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
September 1948
(115) Rainard, L. W., I n d i a Rubber W o r l d , 114, 67 (1946). (116) Rice, 0. K., and Sickman, D. F., J . Am. Chem. Soc., 57, 1384 (1935). (117) Rohrs, W., Staudinger, IT., and Vieweg, R., “Fortschritte der (118) (119) (120) (121) (122) (123)
Chemie, Physik, und Technologie der makromolekularen Stoffe,” Munich, J. F. Lehmanns Verlag, 1943. Rudd, H. W., Paint M a n u f . , 17, No. 3, 72 (1947). Sawdon, W. A . , Petroleum Engr., 15, No. 8 , 162 (1944). Scheiber, J., “Chemie und Technologie der kilnstlichen Harze,” Stuttgart, Wissenschaftlische Verlagsgesellschaft, 1943. Schulz, G. V., Naturwissenschaften, 27, 659 (1939). Schulz, G. V., 2. Elektrochem., 47, 618, 265 (1947). Schulz, G. V., and Blaschke, F., 2. phvsik. Chem., B51, 75
(1942). (124) Shreve, It. N., “Chemical Process Industries,” New York, McGraw-Hill Book Co., 1947. (125) Simonds, H. R., and Ellis, C., “Handbook of Plastics,” New York, D. Van Nostrand Co., 1943. (126) Simpson, W., J . SOC.Chem. I n d . (London),65, 107 (1946). (127) Sittenfield, M., Chem. Eng..,54, No. 12, 129 (1947). (128) Skeist, I., J . Am. Chcm. Xoc., 68, 1781 (1946). (129) Smythe, L. E., J . Phys. & co7loid Chem., 51, 369 (1947). ENG.CHEM.,3 9 , 2 1 0 (1947). (130) Starkweather, H. W., elal., IND. (131) Staudi:,ger, H., “Die hoohmolekularen organisohen Verbindungan, Berlin, Julius Springer, 1932. (132) Staudinger, H., Trans. Faraday SOC.,3 2 , 9 7 (1936). (133) Staudinger, H.. andFrost, W., Ber., 68, 2351 (1935).
(134) (135) (136) (137)
1649
Steegmuller,M., Plastiques, 1, 11,47 (1943). Stockmayer, W. H., J . Chem. Phys., 1 1 , 4 5 (1943). Stockmayer, W. H., and Jacobson, H., Ibid., p. 393. Swain, C. G., and Bartlett, P. D., J. Am. Chem. Soc., 68, 2381
(1946). (138) Taylor, H. S., and Jones, W. H., IbJd., 52, 1111 (1930). (139) Thomas, R. M., Sparks, W. J., Frolich, P. K., and Muller-Cunradi, M., J . Am. Chem. SOC.,62,276 (1940). (140) Twiss, S. B., (ed.) “Advancing Fronts in Chemistry, Vol. I, High Polymers,” New York, Reinhold Publishing Corp., 1945. (141) Vandenberg, E. J., and Hulse, G. E., Chem. Ind., 61, 607 (1947). (142) Vesterdal, H. G . , U. S.Patent 2,397,301 (March 26, 1946). (143) Wall, F. T., J.Am. Chem. Soc., 63, 1862 (1941). (144) Ibid., 66, 2050 (1944). (145) Walling, C., Ibid., 67, 441 (1945). (146) Walling, C., and Briggs, E. R., Ibid., p. 1774. (147) Williams,G., J . Chem. Soc., 1940, p. 775. (148) Winding, C. C., IND. ENG.CHEM.,37, 1203 (1945). (149) Winding, C. C., and Hasche, R. L , “Plastics, Theory and Practice,’‘ New York, McGraw-Hi11 Book Co., 1947. (150) Youker, M. A,, Chem. Eng. Progress, 43, No 8 , 3 9 1 (Aug. 1947). (151) Yurzhenko, A. I., and Kolechkova, &Compt. I., rend. acad. sci., U.R.S.S., 47, 348 (1945). RECEIVED June 10, 1948.
Pyrolysis of Coal and Shale CHARLES H. PRIEN’ UNIVERSITY OF
COLORADO, B O U L D E R , COLO.
A
LTHOUGH this review is primarily concerned with coal and shale pyrolysis-its mechanism and practice-in the interest of completeness the survey was extended to those allied subjects which are of concomitant concern to those interested in this field. Accordingly, an attempt was made to include not only references to the. high and low temperature carbonization of coal and the retorting of oil shale, their mechanisms, kinetics, and application, but also to cover related s‘ubjects such as raw materials, products and by-product characteristics and properties, coke oven equipment and improvements, and coke analysis and testing. The shale review includes papers on shale properties, shale oil characteristics, retort design, and briefly, thermal extraction. References to gasification, where not concerned clearly with oxidation, hydrogenation, or some other unit process, also are appended. The majority of references to recent high pressure gasification processes, subbituminous and lignite gasification and underground gasification have been deleted. The voluminous literature of the period covered, some 1000 separate papers, has been reduced necessarily for inclusion in this review. Two abstracting services in the fuel and allied fields have been instituted in the past several years. The first of these is Fuel Abstracts (95). Published since 1925 for its own use only by the British Fuel Research Board, it has been issued monthly since 1947, for public distribution. The second publication is Synthetic Fuels Abstracts, a bimonthly service of the U.S.Bureau of Mines ($10) begun in 1948; it contains pertinent sections on coal carbonization, oil shale, etc. Mention must be made also of the Annual Report of Research and Technologic Work on Coal, U. S. Bureau of Mines, and of the bibliographies of the Department of ZPresentaddress, Agricultural Industry Service, BOTRA, Shanghai, China.
Commerce, Office of Technical Services, the latter on World War
I1 enemy industry. COAL PYROLYSIS The appearance, in 1945, of the two-volume work on the Chemibtry of Coal Utilization (194), with its individual monographs on coal carbonization, pyrolysis rates and yields, coal pretreatment, coke properties, gaseous constituents, carbonization products and by-products, has furnished a n excellent survey of the literature on coal pyrolysis through the year 1940. I n the following pages, therefore, an attempt has been made t o complete the picture by compiling a resume of advances in this field from 1941 to date. GENERAL
The history of coke making from the 17th century t o modern times has been traced in a recent address (218). The specific historical development of the German coal carbonization industry, annotated with some 111 references, is reviewed for the last 60-year period, by Lorenzen (195). The French coke industry is described by Georges (125). Progress in British industrial fuel practice over the past 25 years is summarized by Sarjant (268) and by Sorley (286). As noted in these papers and elsewhere (25, 44,167, 501), recent years have seen the distinction between the gas and coking industries become progressively weaker, especially in Europe. The original division was primarily one of markets; the gas industry concentrated on lighting and industrial and domestic fuel, the coking industry on metallurgical coke. Present trends are toward the increased production of readily combustible coke (86, 106) and to the adaptation of complete gasification processes de-
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INDUSTRIAL AND ENGINEERING CHEMISTRY
VOl. 13, No. 9
COURTESY
Mine Yard a n d Shale Outcrop, U.
