t s h . , 78, 311 (1948). (262) Zinke, A. G.,Ziegeuner, G., Weiss, G., and Wiesenberger, E., Zbid., 80,160 (1949). (263)Zoss, A. 0.(to General Aniline & Film Corp.), U. S. Patent 2,459,137(Jan. 11, 1949). (264)Zoss, A. O.,Hanford, W. E., and Schildknecht, C. E., IND. ENG.CHEM.,41,73 (1949). RECEIVED June 14, 1950.
Pyrolys Coal and S CHARLES H. PRIEN UNIVERSITY
OF DENVER, DENVER, COLO.
T
H E inclusive nature of the term “unit process” makes it desirable to extend a review of a given process-e.g., pyrolysisto those major corollary fields which are pertinent thereto. This policy, adopted in the two previous reviews on coal and shale, is continued in the current paper. The subheadings shown below are indioative of the related subject matter covered. As in the past, references to gasification, per se, have been omitted except where not clearly concerned with a unit process discussed elsewhere in the series. The period spanned by the references given is essentially that since June 1949, except for the normal lag encountered in the publication of papers and abstracts. The comments are necessarily restricted to the more important literature of the period.
COAL PYROLYSIS GENERAL
A number of reviews of coal pyrolysis have appeared during the past year. Included in these is a historical survey of the field from 1898 to date (99),and a description of modern carbonizing methods (91),both by Gaskill. Ludmila (166)gives a comparison of the processes for coking and semicoking of coal and lignite. Several books on coal carbonization have been published during the past year. The first of these, by Wilson and Wells ($63), ie an excellent compilation of modern coking practice, including coal preparation, oven operation, by-product chemical processing, and the economics and trends in the industry. A chapter on low temperature carbonization is included. Systems of coal classification, in Frame, England, and America, and E review of coal coking properties is given in a book on coal chemistry by Kreulen (140). A manual on the chemistry of brown coal has been published by Thau (846). The gas and coking industries of various countries have been evaluated. Trends in Great Britain are mentioned by Greenwood (IOO), Moignard ( I n ) ,Edington (YO),and others (11,118). The reserves of British coking coals are surveyed by Hicks (11$),
Edington (70), arid Moignard (171). The last-named author presents a comparative study of oven and retort design, and the factors governing tar composition. In discussing future research work on carbonization, i t is pointed out (16)that retort materials, thin-layer Carbonization of gas-making coals in controlled atmospheres, and the use of mechanical conveyer-type ovens are among the most fruitful lines of endeavor. The status of the German by-product coking industry at the end of 1948 has been noted (17), and both present and future problems and economics of the industry have been described by Reerink (806) and by Greenwood (101). Owing to the shortage of coking coals and the fluctuating price of by-products in Germany, it is necessary that increased attention be given, as shown by Plens (198), to complete gasification processes. A detailed statistical analysis of the French gas industry has been compiled (67). A review of the Polish coking industry has appeared (9), as have also historical reviews of the Belgium (40) and New South Wales (44) gas industries. In discussing the Canadian gas and coking industries it ia pointed out ($63)that American influence is dominant in oven design. An eight-point program for avoiding a repetition of the metallurgical coke shortage occurring in America during the war has been outlined by Fieldner (80). Production trends in the United States coking industry are discussed by De Carlo (61). Numerous references to underground gasification of coal, both in the United States and abroad, continue to appear. Attention i8 directed particularly to general reviews of American, Russian, Italian, and Belgian experiments by Bowring (.99), Ignatieff (118), and Krevelen (141), and to particular discussions of Russian and Italian work by Minchin (168) and Struck ($89). The second underground gasification experiment at Gorgas, Ala., is described by Dahlgren (66). Laboratory and field tests on underground electrocarbonization of coal, using controlled electrical heating, ere at present in progress at the University of Missouri ($1). A 500 to 600 B.t.u. off-gas suitable for heating or for synthetic fuel production is said to be produced.
1132
INDUSTRIAL AND ENGINEERING CHEMISTRY
COURTESY U.S. BUREAU OF MINES
V i e w of Shale Oil Refinery, Rifle, Colo. M E C H A N I S M , KINETICS, THERMOCHEMISTRY
In a review of recent research on the physico-chemical phenomena accompanying coal pyrolysis, containing some 30 references, Kipling (130) summarizes work on the chemical reactions resulting in devolatilization, the molecular rearrangements produced in the residual material, and the physical changes responsible for coke properties. The same author has presented data elsewhere (128)on the manner in which these physicochemical changes are related to the properties of activated carbon prepared from coal. He shows that addition of steam during carbonization has little effect on the active carbon subsequently prepared, although the coke obtained as intermediate is altered. The plastic and coking properties of bituminous coals are commonly thought to be due to the presence of fusible components. These constitutents are stated by Berkowitz (36)to be vastly less important than supposed. He suggests that softening and thermal swelling are due, respectively, instead to mobility of micelles and to the pore structure of the coal. It is proposed that the chemical constitution of coal, in so far as coking is concerned, is only of minor influence. An excellent series of papers describing physicochemical and petrographic research on coal, cokes, and graphite, particularly with reference to x-ray techniques, has been published by Mackowsky (168). Included is a comparison between the fine structures shown by these techniques, and those revealed by microscopic exa+nation. Further work on the fine structure of coal (86)and coke (86)is reported by Franklin, from studies on density made with helium, methanol, water,‘and n-hexane a t carbonizing temperatures of 300”to 1650’ C. It is shown that the solids function as molecular sieves, the effectiveness of the sieve in cokes being a function of pyrolysis temperature. Similar conclusions are reported by Bond and Maggs (37), using methanol and dibutyl phthalate as liquids.
