Pyrolysis of - ACS Publications - American Chemical Society

INDUSTRIAL AND ENG INEERING CHEMISTRY

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(523) Warner, R. R., Rubber A g e ( N . Y . ) , 71, 205 (1952). (524) Warrick, E. L. (to Dow Corning, Ltd.), Brit. Patent 682,541 (Sov. 12, 1952). (525) Warrick, E. L., Hunter, M. J., and Barry, A. J., IKD.ENG. CHEM.,44, 2196 (1952). (526) Weisgerber, C. A. (to Hercules Powder Co.), U. 8. Patent 2.592.218 L4oril8. 1952). (527) Westfahl, J. C.: and'sears', D. S. (to B. F. Goodrich Co.), Ibid., 2,587,558 (Feb. 26, 1952). (528) Wheeler, D. H., O&. Dig. Federation Paint & Varnish Production Clubs, No. 322, 661 (1952). (529) Wheeler, 0. L., Lavin. E., and Crozier, R. N., J . Polumer Sci.. 9, 157 (1952). (530) Whetstone, R. R., and Evans, T. W. (to Shell Developnient Co.), U. 9. Patent 2,585,359 (Feb. 12, 1952). (531) White, A. (to Imperial Chemical Industries, Ltd.), Brit. 683,630 (Dee. 3, 1952). (532) Wilson, W. K. (to Shawinigan Resins Corp.), T;. 8. Patent 2,587,562 (Feb. 26,1952). ENG.CHEM.,4 4 , (533) Winding, C. C., and TViegandt, H. F., IND. 2052 (1952). (534) Wingfoot Corp., Brit. Patent 662,682 (Dec. 12, 1951). (535) Wintgen, R., and Jyirgen-Lohmann, L., Kolloid-Z., 122, 143 (\1-Q.51 - - -I., .

(536) Ibid., 123, 11 (1951). (537) Wintgen, R., and Sinn, G., Ibid.. 122, 103 (1951). (538) Wiseman, P. A. (to Firestone Tyre and' Rubber Co., Ltd.), Brit. Patent 675.372 (Julv 9. 1952). (539) Wittcoff, H., and Roach, J."R. (to Geneial lIills), U. S. Patent 2,590,910 1.4prll 1, 1952).

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(540) Wohnsiedler, H. P., IND. Exa. CHEaI., 44, 2679 (1952).

(541) Wohnsiedler, H. P., and Kropa, E. L. (to American Cyanamid Co.), U. S. Patent 2,582,303 (Jan. 15, 1952). (542) Wolf, R. J. (to B. F. Goodrich C o . ) , Brit. Patent 674,080 (June 18, 1952). (543) Wolf, R. J. (to B. F. Goodrich Co.), U. 9. Patent 2,594,375 (April 29, 1952). (544) Ibid., 2,605,254 (July 29, 1952). (545) Ibid., 2,608,549 (Aup. 26. 1952). (546) Wolf, R. J., and Nioolay, ,4. 1.(to B.F. Goodrich Co.), Ibid., 2,605,257 (July 29, 1952). (547) Ibid., 2,608,552 (Aug. 26, 1952). (548) Wooding, N. S., and Higginson, SV. C. E., S. Chem. Soc., 1952, 774. (549) Wrightson, J. &I. (to XI. W.Kellogg Co.), U. S.Patent 2,600,821 (June 17, 1952). (550) Wynstra, J. (to Union Carblde and Carbon Corp.), Ibid., 2,600,457 (June 17, 1952). (551) Yokell, S., Paint Varnish Production, 42, No. 8, 23 (1952). (552) Yost, R. S.,and rluten, R. W. (to Rohm 6. Haas Co.), U. S. Patent 2,616,874 (Nov. 4, 1952). (553) Young, D. W., Sparks, W. J., and Garber. J. D. (to Standard Oil Development Co.). 2.583.504 (Jan. 22. 1952). (554) Yurshenko, A. I., and Tsvetkov, S. S.,Doklady Acud. Nauk S.S.S.R.,85, 1099 (1952). (555) Zimm, B. H., and Bragg, J. K., J . PoZume, Sci,, 9,479 (1952). (556) Zoss, A. 0. (to General Aniline and Film Corp.), U. S.Patent 2,609,364 (Sept. 2, 1952). (557) Ibid., 2,616,879 (Nov. 4, 1952).

Pyrolysis of Coal and Shale CHARLES H. PRIEN, DENVER RESEARCH

INSTITUTE, UNIVERSITY OF DENVER, DENVER I O , COLO. Papers on coal pyrolysis during the past year included several studies on the mechanism of degradation OF the coal macromolecule during pyrolysis and of the structure of the pitch and tar produced. Patents on fluidized carbonization continued t o appear. Interest i n low temperature carbonization i n the United States has been mounting, as has also interest i n the pro. duction of coal chemicals by l o w temperature carbonization, without simultaneous production of metallurgical coke. The physicochemical processes responsible For benzene production during carbonization and elimination of overlapping standard tests for coke properties were studied, U. S. Bureau of Mines activities o n o i l shale included studies on more efficient methods OF mining, revised estimates of the size of U. S. o i l shale resources, further p i l o t plant &velopment of the gas combustion process and cracking processes, additional cost estimates for commercial operations, and a new entrained-solids high temperature retorting process, Research on kerogen composition included a controlled oxidation with alkaline permanganate and a thermal solution OF the shale with associating and nonassociating solvents at 200" C. A high temperature retorting process For shale fines yields oils high i n aromatic hydrocarbons. Shale tar bases have been successfully polymerized t o aldehyde t y p e resins, using formaldehyde. H i g h pressure catalytic hydrogenation of Colorado shale o i l i s reported t o y i e l d a sulfur- and nitrogen-free product suitable for Further standard petroleum processing.