S. Bureau
of Mines,
signed to avoid thc double process of carbonization plus the watergas reaction (113, 343, 301). The latter processes, initiated in Germany (308), require considerable further research prior to coinriiercialiaation. Kuinerous investigations in this field are in An cxcellen t rcvicn. of foreign commercial and suhcomrnci~ialgas making processcs, proposcd American processes, and othcrs, with flow sheets and operating data has been prepared rcceritly by the Institute of Gas Technology (6). \Vartinre progiws in t,he carbonization of coal in the United States iriclutlod (2)8)introduction of new methods in n3ining practicc and mecliariical cleaning, additional research on adaptable coal blends, and considerable iiiiproveiiicnt in the mechanical and elw trical equipnieu t for roal and cokc handling. Much progress \TILS made in secui,iiig greater uniformity of product through suitable blending practicc and mole adequate control of the bulk density of the oven charge. German rcsearch and advances in coal carbonization technology arc described in a reccnt report by Lon-ry ( 1 9 Y ) , on the basis of data accumulated by the Solids Fuels Mission to Germany. Comparisoiis with practice in the Unitcd States have been inade by Hendriclis ( 1 4 6 ) . Specific discussion of the wartime utilization of the low grade fuels of the Ruln., including dq-ing, blending, briquetting, and oven operation has been published ( 2 6 ) . British activities during the war years, and future tre:ids are given in ai1 excellent reviex by King (1701, and in papers by s LIcFayden (ROI), Phillipson (%?do),Foxxell (114):E d \ ~ a r d (103), and others (la,169). The blackout precautions required during air raids are of passing historical interest ( 3 9 ) . M E C H A N I S M , KINETICS, THERMOCHEMISTRY
An excellent book on the physicochemical phenoiilena occurring in carbonization and their relation to coke properties was published in 1942 (895). Included are discussions of heats of carbonization, rates of evolution of products, heat transfer effects in
Oil Shale
Demonstration Plant, RiFle,
u . s.
BUREAU OF MlNEl
Colo.
various zones of a coking oven, coking processes in mixed blends and a detailed description of coal and coke properties. A systematic study of the pyrolysis of coal a t temperatures between 340 ' and 900' C. has been reported in a series of papers by Gillet et al. (130, 131). Progressive losses of carbon, hydrogen, oxygen, and various groups, as functions of temperature are reported for carbonization in an atmosphere of nitrogen. Coniparative studies given for pyrolysis in a stream of hydrogen indicate little change in thcsc results. Stepwise carbonization of a wries of coals of increasing volatile matter content is dcscribed. In a detailed analy9is of thc thcriiial treatment, of coal Kremscr (181) discusses the theoretical aspects of: the softening point of the petrographic coniponcnts; relation bet\?-een liquid product, tar yields, and composition; and various analytical assay methods. Furnaces, products, and t,ypes of heating are surveyed also as to their interdepericlencc. Bennett (43) and Cannon ( 7 4 ) nicntivn a method for following changes in coal during carbonization by determixing the amount of internal surfacc change a,; selected stages, as denoted by heats of wetting Jyith methanol. Both heats of wetting and elcctrical coiiduct,ivity lyrere employed in a series of Russian studies on pyrolysis ( 2 2 8 ) a t 320" to 1000" C. Plastic deforiiiation was recorded simultaneously at the ion-er tempcraturcs. The roles of time and temperature v-erc investigated a t equal rates of heating and cooling. I t is stated that electrical conductivity of coke is neither metallic nor ionic. T h e difficulties in following carbonization reactions by nieaw of expansion pressure, plasticity, swelling, and gas evolution arc reviewed in a papcr by Studemund (as/,). I n a detailed explanation of the mechanism of carbonization of coal (63) it is proposed that highly unsaturated products of coal decomposition a t 350" to 550' C. pass in fine streams through the pores of the primary coke, vhich has attained 450' to 1000" C. Through decomposit,iori these products proclucc hydyogen,
September 1948
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
methane, carbon oxides, and carbon. The latter, by surface deposition, converts the yoft primary coke to hard, high temperature coke. Gas cracking is limited by contact time in the hot zone. On the basis of these postulations the requirements for producing the most reactive type of coke are enumerated, and experimental evidence is presented. Fuchs (120) has outlined a theory of coal pyrolysis on the basis of thermodynamic considerations and kinetics. H e postulates that aliphatic C-C bonds, C-H bonds, and aromatic C-C linkages are severed successively, in the order given, and that oxygencontaining and other heterocyclic groups follow, as the temperature approaches 700" C. The radicals so liberated subsequently decompose to the nitrogen bases, phenols, and other familiar end products of coal pyrolysis. The participation of phenols in the formation of the hydrocarbon end products has been sxperimentally disproved (221). Dehydrogenation of high molecular weight hydroaromatic ring systems to aromatic, with a resulting decrease of the C-C bond distances as pyrolysis proceeds has been shown by Ruston (166). Agreement with portions of the above can be found in an earlier paper (63),which postulates hydrocarbon formation by initial steam distillation of aliphatic compounds, followed by conversion to aromatics by reaction with hot low grade gases from near the oven walls. A series of studies on the stepwise, fractional carbonization of a wide variety of substances, including coal, has been reported by Cobb et al. (69, 81, 213) for temperatures up to 1200' C. Following wide deviations in the preliminary stages up to 600" C., a regular sequence of evolution of gaseous products was shown for the carbonization of all substances thereafter, and rearrangement of solid residues into the familiar hexagonal carbon network of graphite. Descriptions of gas components and the results of x-ray examination are discussed in detail. Increased attention has been given to the role of sulfur during thermal decomposition of coal. Contrary to earlier results (167) of work with peat, Keppeler reports (166) that sulfur does not necessarily concentrate in the peat coke; the major effect of carbonization is reduction of volatile sulfur in the coke. Smith conducted a series of tests on pyritic sulfur decomposition in coal and noted the effects of temperature and pressure on the formation of sulfide, organic sulfur, and gaseous sulfur compounds (284). The distribution of sulfur among coke, tar, liquor, and gaseous products of carbonization a t different retorting rates and temperatures is described by Mandlekar (103). An interesting study of pyrolysis mechanism and the influence of sulfur has been reported by Berkovitch (48), who carbonized coal with successively increasing quantities of admixed sulfur. It is claimed that internaI