Vol. 42, No. 9
As a result of a study of the chemistry of macromolecules Poncins (194) has related the thermal deterioration of these molecules to changes occurring during coking, and to the chemical constitution of the resulting tars and pitches. Rakovskii and Makarov have continued their investigation of the formation of coal tar during pyrolysis, as reported in the previous unit processes review (196). I n their latest paper (199) they show that catalytic processes on the coke surface, m well m a reaction of primary tar with the gaseous environment, are responsible for high temperature tar formation. From the viewpoint of kinetics it ie interesting to examine their statement that the actual pyrolysis reaction requires only some 5 seconds’ contact time for completion of coke and light oil formation, or perhaps even less. As a result of low-temperature oxidation studies on bituminous coals the Carnegie Coal Research Laboratory concludes (116) that modification in coking properties as a result of such oxidation is due to the destruction of those hydrogen-rich structures which are responsible for these properties, rather than to oxygen addition. By contrast, in a correlation of the coking properties of volatile coals--e.g., brown coals-Kardoss (124) claims that “oxygenated” ingredients do play a significant role. I n relating coal petrography to coke formation he postulates that ( a ) the presence of bitumen to serve as raw material for subsequently produced gas and adhesives, and ( b ) vitritous tissue partially to retain bituminous gases and precipitate constituents thereof are necessary requirements of such coals. The desulfurization of coal continues to be the object of research. Brewer and Ghosh report (43) an excellent study, using ammonia, hydrogen, and nitrogen gases &B sulfur-removing agents. Quantitative distribution of sulfur-containing compounds in the coke, tar, etc. were determined. An analytical procedure is presented. Later work by the same authors (96) shows that dry ammonia gas is most effective with high organic sulfur coals, in contrast to those in which pyritic sulfur predominates. Reasons are advanced. Eaton and oo-workers (68) have used 5 5 6 isotope to trace pyritic sulfur through a fullscale coking operation. This is a further report of work by these men mentioned in the previous review. Dehila of the analytical techniques are given. For a study of nitrogen oxide formation during coal pyrolysis see (193). The heat of coking during high temperature carbonization in vertical retorts has been calculated by Tettweiler (943) and compared with results by the Litterscheidt formula. Extensive data required in the computations are given in this series of papers, as applied to Ruhr coals. Heat transfer studies on continuous, intermittent, and batch proceeses applicable to the dry quenching of coke by inert gaees have been described by Brancker (41). I n this connection, data on the fluidized solids technique are given by Jolley (191). R A W MATERIALS AND PROPERTIES
Pretreatment of coal prior to pyrolysis is still a subject of increasing interest to the coking industry. Much greater precision has been introduced into the preparation processes during recent times, according to a review of 20 years of progress reported by Needham (180),who compares the various types of processes. The use of the float and sink method, of the Baum jig, etc., and comparative costs thereon have been deacribed in a review of developments between 1945 and 1949, by Reed (206). The theory and advantages of float and sink methods to cone, topfeed, and bottom-feed classifiers in the metallurgical coke industry are discussed (BO). The application of beneficiation procedures to Russian coals and methods for their evaluabion are described in a series of papers by Ulitskii (%9), Panchenko (184), Fomenko (81), and Toporkov (960). Four separation processes, and their effect on the coking properties of Lorraine including a crushing method. coals are compared by Loison (160), The effect of grinding on coke quality has also been studied for Russian coal8 (961). See also (64).
September 1950
INDUSTRIAL AND ENGINEERING CHEMISTRY
A report of preasures developed by a large number of British coals during carbonization, as tested in a Ruasell expansion oven, is given by Foxwell (88). The swelling properties of certain German bituminous coals were investigated by Ussar (864), who credits the effect to penetration of bitumen into the coal micelles. See also reference (867). The use of gas pressures developed during pyrolysis, as a criterion of coal swelling properties, is said (114)to yield excellent results. By determining the plastic properties of coals by the Gieseler plastometer, and by using correlative data from a movable-wall oven, Russell (816)has been able to correlate laboratory data with full-scale “coking property.” The use of dispersing agents, such as anthracene oil, to improve coal cokability, an extension of studies reported in both previous unit processes reviews (1.96),is described by Onusaitis (181). The development of a new experimental oven for studying coal blending is mentioned by Reed (909). Tests to determine the true density of coals have been outlined (86),as have experiments on their elehtrical resistance &B a function of temperature (4). The reserves of coking coals in the United States have been reviewed recently by Fieldner (79). Further data from the eurvey of the carbonizing properties of individual American coals are reported by Davis (69) and by Toenges (849). Additional data on Indian coals are given by Mene (166). Attention is directed to a series of 13 papers on the briquetting of American coals, as given at a 1949 conference a t the University of Wyoming (93),and to a bulletin of the National Resources Research Institute of this same university, on the briquetting of low-rank western coals, by Boley and Rice (36). HIGH TEMPERATURE CARBONIZATION
In an earlier article Stief stated (886)that combined power generation and coal carbonization in a single plant is economically desirable in Europe. A current paper by the same author (886) describes the production of a soft coke suitable for power generation, using the Stief procesa. Results obtained by carbonizing bituminous coal dust in an open hearth furnace fued with coke-oven gas are reported by Meier-Cortes (164). The production of 305 B.t.u. water-gas in the coke oven itself, by introducing superheated steam through 9 inlets close to the base of each oven wall, is mentioned by hlinchin (169). See also (58). Ramsburg (800) has reviewed United States results in pyrolyzing coal-oil mixtures of 0.25 to 3.5% oil content. The effect of blending high volatile coals with Pocahontas coal on the coke and by-products obtained upon coking has been studied by Reynolds (907). On the basis of preliminary data Sabatier concludes (216) that it is possible to manufacture satisfactory blast furnace coke from Lorraine coals. Current American developments on the application of fluidiaation to coal processing are noted in a recent review (10). For more information see also (147) and (88). A new electric process for carbonization of noncoking bituminous coal was presented in a paper before a 1949 United Nations resources conference (180). The use of approximately 5% blast furnace flue dust aa an additive in the high temperature coking of high volatile coal is the subject of a recent patent (49). The reduction of hydrocarbon cracking during pyrolysis is claimed in a British patent (880). LOW TEMPERANRE CARBONIZATION
Several reviews on low temperature carbonization have appeared during the period. Attention is directed particularly to a paper by Lesher (Ids), a book by Thau (247), and to discussions of recent German developments (14, 81I). Work on the low temperature distillation of coal under pressure, outlined in a previous review, has been continued at 3 atmospheres’ pressure. Yield of semicoke suitable for steel making was increaaed under these conditions (827). The
1733
Blummer %stage, low-high temperature process employing, initially, pressures of 20 to 30 atmospheres at 475” C., has been re-examined by Thau (946). An earlier series of articles on the pyrolysis of mixtures of Asiatic ooals in the presence of additives such as clay or activated carbon, as a step in the preparation of motor fuels, has just appeared (949). Further data on the destructive distillation of Swedish peat have been presented by Christiansson (68). These include studies which were done under vacuum and on a &‘greatly rotted sedge peat.” The new %million dollar low temperature plant of the Disco Company near Pittsburgh, which “pre-roasts” the high grade bituminous coal prior to devolatilization, has been described with accompanying flow sheet (166). See also (146). Wang mentions (966)the application of the fluidized solids technique to coal pyrolysis at low temperatures-e.g., 350’ C. German modifications in the Heliopore process, developed in America and using gas engine waste heat for coal distillation, are esamined by Thau (244). The addition of semicoke to coal to reduce agglomeration during coking has been patented (119). Frozen coal from the Norwegian mines at Spitsbergen disintegrates when thawed, but if crushed and briquetted, or if sulfite lye is added as a binder, it can be coked satisfactorily ( l a ) . For specific papers on the low temperature carbonization of the coals of North Bohemia (896),the Ruhr (111), Hungary (%$I), and Russia (98) the reader is referred to the literature citations here given. Data on Alberta subbituminous coal have been presented by Gregory (109). Low temperature distillation assays of Alaskan and selected western United States coals have been published by Parry, Goodman, and Comer (186),together with an interpretation and correlation of their data. OVEN OPERATION