T IS pertinent to begin this sixth annual review of paper. published in the field of coal and oil shale pyrolysis by restating

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the scope of the coverage undertaken. Although primary effort is devoted to coal and shale pyrolysis as such-its niechanism and practice-to complete the survey, it has been extended to related subjects of concomitant concern to persons in these fields. Bccordingly, an attempt has been made t o include not only references to high and low temperature carbonization of coal and retorting of oil shale, their mechanisms, kinetics, and applications, but also to cover related subjects, viz., raw materials, product and by-products characteristics and properties, coke oven equipment and improvements, coke analysis and testing,

The shale revien includes papers on shale properties, shale oil characteristics,retort design, and, briefly, theimal extraction. The majority of references to high-pressure gasification processes, subbituminous and lignite gasification, and underground gasification processes have been deleted, a8 being more properlyclassifiedasunitprocesses other than pyrolysis. Because a clearcut delineation hereto is not possible, however, certain ieferences to combination pyrolysk-gasification processes a l w a y s n e c e s s a r i l y w a r r a n t inclusion. The period under review is essentially that from June 1952 to 1953, except for previous omissions ariving from the normal lag in the publication of paperP and abstracts. The voluminous literature of the period, some 640 separate papers, has necessarily been reduced for illclusion in this revielv.

COAL PYROLYSIS GENERAL

A number of books and revieas of general interest have been issued during the past year. Sttention is called t o a publication of the rational Coal Board of Great Britain (1514) on metallurgical (not gas) coke processes, to the annual coal

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report of the U. S. Bureau of Mines (W2A), and to the summary report of the work the Fuel Research Board (Great Britain) ( @ A ) ; . Papers from the 1952 meeting of the International Gas Union at Brussels, Belgium, including technical discussions of the dry cooling of coke and of gas-making processes have been reviewed (SSA). At a German symposium on chemical practices in the bituminous coal industry subjects included laboratory control methods in carbonization plants, practical applications of caking tests, ammonia saturator operation, and experiences with various oven refractory materials (180A). Igoe and Rose (96A)have summarized the coal research activities of 46 U. S. companjes and research groups during 1952. -4mong the subjects applicable t o the current review are ( a ) macro and micro pore measurements on coke, by Carnegie Coal Laboratory, ( b ) plasticity testing methods, as developed b y Illinois State Geological Survey, ( c ) studies on devolatilized high volatile coals as raw materials for metallurgical cokes, by ISGS, ( d ) low temperature carbonization research by the University of Kentucky, Pittsburgh Consolidation Coal Co., and Southern Research Institute, and ( e ) subbituminous coal fluidization studies a t the University of Wyoming. An excellent analysis of the economics of coking ovens in Great Britain has been presented by Barritt (9A). An analysis of the 1953 coke supply in the U. S. and the factors contributing t o a coke shortage has been compiled by the Defense Solid Fuels Administration (97A). A few papers have dealt with a survey of the carbonization industry in various individual countries. Reference is made particularly to ( a ) a description of the Japanese industry by Davies (45A), who points out that little or no low or medium volatile coking coals are available there; ( b ) a historical description of the beehive coke industry in Japan, by Nakagawa (160A); ( e ) a review of the Australian industry by Farafonow (67A), and of methods for production of coke and domestic gas in Australia, by Andrews ( 4 A ) ; ( d ) the progress and plans of the nationalized French gas industry, by Kec (106A); and ( e ) the by-product coking industry of Canada, by Burrough ( M A ) . With respect to the latter see also a review on gasification in Canada by Lang (119A). P Among several miscellaneous papers mention should be made of a review of underground gasification of coal as conducted in England since 1950 (9CA); and a general summation of underground gasification experiments throughout the world, by Fies (68A). A discussion of the health hazards in the coking industry is given by Rogan (186.4). The by-product chemicals outlook in the U. S. was reviewed a t a recent meeting of the American Coke and Coal Chemicals Institute. Subjects discussed included ( M A ) competition from foreign nitrogen coal-chemicals, the future role of ethylene and methane, and programs for plant protection. M E C H A N I S M , KINETICS, T H E R M O C H E M I S T R Y

I n applying knowledge of the chemistry of macromolecules to the coal carbonization process Poncins (173A) describes three stages: ( a ) degradation of the macromolecule t o the viscous liquid plus gas stage, during which the pore structure of the coke is formed; ( b ) addition of linear macromolecules to the planes of carbon atoms, with the formation of semicoke; and ( e ) graphitization of amorphous carbon. Pitch and tar macromolecules are described as “zig-zagging” chains of paraffins or condensed rings. Formulas for the latter are proposed. I n discussing the manner in which coal cokes Smith formulates the requirements (198A) of: initial high temperature fusion, simultaneous decomposition and polymerization, and low vapor pressures for the liquids so formed. A series of Japanese papers by Kitazaki, Yagishita, and co-