structural changes are directly correlated with quantities of gaseous decomposition product? (a weakness of the heat of wetting method) in this way. Coke properties are discussed. The occurrence of fluorine in coal, its determination, and its removal during pyrolysis have been reported in a series of papers by Crossley (85). The oxides of nitrogen formed in retorting coal between 600' and 1200' C. have been determined by Plotegher (241). The relation of carbonizing properties of coals to their.chemica1 and colloidal structure has been studied (189, 161) and correlated with certain polymeric properties (cross linkages, surface, etc). Structural changes during depolymerization have been postulated (189). Petrographic properties and their influence on coking are discussed by Kuznetsov (184), Gillet (129),Krevelen (182), Olbricht (.826), and Kinney (172). Close connection betweLn spore and algae content and tar yield has been shown (226). Xethane yields apparently are related t o the transluscent humic matter present (172). The effects of compression of finely divided coal under 10,000 kg. per square em. on subsequent high and low temperature carbonization properties have been reported (302). Decreased tar
1651
yields are noted, as well 8s a redistribution of sulfur forms. A theory on the fusion of coke and compression effects thereon has been given (267). The usual theories on the chemistry and mechanism of coking, and their relation to the plastic and swelling properties of bituminous coking coals have been reviewed in a comprehensive study by Brewer (61). The kinetics of the saturation of coal layers by organic liquids and the relation of natural gradient angle of coal charges to physicochemical properties are presented in a recent Russian study (6). Gerasimov correlates these physicochemical properties with a so-called hydrocarbon bond index and other calculated quantities (197), as a basis for fuel classification. .Mention also should be made of the use of shock cooling of vertical retort charges, as a means of examining the mechanism of carbonization occurring therein (139,309). A calorimetric study of heat consumption during semicoking a t 500" C., using the mixture method, has been reported ( I @ ) , and the relation of thermal changes in thin coal layers to coke cracks and brickwork pressures was investigated (306). A number of papers on the theoretical aspects of heat transfer in solids are of interest in connection with coal pyrolysis. Brinkley (65)recently has derived expressions for heat exchange between a fluid and a porous solid generating heat. Unsteady-state heat conduction in solids having thermal properties which vary appreciably with temperature has been analyzed by Fyres (191). Temperature distribution in heated charcoal beds through which air is passing has been subjected to mathematical treatment by Arthur (99). A related paper, on heat transfer to layers of nonspherical nonuniform particles by hot gases, has recently appeared (79). Radiation heat transfer studies in coke oven heating flues are reported by Schlapfer ($70). The result of thermal conductivity experiments on coal are described (117). The basic problems of temperature measurement within a coke oven have been discussed by Heaton (l43), who recorded retort temperatures a t various selected positions within the retort and near the walls, and by Sosman (987) in connection with techniques of radiation pyrometry in the oven and on the pusheci coke. In connection with fluid flow studies applicable t o coal pyrolysis, it is pertinent to mention an important paper detailing the effect of particle size, bed temperature, and gas properties on gas flow through beds of coke (14.9). The result of coke sponge on gas flow in the oven has been noted (64). A theoretical study on the packing and flow of particles, useful in relation to fuelhandling problems in pyrolysis, has just appeared ( 6 7 ) . A W MATERIALS AND PROPERTIES
An excellent book on the preparation of coal has recently been. published (215). A discussion of the application of various pretreating processes to coke oven charges has been presented by Lessing (192). Typical American practice in preparing coal for coking is described by Potter (241). In this connection also, a recent patent is of interest (245). The U. S. Bureau of Mines also has made active progress in this field, as noted in its annual reports. Particular attention is called to the results of a recent paper on the effects of storage of caking and coking properties of coals (172). A 16 to 1 range in durability of coking power h reported for the fifteen coal beds sampled. The desirable chemical and physical properties of coals used for carbonization and the test methods available for determination of coking suitability have been discussed by Davis (88). The behavior of various classes of coals on carbonization has been (18, 258). I n this described in numerous papers-particularly regard attention is called especially to the Bureau of MinesAmerican Gas Association Survey of the carbonizing propertis of American coals (90, 2.56, 516) which now includes some 90 different beds. Bibliographies of papers on specific samples tested after 1944 are available (107). RBsum6s of work on
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INDUSTRIAL AND E N G I N E E R I N G CHEMISTRY
coals of the western Cnited Statcs have been published (252, $48,854). The use of anthracite fines for by-product coke has been examined (80, 280). The plastic characteristics of United States bituminous coking coals and their correlation with chemical and physical propert,ies and petrographic composition in the ranges used commercially alone or as blends have been investigated by Brewer (60, 6 1 ) . The relat'ion of physical properties of cokes and plasticity indexes from Davis and Gieseler plastometers to proximate analyses of coals has been studied by Lowry (195, 196). Swelling properties are reported in papers by Brewer (61), Frey (116, 116), and Adelsberger (1). The latter study was made using the Asbach automatic swelling apparatus. Frey (11@ reports that the total swelling period of a bituminous coal is a quadratic function of the width of the carbonizing chamber, and can be calculated froin a single swelling-pressure determination. A thermodynamic analysis of the swelling pressures of coal, v4th derived formulas, has been made (119). Inorganic compounds and their influence on the behavior of coals and cokes are reviewed by Arthur (50). The effect of water content on the coking process is noted by Blecher (58); of bulk weight of t'he coal, by Agroslrin ( 4 ); and of resin content, by Davis (89). A pretreatment of bituminous coals with sulfuric acid a t 90" to 250" C., followed by briquetting and carbonizing, k said to permit an increase in the rate of processing (514). HIGH TEMPERATURE C A R B O N I Z A T I O N