Heat economy in the pyrolysis of coal continues to be of major concern. The reduction of heat losses during coke quenching is one means of improving the over-all economy. The use of dry cooling, therefore, continues to be of interest. An excellent review of this subject has been written by Foxwell (83). Further discussions of the advantages and disadvantages of dry cooling, as applied to British coking practice, may be found in (170) and (18). For references to German (6) and Swiss (96) practices, see the papers noted. Another source of heat economy exists in the fuel gases used for the ovens. An evaluation of various gases is given by Galocsy (89), who concludes that oxygen-blown producer gas is slightly superior to coke-oven gas. The effects of lower calorific value fuels on oven economy is examined thoroughly by Raschig ($01). An arrangement for automatically varying gas flow in inverse ratio to calorific value, such that the product of the two quantities is constant, has been described by Delassua (63). A critical review of various means of calculating the duration of the coking period from oven dimensions, etc. has been made by Veit (956). The influence of heating (coking) rate on coke properties has been studied on several Russian coals by Kustov (144). A study of gas pressures in coke ovens, using a battery of 8 ovens with double collecting mains, has been made by Hamilton ( 108),who recomrncnds 2 inches of water as maximum operating gage pressure. An analysis of wall pressures due to differential expansion in silica and semi-silica ovens has been presented (12). The use of a porous granular material to prevent wall injuries due to abrupt expansions late in the coking period, is the subject of a recent patent (195). For papers on the refractory materials used in oven construction, the reader is referred to (167, 190). A description of the evolution of the rectangular type of continuous vertical retort, and the operating characteristics thereof, is given in (46). A
INDUSTRIAL AND ENGINEERING CHEMISTRY
1734
Vol. 42, No. 9
A number of papers on waste disposal problems in the coking industry have appeared. See particularly (8, 29, 46, 73, 179). Rhodes has considered corrosion problems in the by-product plant and in oven auxiliaries (210). 'EOUIPMENT
COURTEBV U.B. BUREAU OF MlNFd
Gas Flow Shale Retort comparison of the performance of rectangular and Iatticeshaped bricks in oven regenerators may be found in a paper by Rakov (198). PRODUCTS AND BY-PRODUCTS
The control of by-products in coke-oven plants operating on various European coals, using either the Bauer or Schroth methods, is reviewed by Hofmeister (113). A technical and historical survey of the by-products of gas generation is given by Wunsch (266),including the present-day importance of cokeoven gas as a chemical raw material. Further data [see 1949 review (196)J on the conversion of coal gas to synthesis gas is presented by Sachsse (817). The separation of hydrogen by liquefaction, as practiced in Europe, is discussed by Guillaumeron (103). Hydrogen manufacture by catalytic hydrolysis is described in (33). Experimenb on the use of coke-oven gas to hydrogenate coal are detailed by Weller et al. (268). The production of ethylene glycol, oxide, and dichloride in Europe is reviewed by Ferrero (76). See also patents (8%9) and (298). Further work on the purification of coke-oven gas has been published. Catalytic removal of organic sulfur Is the subject of a recent British paper (191). The use of certain amine solutions for organic sulfur removal has been patented (2g4). The Staatmijnen-Otto and the autopurification processes are reviewed by Lorenzen (168). The use of water or ammonia liquor for scrubbing out hydrogen sulfide has been investigated further (74). Dry iron oxide removal of sulfur by a fluidized-solide technique has been developed (260). Water and naphthalene removal under pressure with Tetralin has been proposed ($31). The recovery of hydrogen cyanide is suggested by Klempt (131). Precooling of gas with water sprays is said to improve tar removal by subsequent electrostatic precipitation, through formation of a water-tar emulsion on the electrodes (133). The standard by-products of carbonization continue to receive attention, A review of the factors in ammonium sulfate production has appeared (84). Yields of this salt from various American coals have been tabulated and analyzed by Reynolds (208). The recovery of pyridine from various saturator liquors, in Great Britain, is compared by Ashmore (16). A review of the properties of l i g h h i l absorption oils is noted (138). A method for minimizing the thickening of these absorption oils during use involves partial bleed-off and steam distillation (168). A plant for the recovery of light oils by the use of activated carbon has been described by Fielder (78). See also (156).
In this section an attempt has been made to note a few of the more important papers and patents concerned with new and improved equipment for coal distillation. The listings are neceesarily incomplete. A survey of various types of gas retorts, their advantages and disadvantages, was presented at the 4th International Gae Union, London (27). The Carl Stilltall-Chamber coke oven is described by Bagley (30). See also a general article by the same author (31). A new oven design which eliminates cross-over flues has been mentioned ( 1 8 9 ) . For further mention of new oven designs see patents ( 6 7 , 1 6 2 , 1 8 6 , 2 6 1 ) . Davis has patented a new flue design, with built-in Venturi ports having high upflow resistance and low downflow pressure drop ( 6 8 ) . New ceramic fuel nozzles have been patented by Rueckel (214). An oven in which the checkerwork regenerators have been eliminated is mentioned by Melhuish (166). The poasible application of the new Rosenblads exchanger to oven practice has been considered (20). For patents on heat control in retorts see (2, 126). The following references on refractory materials are also of possible interest (1,106,190,228,837). The latest designs of British oven machinery are illustrated by Wood (284). A new charging device has been patented by Wilputte (262). For patents on oven doom and door handling machinery, see (3,146,183,821,866). A review of electrical equipment in the modern coke plant haa been compiled (76). A means for discharging coke into a stream of moving water has been patented by West (269). COKE PROPERTIES
Various papers in the period under review have been concerned with the propertiee of blast furnace cokes. Formulaa expreedng the physical characteristics of metallurgical coke have been deduced by Margarit (163), based on graphite content. See also (94). Possible factors responsible for the cohesion of coke have been examined by Delassus (64). The combustibility of blast furnace coke has been expressed as a mathematical function of various other properties in a Russian paper (49). Statistics on the chemical and physical characteristics of varioue European cokes have been tabulated ( 2 4 8 ) . Kipling has studied the retention of coal sulfur in coke and activated carbons produced therefrom (129). See also patent ( 1 6 7 ) . The manufacture of activated carbon by carbonization of compressed coal is described by Kramers (137). The colloidal nature of coke, as a function of temperature, has been examined by Franklin (84-86). The qualities of domestic coke are reviewed in a paper by Mott (178),and also in a publication of the Institute of Gas Engineers (209). Advances in the use of the downjet method of burning coke in gas producers have been reported by Ross (219). ANALYSIS AND TESflNG
A group of' articles dealing with the laboratory assay of coking coals have been issued during the past year. Mantel examine8 the Hulsbruch formula, based on laboratory data, in relation to plant yields (169). Mott assesses various British assay tests (177). An apparatus for assay of small samples (in the order of 2.5 grams) is said to yield unsatisfactory correlation with the standard Gray-King method (66). The relation of coal oxygen content to gas making properties has been the object of recent research (16). Tests for the coking propertiee of brown coals are discussed by Strohal (238).