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workers are worthy of mention. In the first of these (228.4) coking properties are related to the formation of a two-dimensional lattice of “unit carbon chains” which is transformed subsequently to a “three-dimensional graphite structure,” with the release of gaseous hydrocarbon molecules. The second paper (IlOA)postulates, from x-ray studies, that coking properties are related to the size of the primary macromolecule, larger ring nuclei with more numerous hydrocarbon attachments requiring higher coking temperatures. The third paper (226A)is devoted t o an analysis of the thermophysicochemical nature of the carbonization process. Five steps are postulated in high temperature carbonization: ( a )an endothermic reaction, with loss of moisture; (6) a preliminary, exothermicvolatilization; ( c ) further volatilization and endothermic heat change; ( d ) a further endothermic reaction a t reduced volatilization; and finally (e) an endothermic step with practically no volatilization. The last paper in the series (2.27A)is concerned with the relationship of heats of wetting t o the structure of the coal macromolecule. A Japanese paper by Suzuki ( N 6 A ) analyzes the structure of coal and coke in the light of x-ray evidence. See also an x-ray study of laminated dull and bright coals, by Matsuyama ( l d 6 A ) . A mechanism of coking in relation to the two and three dimensional carbon lattices present and formed has been postulated from x-ray data by Kitazaki (111A). Tawada (,%%A) concludes, from a study of the coalification process, that the bitumen present is depolymerized humin. According to an earlier paper (207A)the gases from this bitumen produce swelling of the coke. The source of asphaltenes in thermal decomposition of coal and other humus fuels is claimed (106A) to be secondary reactions of the products of primary pyrolysis of the humic matter, including phenols. From a test of fifteen coals and nine partly hydrogenated coals it is concluded (149A) that a polar-atom content of less than 5 % results in high thermal stability to pyrolysis, as might be expected. The relationship of ignition temperature to volatile matter in partially carbonized coals has been the subject of research reported in a Russian paper (16bA), wherein it is claimed that low boiling volatile materials formed during ignition do not affect the temperature of ignition significantly. Further studies on the mechanism of evolution of volatile matter during pyrolysis and the nature of the compounds produced are noted in (74A). A report of special significance in the understanding of the coal pyrolysis process has been presented by Hadzi (86A), who examined intermediates in carbon formation during pyrolysis of such simple organic compounds as polyvinyl chloride, tetralin, naphthalene, anthracene, etc. He suggests that large, noncondensed polycyclic molecules first form and subsequently condense to the familiar graphitic lamellas. See also a paper on crystallite growth in graphitizing and nongraphitizing carbons from various organic CompoundR, by Franklin (62A). Fromresearch on thelow temperature carbonization ( a t 350’ C.) of coals of varying degree of pulverization, in vacuo, it is concluded that swelling is related to degree of oxidation, and not to particle size (67A). Fuchs (65A)has related degree of coal carbonization to the original presence of “microorganisms of variable reducing power.” Seyler (19SA) has found ten components of wood in coal, three of which appear in the coke produced therefrom. Further evidence of the cyclic nature of bituminous coal has been deduced from molecular distillation, hydrogenation, oxidation, and solvent extraction, by Howard (9SA). The solvent extraction of slack from coking coal is reported in (109-4.). In an older paper not previously reviewed Orchin (161A) and coworkers have studied the ability of polycyclic solvents to destroy coking properties. The benzene soluble portion of the extract was found to contain the “coking principle.” It is suggested that oxygen cross linkages in lower rank coals, upon destruction by mild hydrogenation, permit new carbon-carbon linkages to form upon subsequent coking.

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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

The mechanism of decomposition of raw peats has been the object of r e s e a r c h ( 2 1 0 A ) . The colloidal substances present decompose by processes controlled solely by the temperature of pyrolysis, and not by time of exposure, at least in so far as the decarboxylationdehydration reactions are concerned. Picon (171A) has thermally fractionated samples of coal aged from 17 to 59 years, and compared the results with those obtained originally for the fresh samples. He found less gas evolution for all aged anthracites and peranthracites, up to 900’ C., than for the prestored samples.

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sized particles with a hydroc a r b o n a c e o u s liquid-e.g., Bunker C fuel oil-capable of inducing Browiian movement. Control methods applicable to the utilization of fine screenings of widely varying nature as blends in the men charge are described in detail by Colson (34A), from Belgian practice. Some economic factors requiring greater future U. S. use of blended oven charges are outlined by Reed (179A). A symposium on the blending of anthracite to manufacture foundry coke in Japan has been presented by Oka and o t h e r s (169A). Space does not permit discussion of details here. In an interesting paper on the thermal metamorphism of cerR A W MATERIALS tain coking coals in Colorado, A N D PROPERTIES Johnson (10ZA)has pointed out Processes for suitable pretreatthat igneous rock intrusions ment of coal prior to charging COURTESY U. 8. BUREAU OF MINES sometimes result in increased Equipment for Studying High Temperature Processing of to the oven, and for preparing Shale Oil coking qualities, while ground suitable blends for carbonization continue to appear in inwater oxidation of the coal has creasing z tendency to reduce or even - numbers. Todd (215A) has presented a general survey of coal washing, destroy much of the coking characteristics. blending, and crushing practices used in Great Britain. Tixier Eniart (66A)has surveyed some of the coking coal resources of ( d 1 4 A ) gives a similar discussion with respect to Lorraine coals, Canada. He suggests the utilization of large deposits in illberta as does also Prax (l75d),who describes a ramming (compression) and British Columbia by employing the slot-type by-product technique employed a t Carling. In the first of two older papers on oven. The U. S. Geological Survey has gathered data on the carbonizing conditions for Lorraine coals Pamart indicates (166A) coking coal deposits of the western U. S. (219A). Mention that control of particle size and moisture can be used in lieu of should also be made of a compilation of the world resources of compression to control porosity. In a second paper (167A) he coal, brown coal, and lignite, together with Rorld production states that as much as 30 to 35% volatile matter (other than statistics, by the U. S. Bureau of Nines (161A). A complete water) yields a more cohesive coke, providing that moisture condiscussion of Australian coals in particular, their classification, tent itself is only 2 to 3%. rank, origin, and metamorphosis is given in (16b’A). Three German processes for preparing ultraclean coals are menHIGH TEMPERATURE CARBONIZATION tioned (SQA),including ( a ) dense-medium washing followed by grinding and flotation; ( b ) jig-washing, flotation, and extraction Patents on fluidized carbonization of coal are still a popular with mineral acids; and (c) a process substituting a dilute caustic subject in the literature. The following eight issues, all assigned soda extraction for the acid in ( b ) . In upgrading certain highto the Standard Oil Development Co. are worthy of attention. sulfur Pennsylvania and West Virginia coals to metallurgical Odell (156A) describes a piocess in which a fluidized stream is quality I t was found (65A)that those in the range 1.81 to 2.27% passed upward through a bed of stationary particles, countermlfur could be treated by low-gravity separation, fine crushing, current to a downward flowing stream of solids. Howard (92A) and froth flotation. and n’elson (l623A) both present features of a fluidized carbonizaBerl ( I d A ) has patented a process for converting noncoking tion process for solids “which become plastic on heating”-e.g., carbonaceous substances into coking substances by treatment coal. Gas velocities of 3 to 30 feet per second and the use of nonwith carbohydrates and/or alkali. A British patent (2.4Ai plasticizing dduent solids are claimed. Reu (183A) mentions suggests separation of petrographic constituents by crushing as the use of “heatrcarrying solids” preheated to 454’ to 760’ C. a means of upgrading poor coking coals. A Dutch patent (51A) prior to contacting with the material to be carbonized. Matheutilizes hydroaromatic and other solvents to improve the plastic son ( I S g A ) has patented a process employing an interface in the properties of the coal. fluidized bed and the use of particles of such size as to maintain Shotts (196A) diluted coals with various proportions of their this interface. Hemminger (88A) claims a fluidization process own high density inorganic constituents (quartz, shale, fusain, for bituminous solids which includes a recycle phase capable of etc.), and found that the free swelling index was decreased thereagglomerating the fines so returned to the process. The addition by, A classification of Japanese coals on the basis of their softenof admixed, preheated metallic oxides in the fluidized bed is ing-swelling curves has been made (68A). For a critical review described by Barr ( 8 A ) . Odell and >latheson (157A) outline a of softening and swelling in high-volatile coals see (158A). The three-stage process of fluidized carbonization by which activated relationship of the banded constituents of coal to their agcarbon may be produced. The use of the electric furnace for glutinizing curves has been studied by Reim (18RA), who concoking continues to receive attention, An experimental U. S. cludes that vitrain is a part of each constituent. furnace with a power requirement of 400 kilowatt hours per ton A patent on the preparation of stable coal suspensions, although of coal, or 250 or lower with heat recovery, is described (168A). not directly concerned with pyrolysis, is worthy of mention. The The use of briquetted coals (Spitzbergen) in an electric furnace to prepare good quality coke has been studied (IWOA). process depends (206A) upon the controlled mixing of closely