Accounts of standard American by-product cokiiig pi act ice and research activities therein have been given recently ( 2 1 , 1-94). The performance of coke ovens and the types of cai bonising plants installed in gas works have been compared ( 1 6 ) , and the factors of importance in coke preparation in the latter industry-for example, reactivity, coke grading, bulk density-are reviewed (122). The effect of the type of oven on the piopcrtics of the coke is the subject of a British publication ( I S ) . A continuous carbonization p1 ocess designed foi both high and low temperature carbonization of Utah bituminous coal is i eady for commercial adaptation (76). Other combination high and low temperature processes also have been described, including the fieters process (166) for metallurgical coke or synthetic aiithiacite, and a method proposed by Spencer (288). The increased coke demands of the war yeais ievived interest in the once predominant beehive coking process ( 1 6 5 ) . The Bureau of llines has published the results of an experimental studv conducted on a beehive oven (876). The fluidized-solids technique of contacting gases and solids (1641, with its improved temperature control, better heat transfer, and higher reaction rates is receiving increased attention as a potential new technique of carbonization (160, 256, 290, 303). Another unusual iechnique is the so-called Heliopore carbonization process, which utilizes the internal combustion engine waste heat (exhaust gases) to carbonize coal or lignite. Relatively low temperatures, approximately 1300" F., are attained in the retort. A detailed experimental investigation of the method is reported (108). The use of coals with low ash content in the manufacture of highly reactive gas cokes, in Great Britain, has been described (17). Alkali activation of high temperature coke before and after carbonization, with sodium carbonate, etc., is revicwed by Askey (52). The results of carbonizing coal sprayed with heavy oil are discussed by AIayfield (208),and of washing coal n i t h gasoline prior t o carbonization, by Agroskin (3). A bibliography on the electrical carbonization of coal, covering the period 1900 to 1940, has recently been published (295). L O W TEMPERATURE C A R B O N I Z A T I O N
A number of excellent reviews of low temperature carbonization processes have appeared during the past 7 years. The most recent is that of Georges (126), which gives a critical historical,
Vol. 40, No. 9
economic, and technological survey of British, French, Belgian, and German methods, with recommendations. The staius of German low temperature coking and the characteristics of coke, tars, and motor fuels obtained therefrom is described by Demann (Qd),and others ($0, 92, 265,$97, 298). Coke properties in particular are surveyed by Thau (297) who also reviews four methods, two involving externally heated and two internally heated ovens, which have evolved from research during the 20-year period 1922 to 1042 (298). British low temperature retorts have been examined (289),and the activities of the British fuel industry explained (ROO). I n a review of Japanese lon- temperature processes (263) it is stated that most' of the operations were of previar German dcsign. A survey of the production of peat coke and it,s by-products has been given ( I N ) , as well as of lignites (190, 233). The KruppLurgi process, with operating details, designs, and cost data is described in a Bureau of Mines publication ($71) and elsewhere ( 1 1 , 199,214). The Lurgi-Spiilgas direct heating carbonization of coal briquets and weakly coking coals has been explained ($14). Processes used for the cooling and aging of low temperature coke in a number of German plants are noted (8); these use brown coal as fuel. Primary tar and light oil yields obtained from some 79 hmerican coals representing 10 ranks have been tabulated and discussed in a recent report ($24). The effect of the method of pyrolysis on the properties and yields of light oil and tar from brown coal has been reviewed by Jahn (169). Recent developments in tar acids and other by-product recoveries has been mentioned by Bristow ( 6 4 ) . The addition of mineral additives t o highly agglutinating coals prior to l o y teinperat,ure carbonization has been patented (191). A discussion of the addition of sodium carbonate, barium oxide, calcium oxide, ferrous sulfate, and salts of fatty acids to lignite and brown coal and their effect on lo^ temperature pyrolysis products, part'icularly tars, has been given by Jappelt (161). OVEN
OPERATION
The question of fuel economy and the utilization of waste heat in coal pyrolysis continues to be a paramount problem. A review of the subject by the British Coal Utilization Research Association summarizes the situation (104) a t present. Discussions of the subject by Mason (6O4),Hall ( I @ ) , and Harrison ( 1 4 1 ) ,and more recently by Finlayon (110) also are of interest. Over-all heat balances and efficiencies of coke ovens, continuous and intermittent vertical ret,orts, and horizontal retorts have been analyzed by Pexton (239). Comparative data and improvcments in operation are discussed for the several typed. A suggested method for defining and calculating the fuel efficiency of a coke-oven battery has been presented by hfetcalf (210). Particular considerations of the heating of Koppers-Becker coke ovens have been noted by Rueckel (264). A major problem in over-all fuel efficiency of the ovens is found in t,he quenching of the coke. Processes of dry quenching, with heat recovery, have continued to be investigated. The bunker, chamber, and five-tube types of dry-cooling plants are described in a recent paper (1.47j. h rccent' S'iTiss installation in yhich dumped coke is cooled from 1000" to 300" C. by an inert gas has been reported (148). A description of the British process a t the Dagenham plant of the Ford Motor Company has been given (856). Details and diagrams of a German plant are noted in (28%). An interesting use of colloidal suspensions, such as coal viashery waste waters, to reduce visibility of quenching operations or glowing coke piles in wartime has been patented ($60). The proper control of bulk densities in by-product coke oven4 has been reported in t,mo recent papers (186, 279). An all-dry coal charge is shown to produce excessively high bulk densities; the effect of moisture is great in thc lower ranges and results in nonuniform operation and possible oven damage. Oil added t o coal is shown to decrease t h e bulk density of dry coal and increase
September 1948
INDUSTRIAL AND ENGINEERING CHEMISTRY
that of wet coal. The influence of water content of coal also is discussed by Blecher (67) and others (151, and of hydrocarbon additions (gasoline os anthracene oil) by Bgroskin (8). A review of British coking practice with dangerously swelling coals of low ash content and the use of laboratory tests to predict and prevent oven damage in their coking has been presented (37).
1653
(137); it includes their utility as fertilizers, disinfectants, fungicides and fumigants, preservatives, food dyes, etc. The differences between gas works and coke-oven plant by-product recovery operations have been compared (299). The economic position of coke in modern-day industry is discussed by Voskuil (307). Particular attention to foundry coke
COURTESY U.