S e p t e h r 1950
INDUSTRIAL AND ENGINEERING CHEMISTRY
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Rapid methods for the determination of ash sulfur in coal and coke are reported in two papers by Kurchatov (143),combustible sulfur in an article by Lifshits (I@), and total sulfur in a paper by Chernyi (48). The latter involves the use of metallic calcium. Difficulties in a modified Eschka method are listed (139). See also an article (106) and a book (107) by Hamaker. An excellent critical review of methods for the over-all analysis of coal and coke ash may be found in a late British publication (69). The conventional shatter and tumbler tests for coke are stated t o be inadequate (164). A new apparatus is presented in a Russian paper (61). See also (60). The reactivity of cokes is measured in a new A.S.T.M. apparatus which utilizes the “crossing-point” method (122). A modified test for coke reactivity to carbon dioxide employs adiabatic cooling (116)in a sample holder of low heat capqcity. True and apparent densities of coke, as measured by various solvents, have been examined by Franklin (86). The volume changes in semicokes subjected to coking at various temperatures were measured by a newly-devieed apparatus called a “contractometer” (71). The carbon disulfide content of light oil, usually determined by separation of the xanthate or by the copper oleate colorimetric method, has been analyzed by two new procedures reported by Kelempt (197)and Hansen (IO@, respectively.
OIL SHALE PYROLYSIS Shale carbonization has as its major objective the production of hydrocarbon mixtures (shale oil) for use as synthetic fuels. Liquid fuels from coal may employ pyrolysis as a first step, but for some other unit process-e.g., hydrogenation-oxidation is always subsequently employed in the over-all conversion process. GENERAL t
A comprehensive review of oil shale and shale oil has been compiled by Prien (197). Included are sections on the history, occurrence, and geologic origin of oil shale; the chemical constitution of the inorganic-, organic-, nitrogen-, sulfur-, and oxygen-containing components; a review of recovery methods, mechanism of pyrolysis, and thermal solution; and a brief discussion of mining, crushing, and refining methods. An excellent compilation of patents on oil shale has been completed by Klosky (I&@, as a sister publication to a similar compendium on shale oil by the same author [see 1949 review (195)I. Cattell has summarized recent United States Bureau of Mines experience on oil shale (47), as has also Harwick (110). A revised bibliography of the Bureau’s published research on shale has appeared (98). See also (232). The most complete summary of the present status of United States Bureau of Mines research on oil from oil shale, however, is to be found in the annual report of the Secretary of the Interior, on synthetic liquid fuels (84). Included are status reports on the mining and processing of shale and shale oil at the Rifle demonstration plant; and research on retorting, refining, thermal solution, chemical constitution, and by-product utilkation at the Laramie laboratories. The mining of Colorado shale is also discussed by Ertl (72)and others (90). A comparative evaluation of the economics of producing liquid fuels from shale, coal, natural gas, and petroleumis given by Roberts (212). The oil shales of individual areas of the world are discussed in a number of papers of the period. Assays on the shales of New Brunswick, originally reported by Ells, [see 1949 review (196)], are extended by Alcock (6,7) and Swinnerton (240)who also describe their method. The Swedish shale oil industry, ita processes and by-products, together with some cost data, is the subject of an article by Linden (149). Oil shale reserves of Brazil and production of shale oil there, together with its future possibilities, are outlined by Froes (8’7).United States assays of Brazilian deposiits are tabulated by Kraemer (135). The develop-
COURTESY Ud. BUREAU OF H l N U
Pillars of Shale, 60 Feet Square, in Underground Mine at Rifle, Colo. ment of fuels from the bituminous schisb of Argentina, and the possibility of by-product cement manufacture have been surveyed by Lombardozzi (161). The shale industry of Australia is noted by Mapstone (160). MECHANISM, KINETICS, THERMOCHEMISTRY
The United States Bureau of Mines has studied the mechanism of retorting of oil shale. They report (24)that no liquid products per se were evolved directly from the shale bed in their glase retort at any time, and conclude that this is evidence of an intermediate bitumen stage. This conclusion has been reached previously by others. Differential thermal analysis showed (24) that conversion of kerogen to oil ia an endothermic reaction. The characteristics of the organic matter were studied through degradation by hydrolysis. A list of organic products so obtained is given by the Bureau. The composition of the gasea from retorting, as a function of temperature, have been plotted. The rate constants for kerogen conversion to oil indicate that, kinetically, this reaction should occur during very much shorter time intervals than usually experienced in retorting practice. Heat requirements and heat transfcr rates for shales of varying richness, during retorting, are reported in the United States report ($4). As a result of a study of the pyrolysis of a bituminous schist, Picon concludes (187) that thiophene in shale oil ie formed from the pyrrole ring of chlorophyll, in which original imino groups have been replaced by sulfur as a result of bacterial action. A new classification of bitumens (89) is of possible interest in connection with oil shale. RETORTS AND RETORTING PROCESSES
The .Bureau of Mines has presented (24) various data on the retorting of United States shales in the report previously mentioned. Included is technical information on the operation of the modified N.T.U. retorts now in use, pilot plant studies on the gas-flow retort designed by the Bureau, and a description of a new %ounterflow retort” in which a hydraulic ram pushes the shale charge through the heated zone, countercurrent to a hot
1736
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