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INDUSTRIAL AND ENG INEERING CHEMISTRY

The British Coke Research Association (iO3A)has extended its research on coking pressure t o include the effects of coke breeze blends, charge heating rate, and bulk density. Graphite formation in coke under conditions of high temperature carbonization has been found (71A) to increase with temperature, heating time, and a decrease in heating rate. Further data on the effect of carbonizing conditions on tar yields and properties have been published (&A). Thau (211A) has reviewed German processes for the manufacture of metallurgical coke from brown coal briquettes. Goswami (77A) describes the use of sea sand and sodium silicate to remove sulfur of certain Indian coals. Sand requires higher temperatures than the silicate, 5% of sand producing approximately the same coke sulfur content a t 1300” C. as 2% sodium silicate at 850” C. Rao (178A)has shown that a suitable foundry coke may be prepared from noncaking coal by low temperature carbonization a t 600’ C., followed by carbonization a t 900” C. During the latter stage a thin stream of crude oil is allowed t o trickle over the coke. LOW TEMPERATURE CARBONIZATION

The use of low temperature fluidized carbonization of coal as a first step in synthetic fuels manufacture is described in a recent process of the Pittsburgh Consolidation Coal CO. (169A). Powdered coal is partially carbonized t o a fine char, tar, and gas. The char (semicoke) could be further gasified or used as a source of Fischer-Tropsch gas. See also a brief account of a fluidized low temperature pilot plant near Chicago (27A). The use of fines as a source of heat for the fluidized bed has been shown by Creelman (41A). Lesher (12%A)has patented a continuous process in which a horizontal retort operates with a protective barrier of preheated char in contact with the walls. See also two U. S. patents on the same process (40A, 123A). The Parry process, which converts raw lignite into crude tars and dry char by fluidized drying followed by low temperature carbonization, has been reviewed

(i56A). The economics of low temperature carbonization in India, especially in relation to the production of chemical raw materials, has been presented (118A). Fuchs (66A) suggests catalytic dehydrogenation of light oil fractions t o aromatics as one way in which the economics of low temperature carbonization might be improved. The cost of producing fuel gas in Pennsylvania, by gasification of low temperature char, has been estimated by Breck (15A),who quotes a figure of 55 cents per 1000 cubic feet for large scale operation. Mazov (136A)studied the possibility of producing semicoke in shaft furnaces by first reducing their caking tendency by oxidation with flue gases. Only partial success was attained. The carbonization of noncaking Indian coals by the Hodsman process is described (99A). See also a patent (ISA),which describes the manufacture of briquets with internal holes. The factors responsible for the disintegration of brown coal briquets during firing have been studied by Rademacher (176A) who cites temperature, weight, and method of formation as the important variables. Annular briquets are stated to be superior to cylindrical forms. Weingaertner (223A) has studied the shrinking process in similar briquets, and has found two major and three minor stages in carbonizations up to 700” C. For a description of the low temperature pilot plant and laboratory a t the University of Kentucky see (107A). OVEN OPERATION

An interesting study of the (‘aerodynamics” of coke-oven heating has shown that better heat transfer design can still be effected. Among the alterations suggested is (126A) improved proportioning of size and shape in turning flues and between heating flues