Shale Oil Retorts of the
E. BUREAU OF MINES
U. S. Bureau of Mines, Oil Shale Demonstration Plant, Rifle, Colo., with Shale Cliffs in Background
The measurement of pressure changes in a coke oven by a gas filtration process through the walls has been described ( 2 ) . Chamber wall temperatures and their influence on types and yields of hydrocarbons were investigated by Grobner (136). A prewar study on the effect of oven free (cracking) space on gas yields from horizontal retorts is reported (171). Experiences with alkali attack on vertical retort refractories over a 17-month period are detailed by Green (135). Further work here may be found in a report of the Gas Research Board of Britain (124). An account of results of spraying reheated coke, a t 150" C., with sodium carbonate solutions is given by Askey (31). PRODUCTS AND &-PRODUCTS
Several reviews of by-product recovery processes have appeared in the past few years (211, 250, 257), detailing advances in equipment and methods for the recovery of ammonia, phenols, light oils, hydrocarbon gases, sulfur, tar acids and bases, and creosote. The economics of the entire by-products field also has been discussed (73, 227), and a survey of the applications of primary and derived chemical products to the chemical industry has been made (71). It is pointed out that information on product costs under expanded uses are sorely needed if these materials are to find wider sales to the chemicals industry. Agricultural uses of coal products are enumerated in an excellent article by Guy
production and standards therefor has been given by Mobley (216). The thermal decomposition of light oils, particularly benzene and toluene, in the oven, with consequent decrease in yields has been receiving increased attention. It is reported that below 600" C. the loss of these two aromatics is 5 to 6%, and at 800' C. toluene decomposition may be as high as 50y0 (178). Prevention of these losses by the use of roof channels (132) and countercurrent cooling with distillation vapors ($20, $661) has been proposed. Employment of azeotropic distillation in the separation of hydrocarbon types from coal light oils, a practice in petroleum refining, has been studied by Coulson (82). Increased interest has been shown in liquefaction processes for the separation of coke-oven gas into its major constituents (144, 315). Ethylene recovery by this method is described in detail by Shuftan (675),who claims that economical ethylene production is possible where a t least 8,500,000 cubic feet of coke-oven gas per day are available. Experiences with the storage of coke-oven gas in natural-gas sandstone strata after removal of vapor-phase gum is reported in a paper by Bircher (65). Operating efficiencies of 97 to 99.8% are quoted. Wartime developments in the production of crude, concentrated mnmonia liquor in five different types of plants are compared by Bell (48). Improvements in the indirect process of
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
ammonium sulfate manufacture have been described (212). Koppers, Inc., has recently patented a process of animonia recovery involving passing coke-oven gas into a saturator containing dilute sulfuric acid; the sulfate precipitates from the supersaturated solution ( 9 ) . The removal of discoloring ime purities (argon sulfite, etc.) from saturator liquor by addition of a slightly alkaline creosote emulsion has been proposed (51). The Mellon Institute has developed a method of using waste pickle liquor (sulfate) to recover ammonia (155). Waste disposal problems in the gas and coke industries have been summarized by Gollmar (153) and Coxon (83), with particular emphasis on sulfur and phenol recovery. Modern sulfur removal methods from both coke oven (188) and domestic fuel gas (244) are reported. The phenolsolvan process of phenol recovery, which employs a mixture of esters of various higher aliphatic alcohols is examined in several papers (96, 261). The use of tritolyl phosphate is discussed by Just (163); and use of benzene wash oil, by Rosendahl (262). EQUIPMENT
The patent literature of the period under review contains numerous new proposals and designs for modifications in procedure and equipnicnt for coal pyrolysis and accessory apparatus therefor. hTo attempt has been made to evaluate this voluminous source material because of time limitations. In the f o l l o ~ ~ i nparag graphs, hon-ever, the more significant articles summarizing ne\\equipment and improvements have been surveyed. As pointed out by Wilputte (31%)changes in coke-oven design have tended toward thicker oven tops, better location of charging openings, the use of reversible compensat,ing mains, and mechanical charging of the coals. The greater fuel economy of the underjet system of flue heating is now recognized. Rcsearch on increasing flame length for rich fuels is in progress. Automatic proportioning of lean gas and air and their introduction in stages in the flues are among recent developments. The use of the Beiman main to increase by-product recovery is discussed (58)in a review of design trends, which also includes a niention of selfsealing doors, top flue location, and recent improvements in Otto oven design. Developments in Wilputte, Simon-Carves, and Xoppers-Decker ovens are noted by Craddock (84). The latter type also is discussed in (98). Experience n-ith Kest vertical ovens has been noted (22). Factors influencing regenerator design have been evaluated in an article by Finlayson (111). An examination of coniinon causes of failures in coke-oven parts, together with suggestions for their correction and prevention, is given in an excellent paper by Owen (830). Tapered ovens 11 inches wide a t the bottom and 7 inches wide at the top, for use in low temperature carbonization, have been developed in Great Britain ( % S I ) ,as has also a neTv xorm estractor for removing coke from the continuous Glover-West retorts C77). The properties of refractories used in coal carbonization and their failure due to attack by slag and alkalies are reviewed by Heaton (142). Metallic aluminum coatings applied in situ to reduce chemical action are under investigation ( 2 4 ) . Silica brick linings used in ovens for a similar purpose and changes in their composition with extended use are noted by Icora (177). Xew silica-lined oven designs have been proposed (257,238). COKE PROPERTIES
The properties of metallurgical cokes, their measurement, and their relation to blast furnace practice have been enumerated and evaluated in a number of publications (197, ZOO', 265). The literature on foundry cokes has been reviewed by Krause (180); also (116). A comprehensive analysis of the combustion characteristics of coke has been made by AIaycrs (206). Physical
Vol. 40, No. 9
properties of 25 cokes prepared under the Bureau of MinesAmerican Gas Association test program (previously mentioned) by carbonization a t 800" C. and 43 cokes from experiments a t 900 O C. have been summarized and compared (855). The density and porosity of experimental and commercial cokes have been measured with helium, Tvater, and mercury by Smith and €Iowarci (285).