carrier gas. The effects of temperature, pressure, time, shale particle size, and retorting atmosphere (especially oxygen concentration) on the products obtained are under investigation. Additional details on the Union Oil retort mentioned in the last review, have been published by Reed and Berg (803). Application of the fluidized solids technique to Alberta bituminous aands is described by Gishler (97). The electrical carbonization of oil shale has been patented (134). A pilot plant layout for shale, by a German scientist, has been set forth in a publication of the Office of Technical Services (188). Swedish retorting practice, including underground gasification, has been reviewed by Demart (66). Borgkvist (38)describes experiments on the concentration of the bitumen in Swedish oil shale, in order to produce coke and simultaneously recover metallic constituents. The application of Swedish retorting methods to Colorado shales ia being tried (22). Delaroziere has sent the author a description (68) of a ‘‘double circulation” transverse gas-flow retort. Recycle gas a t 400” C. is passed a t right angles to the downward shale flow, across the lower half of a vertical retort, and thence passed in a similar manner across the upper half of the bed, being discharged a t 85 C. Shale sizes as small as 3 mm., and perhaps even 1 mm., can be used as feed. Oil yield is 97% of Fischer assay. For further details see a recent British patent (62). Further data on oil shale retorting may be found in patents (117, ZE?),and in a discussion of the pyrolysis of Serbian shale (183). For notes on water and waste disposal problems pertinent to the Green River shales, see a recent article by Savage (880). THERMAL EXTRACTION
Studies on the soluble matter in Green River oil shales have been summarized by Ferris (77), who states kerogen solubility to be an inverse function of particle size and gravity, and a direct function of time of exposure to solvent, temperature, and oil content. The soluble extract is also said to be a function of the compositions of the organic matter (kerogen) and of the solvent. The nature of these latter functions is not stated, however. PRODUCTS AND BY-PRODUCTS
The major product of oil shale pyrolysis is shale oil. I n addition there is obtained spent shale, shale gas, phenolic compounds, quinoline, pyridine, and thiophene homologs. Papers concerned with these materials are noted below. The shale oil refinery a t Rifle, Colo., is described briefly by Guthrie (104), Morris (176), and in (24). The latter reference outlines the problems involved in catalytic cracking, hydrogenation, visbreaking, and similar refinery operations. Refining processes developed by the Union Oil Company, which include preliminary coking and mild hydrogenation, are presented by Reed (204). A series of papers by Mora et al. are concerned with gasoline from shale oil. Included are studies on chemical treatment (1769, catalytic aromatization (l73), and various analytical methods (see below). The cost of diesel fuel from shale oil is predicted by Morris (176). The composition of the naphtha fraction from a Pumpherston-derived naphtha of Colorado shale oil is given by Ball ( W ) ,as a result of chromatographic studies using silica gel as adsorbant. Savage describes (219) a process for cracking shale oil by using spent shale as a cracking medium. Whether the effectiveness of this last-named process is due to the catalytic action of the inorganic matter, or to increased heat transfer area is not as yet known. Desulfohydrogenation of oil from an Italian shale, using molybdenum oxides and sulfides as catalysts, is mentioned by Salvi (818). The uBe of sulfuric acid in the desulfurization, and determination of thiophene homologs in a French shale oil has been given by Picon (188). Shale gas containing, after desulfurization, 70% butane and 30% propane is being marketed in Sweden (19). The use of
Vol. 42, No. 9
shale gas from Baltic shales for supplementing the gas supply of Leningrad has been reported ( 2 5 ) anew. The use of ohale tar bases, principally pyridine homologs, as stabilizers in Australian shale gasoline, by separation and reblending, is suggested by Mapetone (161). The oxidation of a Manchurian shale oil paraffin to fatty acids has been described (125). By-product chemical production from oil shale is discussed by Sherwood ( $ 2 5 ) . See also (94). ANALYSIS AND TESTING
Stanfield and Frost discuss (234) modifications in the Fischw assay of oil shales, as revised from a previous report [see 1948 review (f9S)l. A convenient method of estimating the oil yield of Colorado shales from specific gravity relationships, useful as a control test, is proposed by Frost (88). The determination of aromatics in Puertollano shale oil gasoline, by ultraviolet absorption, is outlined by Ysu (267, 268). The identification of conjugated dienes in the same gasoline, after fractionation, is explained by Mora (174). The use of chromatographic adsorption for shale oil distillates has been estended by Dineen et al. (66). The interference of nitrogen compounds in this technique and methods of separation are considered by Smith et al. ( 2 2 9 ) . The use of a liquid-air-cooled microscope substage for studying shale oil structures has been proposed ( 142). Mapstone devotes some space to a description of chemicnl control methods in shale processing, as utilized a t Glen Davis, Australia ( 160).
ACKNOWLEDGMENT The author desires to express his gratitude for the assistance given by Werner Schnackenberg, Institute of Industrial Research, University of Denver, in the collection of the numerous references for this review, and in checking the bibliographic citations and manuscript.
(1) (2)
LITERATURE CITED Aberg, K., Svenslca Guave-rksfwen.Arsbok, I, 17-42 (1948). Ackeren, J. van (to Koppers Co., Inc.), Brit. Patent 624,082
(3)
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(1949). (1949). (4) Agroskin, A. A., and Petrenko, I. G,, Zavodshaya Lab., 14, 80712 (1948). (5) Ahlers, W., Gas-u. Wasserfach, 91, No. 1, 2-10 (1950). (6) Alcock, F. J., Can. Dept. Mines Resources, BUT.Mines, No. 825, 9-10 (1943). (7) Ibid., pp. 11-18. (8) Anon., Chem. Eng., 56, No. 3, 96-106 (1949). (9) Anon., Coke and Gas, 10, 314 (1948). (10) Ibid., 11, 16-7, 26 (1949). (11) Ibid., p. 71. (12) Ibid., pp. 101-7. (13) Ibid.,p. 152. (14) Ibid., pp. 384-5. (15) Anon., Gus Times, 58, 285-6 (1949). (16) Ibid., 59, 176 (1949). (17) Ibid., 60, 306 (1949). (18) Anon., Gas World, 130, 1257-62, 1302-9 (1949). (19) Ibid., p. 1734. (20) Anon., Le Combustible, 1949, No. 3 4 ,4 M 1 . (21) Anon., Mining Congr. J.,35, No. 10, 57 (1949). (22) Anon., Oil Gas J . , 48, No. 11, 58 (1950). (23) Anon., Univ. w g o . , Nutl. Resources Research Inst., I?Lfornt. Circ. 3 (1949). (24) Anon., U.S. Bur. Mines, Rept. Invest. 4652 (1950). (25) Artyukhov, I. M., Ekon. Topliua, Za, 4, No. 4, 17-21 (1947). (26) Ashmore, S. A., and Thickins, D., Coke and Cas, 11, 307-8 (1949). (27) Association technique de l’industrie au g a l en France, preprint 4th Intern. Gas Union, London, I.G.U. No. 3, 1949. (28) Audas, F. O., and Imperial Chemical Industries, Ltd., Biit. Patent 631,551 (Nov. 4, 1949). (29) Badger, E. H. M., GUSW d d , 130, 2038-40, 2078-81 (1949); 131, 155-6 (1950).,
September 1950