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and generators. Myhill (146A) has examined heat losses in horizontal retorts and continuous vertical retorts. Heat balances on e, battery of 60 Otto ovens are discussed (133A). Heat requirements (including rate) in starting up silica ovens have been studied in relation to refractory properties (19UA). Myhill (i48A)has made comparative heat balances on three types of ovens-vis., horizontal, intermittent vertical, and continuous vertical-and obtained total useful heat values of 81.7, 87.2, and 86.8%, respectively. A detailed analysis of the use of natural gas-air mixtures in the range 520 t o 560 B.t.u. per cubic foot for underfiring ovens has been presented (226.4). Mortimer (143.4) describes a B.t.u.-recorder for controlling the dilution of coke oven gas with producer gas, in oven firing. Dry quenching continues t o be the subject of attention. The British Coke Research Association (19A) has published a bibliography on the subject for the past 8 years, including data on sulfur removal. Supplemental generation of waste heat by burning coke fines, in addition t o steam from quenching, has been patented (116.4). Melan (138A)has proposed a so-called ifnew” process for dry quenching with power generation. Hersche (89A) analyzes modifications in known dry-quenching techniques, but discusses no new processes. Pieper has conducted yet another study on carbonization time as a function of oven width (172A). For a conventional oven he concludes that carbonization time (2) i s related to internal oven diameter (s) b y the equation z = cs”, where n is approximately 1.5, and c i s a function of the temperature gradient. High swelling pressures in the coke oven are critically examined in a British Coke Research Association report (18A),including their origin, and the influence of both bulk density and rate of heating. Simek (1S7A) compares various laboratory methods for pressure measurement. Myhill (147A) states that porosity of refractories and gas degradation through hydrocarbon cracking are the two most important factors making pressure control necessary. Methods for broadening the plastic zone are diagrammatically presented in a paper by Terbeck (209A1. ‘ A French patent (WOIA) deals with the use of low amplitude, high frequency vibrations to impart vibrations to the oven charge. Prevention of graphite deposition on the vault of the gas-collecting chamber, by the introduction of saturated or superheated steam, is described in a second French patent (2OUA). See also a Dutch patent (6OA)on the same subject. PRODUCTS AND BY-PRODUCTS

The relationship of coke oven products to wartime demands for raw materials, and the outlook for the future in this regard is the subject of a general paper (142A). West German production of coke oven products during 1951 has been surveyed (29A) in a report which indicates the need for the erection of new batteries there if capacity is to be increased. The future outlook for coke oven chemicals in the U. S., particularly hydrogen, methane, and ethylene, is bright with ample markets, according to a report a t a recent meeting of the American Coke and Coal Chemicals Institute (28A). Present annual chemical demand for the three gases mentioned was stated to be 170 million cubic feet of hydrogen, 100 million cubic feet of methane, and 2.4 billion pounds of ethylene. Potential coke oven production is estimated to be 3.1, 2.8, and 1.1 times present production, respectively. I n a study of the factors inffuencing by-product recovery in both high and low temperature carbonization Tomk6w (216A) lists temperature in the “cracking space” as the most important variable. The effect of recycling coking gas through the charge was examined and found t o increase benzene yield by 27%. In a theoretical study of the effect of temperature and gas contact time on by-product yield Trefny (818A)concluded that 700” to 800’ C. and 1 to 10 seconds represented the optimum conditions.

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INDUSTRIAL AND ENGINEERING CHEMISTRY

COURTESY U. S. BUREAU OF MINES

Figure 1.

N e w Gas Combustion Demonstration Shale Retorting Plant, Rifle, Colo.

The use of warning controls to indicate temperature in the L‘cracking space” (above the charge) is mentioned (85A). The economics of gas production in coke ovens, and in horizontal and vertical retorts in Great Britain has been summarized ( 1 5 4 4 ) . In a correlation of laboratory and plant data on various coke oven gases and their constituents mavimum and minimum limits for calorific value, gravity, and sulfur and nitrogen are given (Z31A). h new process for separating the constituents of coke oven gas has been patented (87A). Liquefaction removes benzene, propylene, ethylene, methane, and carbon monoxide, but not hydrogen. See also (4QA). A Japanese paper reviews methods of hydrogen recovery ( 3 A ) . RIichel(139A) and Barlet ( 7 A )both describe the Bueb-Guillet process for removal of ryanidea from gas, by washing with ferrous sulfate, folloqed by treatment ivith lime, potassium chloride or sodium carbonate, and finally potassium carbonate. A general review of current research on hydrogen sulfide removal has been compiled by Hollings (QfA), and a survey of present-day sulfur removal practice by Sen (1Q2A). I n an account of German practice (213A) it is indicated that very few liquid purification processes are in use in that country. The patent situation in regard to sulfur recovery processes is discussed by Waeser (221A), who also includes processes for direct recovery from coal itseIf. The catalytic oxidation of organic sulfur by contact with nickel subsulfide is said (7QA) to reduce sulfur content (except for thiophenes) to about 2 grains per 100 cubic feet, JT-hen used on an industrial scale. Ac: usual, ammonia recovery has been the subject of additional papers and patents. A detailed analysis of ammonia saturator operation and design is given in an excellent paper by Mantel (132*4),including photomicrographs of sulfate crystals. I n a symposium mentioned earlier (18OA) it is stated by Klempt (114A) that an iron content of the order of 1 gram per kilogram of saturator liquor yields the best crystal form. For a survey of