Thermal properties of coke and the effect of moisture content thereon have ,been determined (118). Thermal conductivity, specific heat, and thermometric conductivity are included in the discussion. The use of electrical conductivity of coke as a n index t o its quality has been suggested by results recently obt,ained (222). The ash struct,ure of coke prepared v-ith and without breeze blending has been described from work on thin sections (273). Formulas for converting coke analysis to a mineral matter-free basis are reviexwl by Alott (219). The effect of acids and alkalies of coke properties has been studied by the U. S. Bureau of Mines (62) and others (283). Changes in reactivity n-ith various mineral additives-ferric, calcium, and magnesium oxides-are reporkd. Wood charcoal. slaked lime, and iron ore additives and their effects on initial burning point and ash fusibility have been noted (183). ANALYSIS AND TESTING
Korlring details of the various laborary scale carbonization assay methods have been reviewed and compared in a comprehensive paper by Brown (S6j ; this includes difi'erential cracking and constant cracking types employing tube retorts and, as further subdivided, those mcthods which heat the coal in successive portions, and those m-hich heat the vhole charge; also (163). A laboratory procedure involving an iron retort containing several trays has been proposed for low temperature carbonization (14.9, as has also a short method employing a simple glass retort (3OOj. The problems of isolating t.he effects of individual variables in large scale pyrolysis tcsts have been notcd ( 1 9 ) . An experimental, sole-t,ype oven electrically heated for coking studies and the correlation ol results therefrom with commercial practice has been described (249). A new engineering design of an oxperimental oven said better t o reproduce the various behavior charact,eristics deve!oped duriiig carbonization has been proposed (296). A laboratory test for dekermining the free-sivelling index of coals 11-hose coke buttons s h o no ~ relation t o t,he standard profiles has been reported ( 2 7 7 ) . Brewer has reviewed the entiye problem of the plastic and s i d l i n g properties of coking coals and the testing methods therefor (61). For a specific review of mcthods for determining coal plasticity see (154). A carbonization pressure gage utilizing c:hanges in gas pressure n-ithin a flexible metal envelope has been clevelopeJ ( 2 0 7 ) . Expansion characteristics of coal have been measured in a new apparatus involving a porcelain tube heated a t opposite ends by tn.0 intergeared movable ovens (1 ea). The reactivit,y of coke in a water vapor-nit,rogen environment, as a means of evaluating its suitability for watey gas and producer ga.s manufacture has been studied by Delassus (93). An apparatus for exaniining coke reactivity to carbon dioxide, which is based on following conversion to carbon monoxide, has been proposed (152'). h reactivity test involving following the rate of temperature rise of the sample in air, oxygen, or nitrogen is discussed by Orning (229). The -k.S.T.M., the cone, and the dropped-coal laboratory methods of duplicating the bulk density characteristics of coal charges in practice, their application, and precision have been compared ( 3 4 ) . A new two-stage, two-furnace method of detcrmining ash in coal and coke, said to correct for errors due to sulfur, has been proposed (223).
September 1948
INDUSTRIAL AND ENGINEERING CHEMISTRY
CUURTESY COLORADO FUEL AND IRON CORPORATIOI
Pushing the Coke at Koppers By-product Coke Oven Battery, Colorado Fuel end Iron Corp., Pueblo, Colo.
OIL SHALE PYROLYSIS While the pyrolysis of coal is conducted for the primary purpose of producing netallurgical coke or fuel coke for conversion to gaseous fuel, shale carbonization up to the present time has had as its objective the direct recovery of petroleumlike hydrocarbons (shale oil). Syntheses of liquid fuels from coal may utilize pyrolysis as a first step, but the actual hydrocarbon-producing step is a subsequent operation usually involving some unit process other than pyrolysis-namely, hydrogenation, oxidation, etc. The distinction is admittedly one of classification, but is believed helpful as a guide in studying commercial developments of the two raw materials, and is, as well, a pertinent illustration of the application of the unit process concept. GENERAL
No over-all compilation of the literature on oil shale has apCHEXICAL peared since the publication of the early AMERICAN SOCIETY monograph on the subject by McBee (ZOZ), and a book by the Institute of Petroleum (London) (67). The U. S. Bureau of Mines is in process of collecting all patents pertaining to oil shale and its products, and recently has issued a progress report of its activities hereto (17’8). A bibliography of the bureau’s own investigations on oil shale up to 1945 has been published ( l o g ) , as well as an incomplete compilation of important articles
on synthetic liquid fuels, including shale, over the past 25 years
(V. Little active work on oil shale has been conducted in the United States since about 1927. However, interest in the field was revived some 3 years ago as a result of Public Law 290, 78th Congress. A comprehensive program of government-sponsored research has been instituted (36, 179) into all phases of tho oil shale program as a result of funds so provided. Progress t o date has been heartening (IO, ,974 and undoubtedly will stimulate more private research in this field as well. I n contrast to the above, European interest in the pyrolysis of shale has continued during the past several decades, and is the source of the majority of papers which have appeared in the period under review. Attention is directed particularly t o recent r6sumks of modern methods of treating shale in use abroad (70, 225, 292). For comprehensive discussions of the world’s oil shales, their occurrence, exploitation, and modern retorting techniques, the reader is referred to a review by Cadman (70) and to (69, 175). Descriptions of the oil shale activities of individual countries have been published for selected areas, in the 6-year period under review. The bituminous shale oil industry of France, the classification and petrography nf the deposits there, and a description of the
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INDUSTRIAL AND ENGINEERING CHEMISTRY
retorts used are given in a recent book (49), and in a publication by the Department of Commerce, Office of Technical Services ( 1 1 2 ) . The latter examines the carbonizing methods used for the rich deposits at Autun and St. Hillaire in central France for their potential value for application to United States shales. Of the four commercial plants in operation, only one retort design, the externally heated, horizontal, rotary Petit furnace a t Grenoble is believed of interest for American oil shales (see also 305). The present status of the Swedish shale oil industry has been surveyed by Egloff (105). Pour processes are examined in detail: the Bergh continuous process using an externally heated retort, the Roclresholm process, which employs a modified Pumpherston retort originally developed in Scotland; a tunnel retorting process using two horizontal, circular furnaces containing special periorated steel cars; and the Ljunstrom process, which distills the shale in situ by electrically heating the shale bed. The Russian shale oil industry ]$-asrecently surveyed by Klosky (17.4) from an examination of some 300 papers in the Russian literature. The data collected refer primarily to prewar developments. Retort designs for both gasification (modified Estonian) and distillation are described. An excellent microfilm of these papers, which are somewhat difficult of access, is available from the Library of Congress, Washington, D. C. Estonian progress, a review of the deposits, their petrography, retorting methods, products, and uses have been reported by Anwander (28). British and Amcrican activitics in oil shale and shale oil have been noted by Williams (811) and others (41, 133). Three processes for oil shale retorting were developed in Germany during the war. These include: the hleier-Grolman vertical retorting method (the spent shale from this process is used for cement manufacture) ; the Meiler process; and a modified underground distillation process similar to underground coal gasification processes (235). M E C H A N I S M , KINETICS, THERMOCHEMISTRY