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Brandon, G. E. (to Allied Chem. & Dye Corp.), U. 9. Patent 2,473,987 (1949). Brewer, R. E., and Ghosh, J. K., IND.ENG.CHEM.,41,2044-53 (1949). Brown, A. T.,Natural Gas Bull. Australia, 12, No. 5, 22-5 (1948). Bundy, K. N.,and Jordan, P. E., Savage Works J . , 21, 694-9 (1949). Burns, J., and Weston, F. R., Gas World, 130, 1966-70,2002-6 (1949). Cattell, R. A, J . Inat. PetroEeum, 35, 841-7 (1949). Chernyi, A. T., and Podoinikova, K. V., Zavodskuua Lab., 15, 1002-3 (1949). Chernyshev, D. M., Stul, 8,589-91 (1948). Chernyshev. D. M., and Brutcher, H.. Zavodekuua Lab., 14. 285-90 (1948). Chizhevskii, N. P., and Chernyshev, D. M., Stal, 8, 495-8 (1948). (52) Christiansson. B., Iva, 19,215-27 (1948); 20,119-28 (1949), (53) Compagnie g6n6rale de construction de fours, Brit. Patent 611,721 (1948). Czyzewski, M., and Byrtus, F., Prace Badawcze G h n e g o Inst. Met. i Odkw., 1949, 73-81. Dahlgren, E. G., Gas, 25, No. 4,40-1 (1949). Dancy, T. E., and DeJersey, N. J., Fuel, 28,109-13 (1949). David, E., Malissard, G., and Dutin, J., Fr. Patent 872,454 (June 10. 1942). Davis, G. A. (to Allied Chem. & Dye Corp.), U. S. Patent 2,488,175 (Nov. 15, 1949). Davis, J. D., U.S. Bur. Mines, Tech. Paper 711 (1949); 712 (1949); 720 (1949); 726 (1950). Davis, N. L.,Iron Steel Engr., 26, No. 3,7944 (1949). De Carlo, J. A,, and Corgan, J. A., U.S. Bur. Mines, Inform. Circ. 7504 (1949). Delaroziere, F., private communication; see also Brit. Patent 627,219 (Aug. 1949). Delassus, M., Compt. rend. 66th congr. aaaoc. tech, industr. gaz France, Paris, 1948, 258-62. Delassus, M., Georgiadis, C., and Montigny, P., Communic. 66th congr. aasoc. tech. industr. gaz France, 1949. Demart, P., Proc. Intern. Conf. Pure & Applied Chem. London, 1948, 249-55. Dineen, G. U.,et al., Anal. Chem., 22,867-76 (1950). Dury, R., J. usines gaz, 72, No. 12,261-3 (1948). Eatan, 8. E., Hyde, R. W., and Rood. M. H.. Anal. Chem.. 21. 1062-6 (1949). (69) Edgcombe, L. J., et al., Dept. Sci. Ind. Research (Brit.), Fuel Research Survey Paper 50 (1949). (70) Edington, M. D., Engineering, 168, &6 (1949). (71) Erkin, L. I., and Gorbunova, L. I., Zavodskuya Lab., 14,801-7 (1948). (72) Ertl, T., Mech. Eng., 71,478-80 (1949). (73) Ettinger, M. B., and Ruchhoft, C. C., IND.ENO,CHEM.,41, 1422-7 (1949). (74) Eymann, C., Gas-u. Wasserfach, 90, 505-12, 534-8, 668-70, 577-81 (1949). (75) Ferranti, M. de, Blast Furnace Steel Plant, 37, 1087-91 (1949). (76) Ferrero, P., Chem. Trade J., 124,726 (1949). (77) Ferris, B. J., Mines Mag. (Cob.), 38, No. 9, 19-22,B (1948). (78) Fielder, H. J., Gas World, 131,270-1,278 (1950). (79 Fieldner, A. C., U . S. Bur. Mines, Inform. Circ. 7559 (1950). (80f Fieldner, A. C., and Newman, L. L., Scientific Conference on Consenation and Utilization of Resources, Economics and Social Council, United Nations, Lake Success, E/Conf., 7/ sect./w. 183, 1949. (81) Fomenko, T. G., Stal. 8,1063-9 (1948). (82) Foxwell, G. E., Coke and Gau, 11,7-13 (1949). (83) Foxwell, G. E., Gas World,130,1886-93,1979-83 (1949). (54) Franklin, R. E., Bull. soc. chim. France, 1949, D53-4. (S5) Franklin, R. E.. Trans. Faraday SOC.,45,274-86 (1949).
1737
(86) Ibid., pp. 668-82. (87) Froes, A. S., Bull. Am. Asuoc. Petroleum Gaol., 33, 1590-9 (1949). (88) Frost, I. C., and Stanfield, K. E., Anal. Chem., 22, 491-2 (1950). , (89) Galocsy, Z., Schweiz. Ver. Gas-u. Wasser/ach. Monats-Bull., 29, 69-77 (1949). (90) Gardner, E. D., and Sipprcllc, E. M., Mining Eng., 1, No. 9 Mining Trans., 317-23 (1949). (91) Gaskill, M. S., Gas. J.,259,319-20,325 (1949). (92) Gaskill, M. S.,Gas Times, 60,96-8 (1949). (93) Gebler, I. V., Izvest. Aknd. Nauk S.S.S.R., Oldel, Tekh. .Vauk, 1948, 873-82. (94) Georgiadis, G., Compt. rend. 66th congr. aasoc. tech. industr. gaz France, Paris, 1948,389-97. (95) Ghosh, J. K., and Brewer, R. E., IND.ENQ.CHEM.,42, 1550 (1950). (96) Giesing, K., Gas-u. Wasserfach,91, No. 1, 11-3 (1950). (97) Gishler, P. E., Can. J.Research, 27F, 104-11 (1949). (98) Golumbic, N., et al., U . S. Bur. Mines, Inform. Circ. 7534 (1949). (99) Gothan, W., Erdol u. Kohle, 2, 173-5 (1949). (100) Greenwood,H. D., Gas World,131, No. 34125 Coking Sect., 2-10 (1950). (101) Greenwood, H. D., and Branson, W. R., Gas J., 259, 99-101 (1949). (102) Gregory, J., and McCulloch, A., IND.ENQ.C H ~ M41, . , 1003-11 (1949). (103) Guillaumeron, P., Chem. Eng., 56, No. 7, 105-10 (1949). (104) Guthrie, B., and Cameron, R., Petroleum (London), 13, 36-8 (1950). (105) Hachet, L.,Ind. cdram., 1948, No. 385,80. (106) Hamaker, J., Chem. Weekblad, 45,364-7 (1949). (107) Hamaker, J., Inat. vow Warmte-Econ, Gravenhuge, Rept. No. 8. (108) Hamilton, J., and Kennaway, T., Gas World, 130, No. 3377, Coking Sect. 47-61 (1949). (109) Haneen, H., Brennstof-Chem., 30,419-20 (1949). (110) Harwick, R., Oil Gas J . , 48, No. 49,75-6,88 (1949). (111) Heynen, H., Braunkoohlenarch.,56, 1-28 (1949). (112) Hicks, D., and Lee, G. W., Coke and Gas, 11,361-6 (1949). (113) Hofmeister, B., et al., Bergbau-Archiv., 80-95 (1947). (114) Hofsass, M., Gas J., 260,476 (1949). (115) Hou, H. L., and Orning, A. A. preprint, Division of Gas and Fuel Chemistry, 116th Meeting AMERICAN CHEMICAL SoCIETY,Atlantic City, N. J. (116) Howard, H. C., Bituminous CoalResearch, 8, No. 4,13 (1948). (117) Huff, L. C. (to Universal Oil Products Go.), U. S. Patent 2,463,693 (March 8, 1949). (118) Ignatieff. A., Tran. Can. Inst. Mininu Met., 52, (also in Can. Mining Met. Bull. 4511,599-603 (1949). (119) Institute of Gas Technology, Brit. Patent 632,155 (1949). (120) Jensen, O., Scientific Conference on Conservation and Utilization of Resources, Economics and Social Council, United Nations, Lake Success, E/Conf., 7/Sect./w. 226,1949. (121) Jolley, L. J., Fuel, 28, No. 5, 114-15 (1949). (122) Jonakin, J., et aZ., Am. SOC.Testing Materials, Proc., 48, 1269-89 (1948). (123) Jovanovic, S. L.,et al., Glusnick Khem. Drushtva Kraljeuine Jugoslav., 12,143-60 (1947). (124) Kardoss, E. S., Bdnydsz. Kohdsz. Lapok, 82, 173-8 (1949). (125) Kawai, S., and Morita, K., J . SOC.C h m . Ind. Japan, 44, 702-4 (1941). (126) Keeling, W. 0. (to Koppers Co., Inc.), Brit. Patent 616,258 (1949). (127) Kelempt, W., and Huck, G., Brennstof-Chem., 30, 319-21 (1949). (128) Kipling, J. J., Fuel, 29, No. 2, 42-7 (1950). (129) Ibid., No. 3, 62-3 (1950). (130) Kipling, J. J., SFience Progress, 37,657-69 (1949). (131) Klempt, W., Brennstof-Chem., 30, 148-58 (1949). (132) Klosky, S., U.S. Bur. Mines, Bull. 468 (1949). (133) Kolbe, F., Stahlu. Eisen, 69,552-4 (1949). (134) Koller, K., and Esztergaly, F., Brit. Patent 630,048 (1949). (135) Koppers Co., Inc., Brit. Patent 613,533 (1948). (136) Kraemer, A. J., U.S.Bur. Mines,Rept. Invest. 4655 (1950). (137) Kramers, W. J., and Pirani, M., Brit. Patent 623,764 (May 23, 1949). (138) Krasnodebski, K., and Mlynarski, A., Przqlad Gorniczy, 5, NO. 1, 21-7 (1949). (139) Kreulen, D . J. W., Chem. Weekblad, 45,76 (1949). (140) Kreulen, D. J. W., GasJ., 257, 188 (1949). (141) Krevelen, D. W. van, and Loon, W. van, Chem. Weekblad, 45, 233-45 (1949). (142) Kroger, C., and Hedicke, O., Brmnslof-Chem., 30, 347-56 (1949).