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ammonia recovery techniques in France, England, and Germany, see (lef-4). Among new patents on ammonia recovery are absorption processes utilizing (a)a spray tower employing acidified ammonium sulfate liquor ( 1 8 3 8 ) ; ( b ) spray or packed towers using iron-free ammonium sulfate from spent pickle liquor (1S7A); and ( e ) a “narrow, elongated absorption zone” through which coke oven gas flows horizontally ( 1 A ) . See also (8OA) for a patent on spraying crude ammonia water over packing, countercurrent t o air or oxygen. The world benzene situation and its future development.. especially in relation to coal carbonization, are reviewed together with the economics, in an excellent paper by Krevelen ( 117Ai. Among the processes discussed is carbonization without metallurgical coke production. The physical and chemical reactions responsible for benzene production in the carbonization process in regenerative-type ovens are critically surveyed by both Rosendahl (187A) and Warmuzinski (222A). The latter author, in an analysis of the effects of pressure and temperature, suggests that llOOo C. is the optimum temperature for benzene production and 800’ C. for toluene. S e w developments in benzene recovery and refining proceeses are discussed (Q6A),including the admixing of petroleum distillates with the oven charge to increase benzene yield, and catalytic refining. Claxton (SZA) examines the refining methods employed to produce nitration-grade benzene and the action of the sulfuric acid wash on the various unsaturated impurities present. Among recent patents relating to benzene recovery are ( a ) absorption from oven gas in an aqueous solution containing calcium chloride, a nitrate, and a glycol or glycol ether, followed by absorption in a hydrocarbon (19QA);( b ) a process for separation from acid wash residues, using direct steam distillation ( 1 6 4 4 ) ; and ( c ) the use of vapor-phase polymerization in recovering cyclopentadiene from the light oil, by formation of the diene dimer (202A). A number of patents on the recovery and purification of naphthalene are worthy of mention. The use of methyl alcohol for upgrading is proposed by Scott ( I d O A , 1Q1A). Liquid ammonia is suggested by Jarry ( I O O A ) . Phenol recovery from carbonization plant wastes, as usual, has been the subject of additional research. The use of a modified Phenolsolvan process in a lignite, low temperature carbonization plant is described ( l d 7 A ) , together with an economic analysis of plant sizes, Kleinert (11SA) proposes “technical lignins”-e.g., saccharified wood-as an adsorption agent, followed by elutriation with dilute alkali. Finely ground bituminous coal has also been used for removal (&$A), but without subsequent recovery of the phenol. For further waste treatment without recovery see the findings of a cooperative study in which (32A)chlorine, ozone, and chlorine dioxide \yere added as oxidizers. h series of three patents (QOA)outlines use of saturated hexamethylenetetramine solutions to isolate phenol from coal tar, follorved by a pentane wash, and ether decomposition of the amine-phenol complex. Liquid-liquid extraction of tar fractions has shorn-n decreasing effectiveness for the solvents glycerol, triethylene glycol, ethylene glycol, diethanolamine, and triethanolamine, in the order shown (@A). Attention is directed to a series of papers on the general characteristics and chemical compositions of tars from down-jet combustion of bituminous coal (22OA); to the composition of the principal fractions of tars derived from coke oven, horizontal, and vertical retorts, and from water-gas generators (GOA); and to a series of papers on the chemical products from low-teniperlture Coalite process tars (174A). EQUIPMENT

References in this section have been limited to only the most important papers and patents. Simple listings of patent references not discussed have been made in certain equipment cate-

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INDUSTRIAL AND ENGINEERING CHEMISTRY

gories, as an aid to the reader interested in pursuing these subjects further. Even in these cases, however, the tabulations are necessarily incomplete. Reid (181-4) has reviewed the technical and economic aspects in the choice of various types of retorts, particularly in Australia. A similar, shorter survey has been made in a Polish paper (76A), including oven dimensions, refractories, regenerators, and gas collecting devices. The “Stilcok” process, involving an allwelded apparatus with a centrally located heating service, is the subject of a recent booklet (WO4A)and a patent (38A). A comprehensive review of the mechanical engineering involved in coke plants has been published (64A), including the by-product operations. Patents on new or improved designs of coke ovens may be found in special references (IB-BIB) in the literature citations. Francombe has summarized the salient characteristics of electrostatic tar collecting devices in coke plants (61A ) . A new collision-type detarrer, consisting of a network of Plexiglas threads, has been investigated on a laboratory scale (WA). Reyes (184.4) has compiled an excellent paper on the chemical, physical, and thermal properties of fireclay and silica refractories for coke ovens. See also (145A). Phase changes occurring in refractories used in gas retorts are the subject of a discussion by Firkin (69.4). Mantel (13OA) has examined the applicability of laboratory technique for refractory study, particularly photomicrographic and polarized light methoda, to results obtained in the coke plant. Technical factors in the use of refractory cements in coke ovens have been outlined (185A). A list of patents on refractories, various types of oven machinery (pushers, doors, etc.), and other coke plant accessories is given in special references ( I C - I S C ) a t the end of this review. COKE PROPERTIES

From a study of the state of carbon in metallurgical coke (47A)

it was found that no direct relation exists between cohesive

-

strength, graphite content, and resistivity. Campbell (W5A) has evaluated a number of standard tests usually applied to coke, particularly as to overlapping information so obtained. (For example, shatter and screen tests are said to be 94% a measure of the same property.) As a result moisture, volatile matter, ash, sulfur, screen test, tumbler test, and bulk density are recommended as yielding the characterization data required. The structure of coke, as revealed by x-ray and solvent extraction studies, is discussed in a recent lecture (53.4). As a result of studying coke densities Thibaut (MWA) lists particle size and shape, packing, and mechanical forces involved as the controlling variables, and describes methods of measuring each. A quantitative formula expressing the electrical resistivity of lime-coke mixtures is given by Aono (6A). A thorough study of the reactivity of coke, using adiabatic selfheating in a stream of air or oxygen, has been made by Weisz and Orning (WW4A). The most important coke property was found to be its chemical nature, as measured by its volatile matter content, the latter being quantitatively related to reactivity. Pore surface distribution, although a significant property, was minor in comparison with the above. A new apparatus for measuring reactivity, using steam, has been tested (16A). The conclusions are those expected with respect to rate, carbon monoxide, and carbon dioxide content. The reactivity of coke has been related t o the mechanism of its formation, as a result of research conducted with a thermobalance (IIWA), and particularly t o its hardness and strength. The growth of carbon grains is postulated as the controlling step. The influence of certain salts on reactivity has been examined in an older Russian paper (116A)only recently translated. The reactivity of three industrial cokes a t 900’ C. was examined after precipitation of metal hydroxides in the coke pores. Salts of aluminum, calcium, manganese, iron, and copper were employed.