Little fundamental u ork has been done in the past few years on the chcmical constitution of oil shale or the mechanisms involved in its thermal decomposition. Probably the most iiotei\ orthy paper on constitution of the period is one by Cane (73) on the chemical structure of iiustralian torbanite kerogen (the bitumen of shale). This author concludes that kerogen is a degraded polymer of unsaturated fatty acids, such as eleostearic acid, n hich undergoes decarboxylation on pyrolysis. As support for his theory he points to the close resemblance between the physical properties of certain plastic polymers and kerogen. By contrast, recent work by Down and Himus (70) suggests that certain kerogens possess a benzenoid structure. I n a discussion of the thermochemical decomposition of Australian shale, Cane proposes the following mechanism (72): Sulfur and oxygen compounds are the first to decompose, producing carbon dioxide, hydrogen sulfide, and water. This is followed by endothermic cracking of hydrocarbon residues (259). The kinetics of the thermal decomposition of oil shale were recently investigated by Zarenibo (516))who found two maxima in the rate of evolution curve for volatile matter from a Russian shale, and similar maxima in the rate of water evolution curve. This is believed by the author to be additional evidence of the stagewise decomposition of kerogen long postulated. Primary cracking of bulk organic matter, followed by secondary cracking, a t grain interfaces, of the original fragments was deduced from later experimenh by the same investigator. I n an extremely lucid treatment of the problems involved in determining the composition of oil shale kerogen, Himus concludes that little evidence exists of chemical combination between organic matter and shale inorganic matter, with the possible exception that small portions of iron may form an essential part of the kerogen structure (150). This is somewhat contrary to earlier
Vol. 40, No. 9
work by Carlson (76). EIoivever, a recent study by Barlot ( 3 6 ) , in which calcium carbonate was removed from a calcareous shale prior to pyrolysis, indicated definite resulting effects on pyrolytic product yields. The quantity of oil obtained was decreased, and phenol production increased. A contribution to subsequent deductions on the mechanism of shale decomposition may eventually be found in the results of a complete analysis of the gas from shale pyrolysis, as obtained b>Bergh (46). RETORTS AND RETORTING PROCESSES
Numerous methods for retorting oil shale have been proposed in the past. All are dependent on providing a suitable apparatus in which the shale rock can be heated to 350Oto 500" C. and volatile products removed with as little cracking due t o contact with h o t surfaces as possible. Heat economy has been a major consideration in design. Two major types have been cvolved-externally heated retorts and internally heated retorts. These categories, with modification, have continued to characterize designs proposed during the period under review. A partial survey of the patent literature on retort design has been given by Klosky (173), who summarizes the many different designs for eduction of oil from shale. As stated, the British have continued to rely on vertical retorts of the Pumpherston type; the Swedes have developed tunnel kilns and more recently underground retorting; the Estonians have developed t,unnel and rotary retorts; the French have modified existing designs; and the Australians have modified the Pumpherston retort and have pioneered in the development of a retort designed to operate under pressure (158, 259). The German approach up to the war was mainly chemical; interest was shown in thermal extraction of shale. A4summary of European retort' designs developed during the war, with diagrams, may be found in (225). Recent Australian patents on shale rctort>inginclude a means for pyrolyzing the shale by direct contact with a molten metal bath (176). A similar process was developed to the pilot plant stage in Germany (235). Other designs are described in Bustralian patents (3.9). d French patent describes a pyrolysis process involving pasting the shale with a heavy oil and retorting in a three-zone vertical furnace (138). The Sx-edish Bergh process, in which shale is distilled from a large number of small cast iron retorts grouped into a furnace block continuously controlled, has been explained by the inventor (45). Swedish underground gasification is summarizcd by Egloff (lob'),aRussian method by Chukhanov (?'@, and a German process by Ode11 (3%). lleccnt United States patents on shale include a process for heating shale on a bcd of coal by means of superheated steam (247); a stepwisc fractional eduction process employing hot, lean shale gas in two stages ( 1 6 2 ) ; and a recirculation process employing gaseous shale distillation product as a heat source (91). The Thermofor catalytic conversion principle involving countercurrent flow of product gases also has been investigated for shale on a pilot plant scale ( d 3 4 ) . .The fluidized-solids technique of the petroleum industry has been applied to oil shale retorting. Raw shale is ground to 0.25Inch size, preheated to 300" t,o 500" F., and discharged into a fluidized bed of spent shale a t 1000" to 1600" F., contained in a vcrtical retort 4 inches in diameter bv 10 feet high (56). See also U. S. patents (80.4) and British pat'ents (65). T H E R M A L EXTRACTION
Thermal extraction of shale may be considered as pyrolysis of shale with simultaneous extraction of the organic matter. I n a typical process the shale is ground to 32 to 60 mesh, mixed with an equal quantity of solvent, heated in an autoclave to 380" to 430" C. for 3 to 30 minutes, distilled to remove light fractions, and centrifuged (101, 102). Up t o 90% of the organic matter is re-
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1948
ported as soluble by this method. The solvent is almost completely regenerated during the process. Pressures required usually range from 20 to 30 atmospheres. Among the solvents reported in the literature are Tetralin (101). Tetralin plus 10% naphthalene, phenol plus a thinner (269), anthracene oil, primary tar, fuel oil, mazut, gas oil, shale distillate (99-101), shale tar (102), and hydrogenated tar (100). PRODUCTS AND BY-PRODUCTS
The major products from the pyrolysis of oil shale are shale oil, spent shale, and gas. I n addition, polyphenols, phenolic ethers, pyridine and quinoline derivatives, and thiophene homologs are produced as by-products. A number of papers dealing with these substances have been published in the past six years. An excellent study of the constituents of shale oil naphtha from Colorado shale has recently been published by Ball. Individual hydrocarbon types, various tar acids and bases, and certain sulfur and nitrogen groups were identified (35). The (3x0 CISolefin fraction of shale has been suggested as a source of raw materials for the manufacture of detergents (87‘). Shale oil sludge has been proposed as a vehicle for coal hydrogenation (217). A phenol, 2,6-dimethylhydroquinone,has been isolated from Estonian shale (187). Certain ammonium sulfonates obtained as by-products of shale oil refining in Russia have bpen suggested for use as emulsifiers in the place of soap (47’). The therapeutic action of these sulfonates has been renoted by Reichert (652). An extraction process for recovering the organic nitrogen bases from crude shale sludge has been patented (185). A recent British article (14) describes a number of by-products produced from shale, and the processes therefore, including ammonium sulfate, candles, and bricks (from spent shale). Little new information is offered, however. Tho use of the spent shale as a raw material for a variety of products has been reported from time to time in the literature. Recent suggested Processes have included the manufacture of rock wool ($Os), the extraction of alumina by a variety of methods (946), and the recovery of vanadium, molybdenum, titanium, and tungsten (40, 68). The potential use of shale as a source of uranium has been discussed (70).