.-
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INDUSTRIAL AND E N G I N E E R I N G C H E M I S T R Y
(148) Kurchatov, BI. S.,dnnuaira u n w . Sofia, Facult6 phys-mat., Liwe 2,43,229-34,235-42 (194647). (144) Kustov, B. I., and Kopelovich, 1. h.,Stal, 8, 581-8 (1948). (145) Lavely, P. H., and KOPPCWCo., Inc., Brit. Patent 611,521 (1948). (146) Lesher, C. E., preprint, Divit;ion of Gas and Fuel Chemistry, 114th Meeting, A M E ~ I C ACHEWICAL N SOCIETY,St. Louis, Mo. (147) Leva, M. e t d . , IND.ENO.C H E M41, ~ , 1206-12 (1949). bifshits, M. M., and Minenko, 0.A,, Zavodskaya Lab., 15, 1000-2 (1949). Linden, H. E., World Oil, 129, No. 6, 213-20 (1949). Loison, Et., and Blanzat, A., Centre &des rscherches charbonnages France, note tech. No. 48, 12 (1948). Lombardozzi, U. P., and Schilling, C., Ezperintenta Mendoza, 1, 62-75 (1948). Lorenzen, G., Bwnnstoff-Chem.,30, 393-8 (1949). Ibid., PB. 430-1. Lowrv, H. H., and Epstein, B., Blast Furnace, Coke Oven, and R& Materials (Proc. C o d . ilni. Inst. Mining Met. Engrs.) 1948, 3-22. budmila, J., Paliva a voda, 27, 1-7 (1947). McBride, R. S., Chen. E'ng., 56, No. 6, 112-14 (1949). McIntire, F. L . , I r o n &; c'oal Trades Rev.,158, 1348 (1949). Mackowsky, M. T., BTennstof-Chem., 30, 44-60, 141-7, 218-25 (1949). Mantel, W., BrennsCof-Chem., 30, 385-91 (1949). I &. Proc., 16, 120-42 Mapstone, 6. E., Australian Chem. Inst. , (1949). Mapstone, G. E., Petroleum. Refiner, 28, No. 10, 111-13 (1949). Marecaux, P. (to SociBtB Anonyme Louvroil Montbard-Aulhoye), U. 6 . Patent 2,478,295 (1949). Margarit, M., Rev. ind. ?/ fabril ( M a d r i d ) , 4, No. 29, 78-85 (1949). Meier-CorteR, E., Stahl u.Eisen, 69, 476--80 (1949). Melhuish, H., et al., Brit. Patent 625,879 (1949). il/lene, P. S., and Pande, R. K., Quart. .T. Geol. M i a i n g Met. SOC. I n d i a , 19, 141-4 (1947). Miles, J., et al., Brit. Patent 620,588 (1949). Minchin, L. T., Gas World, 129, 931-2 (1948). Tbid., 130, No. 3381, Coking Sect., 73-7 (1949). Ministry Fuel and Power, Grea.t Britain, "Dry Cooling of Coke," London, The Ministry, October 1943. Moignard, L. A., Road T a r , 2, No. 4,3-8 (1948). Mora, A,, and Blasco, E., I . N . T . A . (Inst. nacl. t e m o l . aeronnut.) ( M u d r i d ) ,Comun. No. 4 (1944). Tbid., No. 8 (1945). (174) Ibid., No. 13 (1945). (175) Morris, H. B., and Gilbertson, 11. L,Diesel Progress, 15, No. 9, 42-3 (1949). (176) Morris, H. B., and Gilbertson, D. L., Petroleum Eng., 21C, No. 9, 26-32 (1949). (177) Mott, R. A., Gas W o r l d , 130, Coking Sect. 7-16: 91-9 (1949).