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Sawai (188A) has studied the reactivity of coke to carbon dioxide. He states that below 1000’ C. reaction kinetics control rate and above 1400’ C. diffusion is controlling. Ershov (56A) describes a careful study, including experimental details, of the same reaction, in the range 600’ to 1000’ C. Lewis(lW4A) states that cupola cokes produced in South Africa, India, and Australia are much higher in ash content than those produced in the Northern Hemisphere, although the ash content of American and European cokes is gradually rising. Stephens (W03A)has reviewed the foundry coke situation in Aust>ralia. As a result of a study of 15 cokes it is concluded (’MA) that coke dust explosions are highly improbable in plants employing electrical handling equipment. A mathematical analysis of the process of ignition of coke dusts has been made by Chukhanov (EM), who concludes that “a decrease in primary air, down t o a definite limit, facilitates ignition.” A review on the quality of blast furnace and foundry coke in Great Britain and trends therein has been published (78A). Dudderar (53A) has compared the beehive cokes produced in nine U. S. Steel Co. plants, using ash, sulfur, screen analysis, and drum tests. He concludes that ( a ) 48-hour coke was in general better than 96-hour coke, ( b ) beehive coke showed higher “fuel values” (tumbler test) than by-product coke, and (c) a by-product coke showed better size than six beehive cokes from the same coal. ANALYSIS A N D TESllNG

References on methods of coal analysis have been numerous during the past year. An effort has therefore been made t o restrict comment to those which are deemed to be particularly significant. A general survey of all standard methods of coal and coke testing from both the theoretical and practical point of view has been made (144.4). The work of the International Standards organization with respect to each test is discussed by King (108A). A review of control methods employed in the German coking industry has been presented (817d). A series of French reports is devoted to methods for proximate analysis (36A); for carbon, hydrogen, and inorganic carbonates (36A); and for sulfur (37A). With respect to individual items in the proximate analysis attention is called to the following papers: For moisture, a direct gravimetric method (&A) in which oxygen-free nitrogen a t 105” C. expels water, the gas being collected in a tube containing a desiccant. Also an indirect method (43A) based upon weight loss after vacuum drying a t 3 to 5 mm. prepsure. Goodman (76A) has concluded, from a recent comprehensive study, that the usual oven-drying methods are inadequate to determine the moisture content of low rank, high moisture coals, and recommends volumetric procedures instead. For ash, a rapid method based upon a correlation between specific heat and thermal conductivity of coal, and ash content (196A). In a British study (WIA)it has been shown that mineral matter in coal can be estimated with sufficient accuracy from a determination of only ash, total sulfur, and carbon dioxide, using a correlation formula based upon some 1400 analyses made by the more lengthy King-Maries-Crossley procedure, Jerger and May (1OIA) have studied over 400 coals in an attempt to estimate ultimate analyses from proximate analyses and higher heating values. Correlations were found for carbon and for available hydrogen, but not for sulfur. With respect to individual items in the ultimate analysis of coal and coke attention is directed to the following: ( a ) an improved Eschka method for sulfur, details of which are given by Rademacher (I77A), and a modification of the bomb-washings method, based upon conductometric titration with barium hydroxide (64A); (a) a wetcombustion method for chlorine, using sulfuric acid, potassium dichromate, and silver sulfate (11A); ( c ) a modified Kjeldahl method for phosphorus (WMA); ( d ) the direct determination of

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INDUSTRIAL AND ENGINEERING CHEMISTRY

oxygen by hydrogenation of oxygen-containing products of pyrolysis (MA), by pyrolysis under vacuum (81A), and b y various modifications of the usual carbon reduction method (IOA, 14A, 72A, 81A). I n the case of the oxygen methods, it is stated ( 1 8 9 A ) that none of the “direct” methods is as accurate as a modification of the usual differential method, in which corrections are applied for carbonate carbon and mineral matter. Maim (129A)has examined the various tests of cokability used for coals and their significance, as has also McKee (128A). A glass apparatus for low temperature laboratory carbonization tests, involving a tube divided into three sections, is said (6A) to yield results comparable to the Fischer retort. A new experimental test oven has been designed by the U. S. Bureau of Mines (7OA), with particular attention to improved heat transfer characteristics. Peytavy ( 17OA) describes an x-ray technique by which cracking and movement of the plastic zone may be followed in a sample of coal undergoing carbonization. Bresler ( I 7 A ) has used a large plastometer and recorded the moment of cracking electrically by “the breaking of a fine horizontal conductor which has been gripped by the coal as it became plastic.” An ultraviolet light technique for determining the fissuring of coke, involving a dry sample with chalk cross hatching on its external facets, has been tried (16OA). A recording dilatometer has been used (104A) to detect the threshold temperature of coking and the extent of volume change. Naugle (152A) has evaluated expansion pressure tests on coals statistically, and related them to other coke properties. Gayle ( 6 9 A ) has subjected the standard screen tests to statistical analysis. British standard sieving procedures are dealt with in detail in a recent bulletin (2OA). Shaw ( 1 9 4 A ) describes a method of analysis for phenols in aqueous coke plant wastes, and claims a sensitivity of 20 parts per billion. For a review of methods of phenol analysis, not only in plant wastes, but also in tars, tar oils, and tar acids, see ( 2 6 A ) .