-
A N A L Y S I S AND TESTING
Carbonization assay methods of evaluating oil shales for pyrolysis are reviewed briefly and compared by Berthelot (60). 9modified Fischer retort for assaying shale, similar to the aluminum retorts used for assays on coal by low temperature carbonization is described by Stanfield (291). Data showing the effects of different experimental conditions on oil yields by this and the conventional Bureau of Mines assay method are given. The adaptation of the silica gel adsorption method of hydrocarbon identification, developed originally by the National Bureau of Standards, to analysis of shale oil fractions and suitable apparatus for this purpose have been presented in a paper by Dineen et al. (97). Various physical properties of oil shale and shale oil have been reported, including data on the specific heat of Colorado shale (281) and on the coefficient of thermal expansion and heat of combustion of shale oil (72). It is stated that the expansion coefficient varies inversely with the gravity and viscosity.
LITERATURE CITED (1) Adelsberger, A,, and Asbach, H. R., Tech. M i t t . Krupp., A. Forschungsber, 4, 172 (1941). (2) Agroskin, A. A., B u l l . acad. 8ci. U.R.S.S., Classe S C ~ .tech., 1940 (fi), 85. (3) Agroskin, A . A,, Compt,rend,acad. sci. U.R.S.S., 49,273 (1945).
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(4) Agroskin, A , A., et al., Bull. acad. sci. U.R.S.S., Classe sei. tech., 1947. 205. ( 5 ) Agroskin, A. A , and Petienko, I. G., J . Applied Chem. ( U . S . S . R ) , 19, 461 (1946). (8) American Gas Association, “Gas Making Processes,” New York, Am. Gas Assor., 1945. (7) Anon., “Bibliography of Synthetic Liquid Fuels,” P B 1752, Washington, D. C., Hobart Publishing Co., 1947. (8) Anon., Braunkohle, 41, 85 (1942). (9) Anon., Chem. Age (London),56, 683 (1947). (10) ilnon., Chem. Eng. News, 26, 610 (1948). (11) Anon., Coke and Gas, 8 , 103 (1946). (12) Ibid., 9, 81 (1947). (13) Anon., Dept. Sci. I n d . Besearch (Brit.), Fuel Research 1946. (14) Anon., Elect. Review (London), 139, 863 (1946). (15) Anon., Fuel Eff. Comm. of Colung Industry (Brit.) Bull. 2, 11946). ~~. -., . (16) Anon., Gas J., 249, 311, 384, 367, 452 (1947). (17) Ibid., 250, 36, 39 (1947). (18) Anon., Gas Review, 1, 166, 227 (1946). (19) Ibid., 1, 539 (1947). (20) Anon., Gas Times, 49, 136 (1946). (21) Ibid., 51, 428 (1947). (22) Anon., Gas World, 117, 560 (1942). (23) Ibid,. 125. 451 (1946). Ibid.;p. 728. Anon., I r a n & Coal Trades Rev., 153, 1047 (1946). Anon., Oil Gas J.,45, No. 17, 68, 9 7 , 9 8 , 100 (1946). Anon., “Oil Shale and Cannel Coal,” London, Institute of Petroleum, 1938. Anwander, G., Gluckauf, 79, 283 (1943). Arthur, J. R., andLinnett, J. W., J . Chem. Soc., 1947, p. 416. Arthur, J. R., and Wadsworth, K. D., Bull. Brit. Coal Utilization Research Assoc., 8, 296 (1944). Askey, P. I.,Gas World, 124, No. 3205, Coking See., 3-7; No. 3209, Coking Sec., 13 (1946). Askey, P. J., I n s t . Fuel (London) Bull., June 1946, p. 216. Australian Patents 115,042; 115,159; 115,573; 115,991; 116,296; 117,325; and 118,061. Auvil, H. S., et al., U . S. B u r . Mines Repts. Invest. 3935 (1946). Ball, J. S., et al., preprint, Div. Petroleum Chem., 113th Meeting AM. CHEM.SOC., Chicago, Ill. Barlot, J., B u l l . soc. chim., 7, 761 (1940). Barritt, D. T., Gas J., 250,33 (1947). Barritt, D. T., and Barritt, E.J., Gas World, 120, No. 3118, Coking Sec., 57, 66 (1944). Barritt, R. J., and Newby, C. H., Ibid., 116, No. 3018, Coking See., 34 (1942). Barth, O., Tek. Tid., 77, 423 (1947). Baxter, R. A,, and Buell, A. W., Mines Mag. (Colo.), 34, 493 (1944). Bell, J., Gas World, 126, No. 3272, Coking Sec., 55, 60 (1947). Bennett, J. G . ,Zbid., No. 3070, Coking See., 80 (1943). Bennett, J. G., Trans. Inst. Chem. Engrs. (London), 22, 43 (1944). Bergh, 5 . V., Oil Gas J.,45 (52), 250 (1946). Bergh, 9. V., Tek. Tid., 71 (10) ; Uppl. A-C, K e m i , 21-4 (1941). Berkenheim, A . M., and Berkenheim, M. A., Org. Chem. Ind. (U.S.S.B.) 7 , 4 3 7 (1940). Berkovitoh, I., and McCulloch, A., Fuel, 25,69 (1946). 1
~~I
Berthelot, C., “Bituminous Shales, Asphalts, Petroleum,’’ Paris, Dunod, 1943. Berthelot, C., Chimie & industrie, 46, 757 (1941). Biddulph-Smith, T., Coke Oven Managers’ Assoc. Yearbook, 1942, p. 152.
Biddulph-Smith, T., Gas J.,246, 5 6 , 5 9 , 65 (1945). Biddulph-Smith, T., Gas World, 113, No. 2922, Coking Sec., 62 (1940). Tbid., 116, No. 3001, Coking Sec., 11 (1942). Bircher, J. R., Chem. Eng. Progress, 43,453 (1947). Blanding, F. H., and Roethli, B. E., Oil Gas J.,45, No. 41, 84-8, 96 (1947). Blecher, G., GZiickauf, 80, 125 (1944). Blecher, G., Stahl u Eisen, 64, 490 (1944). Bolton, K., et al., J . Chem. Soc., 1942, p. 252. Brewer, R. E., IND. ENG.CHEM., 36, 1165 (1944). Brewer, R . E., U . S . B u r . Mines Bull. 445 (1942). Ibid., Repts. Invest. 3726 (1943). Brinkley, S. R., J . Applied Phys., 18, 582 (1947). Bristow, W. A.,lron & Coal Trades Rev., 154, 299 (1947). British Patents 584,386 and 586,992. Brown, J., FueZ, 26, 5 (1947). Brown, R.L., and Hawksley, P. G. W., Ibid., p. 159. Brundell, P. G . , and Tjernstrom, S. H., Brit. Patent 590,552 (July 22, 1947).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
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