Vol. 42, No. 9
(178) Ibid., 131, No. 3420, Coking Sect., 25-30 (1950). (179) Murdoch, D. G., and Cuckney, M., Trans. Inst. Chem. Engrs. (London), 24, 90-101 (1946). (180) Needham, L. W., J . Inst. Fuel, 23,70-7 (1950). (181) Onusaitis, B. A., Zzvest. A k a d . N a u k S.S.S.R., Otdel. Tekh. N a u k , 1947, 907-11. Oppelt, W. H., U. S. Dept. Commerce, O T S Re@,, PBL 89704 (1946). Padgett, G., U. S. Patent 2,475,512 (1949). Panchenko, 8. I., Stal, 8, 397-403 (1948). Parry, V. F., et al., Quart. Colo. School Mines, 45, No. 2A, 13362 (1950). Peaudecerf, M., and Lassalle, P., Fr, Patent 872,551 (June 12, 1942). Picon, M., C a p t . rend., 227, 1381-2 (1948). Zbid., 228, 251-3 (1949). Pinckard, P. M., Steel, 126,No. 8, 96-9 (1950). Pirogov, A. A., et al., Ogneupory, 13,492-502 (1948). Plant, J. H. G., and Newling, W. B. S., Inst. Gas Engrs., Copyright Pub. 344/157 (1949). Plenz, F., Gas-u. Wasserjuch, 90, 441-7 (1949). Plotegher, F., J . usinesgaz, 1949, No. 3,5343; No. 4 , 7 9 4 3 . Poncins, P. de, Communic. 66th congr. assoc. tech. industr. gaa France. Paris. 1949. Powell, A. R. (to Koppere Co., Inc.), U. S. Patent 2,495,763 (Jan. 31, 1950). Prien, C. H., IND. ENQ.CEEM.,40, 1649-59 (1948); 41, 190614 (1949). Prien, C. H., preprint, Second Oil Shale and Cannel Coal Conference, Institute of Petroleum, Glasgow, July 3-7, 1950. Rakov, V. V., Stal, 8,870-3 (1948). Rakovskii, E. V., and Makarov, G. N., Zhur. Priklad. Khim.. 22, 400-8 (1949). Ramsburg, J. C., and McGurl, G. V., Rev.gbn. gaz, 71, No. 2, 50 (1949). Raschig, M., Gas-u. Wasserfach,90, No. 5,97-9 (1949). Reed, F. H., et al., Am. I n s t . M i n i n g Met. Engrs., Tech. Pub. 2491 (1948). Reed, H., and Berg, C., Mech. Eng., 71, 639-42 (1949). Reed, H., etal., Petroleum Processing, 4, 341 (1949). Reed, W., J. Inst. Fuel, 22,365-8 (1949). Reerink, W., Bergbau-Archiv., 9, 85 (1948). Reynolds, D. A., U.S. Bur. M i n e s , Rept. Invest. 4552 (1949). Reyzolds, D. A., and Wolfson, D. E., U.S. Bur. M i n e s , Rept. Invest. 4526 (1949). Rhead, T. F. E., and Pickering, E. T., I n s t . Gas Engrs., Copyright Pub. 343/156 (1949). Rhodes, E. O., Gas, 25, No. 12, 32-7 (1949). Rhodes, E. O., U.8. B u r . M i n e s , Inform. Circ. 7490 (1949). Roberts, G., Jr., and Schultz, P R., Petroleum Refiner, 29, 1048 (1950).
Underground Rooms in Shale Mine, Rifle, Colo.
September 1950
INDUSTRIAL AND ENGINEERING CHEMISTRY
Ross, F. F., and Sharpe, G. C. H., J . Inst. Fuel, 23,20-4 (1950). Rueckel, W. C. (to Koppers Co., Inc.), U. S. Patent 2,470,112 (1950).
Russell, C. C., and Perch, M., preprint, Prod. Chem. C o d . , Am. Gas Assoc. (May 23-5,1949). Sabatier, J., Scientific Conferenceon Conservation and Utilization of Resources, Economics and Social Council, United Nations, Lake Success, E/Conf., 7/sect./w. 321,1949. Sachsse, H., Chemie-Ing.-Tech., 21, 129-35 (1949). Salvi, G., Riv. cmbustibili, 3 , 369-82 (1949). Savage, J. W., Rocky Mt. Oil Reptr., 6, No. 16,6 (1949). Zbid., 7, No. 10, 29 (1950). Semet-Solvay Co., Brit. Patent 612,076 (1948). Shaw, J. A,, and Koppers Co., Inc., Brit. Patent 621,873 (1949).
Shaw, J. A. (to Koppers Co,, Inc.), U. 8. Patent 2,471,550 (May 31, 1949). Zbid., U. S. Patent 2,490,840 (Dec. 13,1949). Sherwood,P. H., Chem. Eng., 56, No. 9,99-101 (1949). Simek, B. G., and Ludmila, J., Paliva a voda, 29,33-8 (1949). Simek. B. G., et al., Ibid., 29, 97-100 (1949). Smelyanskii, I. S., and Tsigler, V. D., Ogneupory, 14, 9-21 (1949).
Smith, J. R., el ul., Anal. Chem., 22, 867-40 (1950). Smith, T. B., Brit. Patent 572,917 (Oct. 29,1945). Smoluchowski, K,, Gaz, Woda i Tech. Sanit., 23, 160-2 (1949). Sneddon, R., Petroleum Eng., 21C, No. 7, 36-7 (1949). Standard Oil Development Co., Brit. Patent 630,458 (1949). Stanfield, K. E., and Frost, I. C., U.S. Bur. Mines, Rept. Invest. 4477 _ _ . 11949) . I
Stief, F., G‘trs-u.Wusserfuch,89, 193-9 (1948). Ibid., 90, 403-10 (1949). Stott, V. H.. and Hilliard, A., Iron & Coal Trades Rev., 158,256 (1949). Strohal, D., Arhiv. Kem., 18,81-6 (1946). Struck, P., Qas-u. Wasserfach,91, 16-20 (1950). Swinnerton, A. A., Can. Depl. Mines Resources, BUT. Mines, No. 825,19-24 (1943) (published 1948). Szasz, O.,Bdnydss. Kohdsz. Lapok, 81,86-91 (1948). Takizawa, M., Bull. Znst. Phgs. Chem. Reaearch (Tokyo), 20, 920-34 (1941); 21,83-7,375-9,438-47,644-50(1942).
1739
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Pyrolytic a Decomposition of Hy .
VLADlMlR HAENSEL and MELVIN J STERBA UNIVERSAL OIL PRODUCTS COMPANY, RIVERSIDE, ILL.
I
N COMMON with the first two literature reviews (33, 34) of hydrocarbon decomposition reaotions, this summary includes a compilation and brief digest of material that has appeared in the literature during the year ending in May 1950. During this past year there have appeared important contributions to the explanation of the mechanism of catalytic cracking. The first commercial Platforming unit went on stream in 1949, and the chemistry of the process waa disclosed early in 1950. The petroleum refining industry has continued to expand and modernize its cracking facilities, and has made use of the graphic panel to compact the instrumentation of certain new installations. THERMAL CRACKING The literature of the past year suggests that most of the recent fundamental studies in thermal decomposition reactions have been concerned with reaction mechanisms, and that industrial developments are being directed toward the processing of heavy residual fractions, largely by methods which make coke and distillates as products. Partington, Stubbs, and Hinshelwood (67)have described the normal thermal decomposition of n-pentane as consisting of a
molecular rearrangement process and a chain reaction repressible by nitric oxide. Primary decomposition products, obtained in the presence of nitric oxide to suppress the chain reaction, indicate that the probabiKty of initial rupture at the C(2-3) linkage is about twice that at one of the C42-s) bonds. Furthermore, when the break occurs at the C(2-s) linkage, ethane and propylene are formed more frequently than ethylene and propane. The nature of the decomposition reactions of methane, ethane, and n-butane on an incandescent platinum filament at pressures of 10-6 mm. has been examined by Robertson (81) by the use of a mass spectrometer of high sensitivity. Ne concludes that the primary dissociation of methane on platinum at 1000” C. resulted in the formation of methyl radicals, but no methylene radicals could be detected. Ethane, propane, and butane were formed by radical recombination and hydrogen transfer. At 1050’ C., butane appeared to undergo a selective fission a t the central C-C bond because the main products were ethane and ethylene, no CShydrocarbons and only traces of methane being observed. This selective type of rupture was attributed to the catalytic effect of the platinum filament rather than to the nature of the butane molecule ihelf.