OIL SHALE PYROLYSIS GENERAL

The U. S.Bureau of Mines has issued its usual annual report ( 6 6 0 ) of its progress in oil shale research during the past year. Activities during 1952 included studies on more efficient methods of mining, revised estimates of the size of U. S. oil shale resources, further pilot plant development of the gas combustion retorting process and erection of a 50-ton-per-day unit, additional improvements in recycle cracking and visbreaking refining techniques, and additional cost estimates for commercial operations. The Laramie laboratories continued investigations on entrained solids retorting to high quality fuels and aromatic chemicals, on solvent extraction and hydrogenation for the production of Diesel fuels and high octane gasolines, and analytical research on the composition of shale oils and their fractions. Further details will be found in the sections of this review which follow. Another review of the well-known Scottish oil shale industry has appeared ( 3 9 0 ) , including a description of the 104 retorts a t the Westwood plant, the crude shale refining operations, and the synthetic detergent plant. Richards ( 4 2 0 ) has presented a survey of 1950 literature on oil shale activities in Great Britain, Germany, Sweden, South Africa, aqd other countries. Included also are bituminous tar sands, peat, wood, low and medium carbonization processes. Heat balances and cost data for the Sn-edish oil shale industry are presented in an OEEC report (37B),which also includes details on material balances and chemical analyses of the products. Savage ( 4 6 0 )gives details of pilot plant tests on the processing of 80 tons of Colorado oil shale at Kvarntorp, Sweden, in one of the HG retorts of the Swedish Oil Shale Co. The shale oil obtained was of lower specific gravity and pour point than that

Vol. 45, No. 9

produced from the same shale by the U. S. Bureau of Mines or the Union Oil Co. retorts. Economic data are shown comparing commercial-scale operations using such retorts with methods of the U. S. Bureau of Mines and other U. 5.processes. For further information the reader is referred to the author, since certain portions of this paper are of a restricted nature. The applications of known retorting methods to the commercialization of the shale deposits of Vale do Paraiba, Brazil, have been discussed (540). Faber ( 2 1 0 ) has reviewed the attempts made to date to recover oil from the Wurttemberg shales of Germany. For results of new attempts to process eastern European shales, see (550). M E C H A N I S M , KINETICS, T H E R M O C H E M I S T R Y

Robinson and coworkers ( 4 3 0 ) have subjected Colorado oil shale kerogen to oxidation with alkaline permanganate and analyzed the products obtained, as an aid in deducing information as to the structure of kerogen. Pertinent conclusions from this work include the following: ( a ) Kerogen appears to be essentially nonbenzenoid in character, in contrast to such humic substances as coal. This, in spite of the fact that 80% of the kerogen can be converted to “regenerated humic acids” by stepwise oxidation; ( b ) Molecular structure types which are indicated as perhaps being present in kerogen include noncondensed heterocyclic rings, noncondensed hydroxyl or methoxy substituted benzene rings, aliphatic chains, noncondensed aromatic ethers and aldehydes, noncondensed saturated cyclic ketones, monocyclic terpenes, and carbohydrates. Prien and Schnackenberg ( 4 6 0 ) have subjected kerogen (as shale) to thermal solution in solvents of various molecular configurations, at a temperature well beloTy that a t which thermal cracking occurs. Total yield of product oils was found to be a function of the molecular volume of the solvent. The carbonhydrogen ratio of these “oils,” as Fell as their nitrogen and sulfur contents, were found to be functions of the internal pressure of the solvents and their associating characteristics. From the data it ivas postulated that two forms of kerogen exist-viz., a low carbon to hydrogen ratio form rich in nitrogen and sulfur, containing 3 to 10% of all organic nitrogen and 10 to 20% of all organic sulfur; and a high carbon to hydrogen ratio (hydrocarbonlike) form poor in hetero atoms in relation to carbon, but containing the greater proportion of original kerogen nitrogen and sulfur. The authors further postulate that there is some evidence to suggest that kerogen is physically adsorbed on the inorganic matter of the oil shale. If this can be substantiated, it may be possible to establish that oil shale and petroleum are geologically related. A method for obtaining kerogen in more concentrated form for laboratory study has been evolved by Hubbard et al. ( Y O ) , using a combination of treatment with dilute acetic acid and sinkfloat separations. The carbon-hydrogen ratios of the kerogen concentrates were essentially the same as those of the original kerogen in the shale itself. R A W MATERIALS

A review of the geological distribution of the oil shales of France has been prepared (140). The 14 main deposits are described, only one of which, the ilutun, is at present being worked. In the author’s opinion French oil shale resources have been sadly neglected. -4flotation process for Baltic oil shale has been investigated in the laboratory ( 4 1 0 ) . Raw shale containing 30 to 35% organic matter is said to convert to a concentrate containing 90% organic matter, and a limestone fraction with 82 to 85% calcium carbonate, The latter is proposed as a raw material for cement Runnels ( 4 4 0 ) reports oil shale of 6 t o 12 gallons per ton richness in Kansas. A total of 3 billion barrels of oil are said to

.

September 1953

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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

2029

be available in beds of 3 feet minimum thickness and averaging 5 gallons per ton, Ertl (900) describes core drilling and logging of the shales of the Piceance Creek basin in northwestern Colorado. The Bureau of Mines (660) has re-examined the specific gravity to oil yield relationship of shales from the Mahogany Ledge, and reports a new curve on the basis of the data. The decomposition rates of the carbonates (dolomite and calcite) in Colorado shales have been studied in the range 1050' to 1600" F. (650). It is stated that carbonate dissociation in shale begins a t a temperature about 450" F. lower than for the corresponding pure carbonate. The rate of dissociation for calcium carbonate in shale equals that for pure carbonate a t temperatures 200" F. below the pure carbonate. The Sinclair Refining Co. (160) has patented a process in which oil shale is ground to a slurry in water acidified with hydrochloric or hydrofluoric acid, in order "to convert part of the inorganic constituents to active catalysts." Upon filtration, drying, and retorting a t 850' to 1000"F. an oil of lower specific gravity containing a greater proportion of gasoline is produced. Recent advances in blasting researchat the U. S. demonstration mine a t Rifle are discussed by Wright (590) and in the bureau's annual report (560). The latter reference also outlines changes made in the production mine, and research on drilling bits. A masonry-type bit has given best performance so far. RETORTS AND RETORTING PROCESSES

*

In a series of three articles (47D-490) Sherwood has reviewed the world oil shale situation, and particularly the advances in U. s. technology. In the second of these papers (480) the author points out that recent American retort development has been concentrated mainly on the internally heated type. Descriptions are given. The third paper (490) includes descriptions of various foreign retorts, and of retort auxiliaries. Mention is made of the use of filtration in the presence of a filter aid precoat, and of a bed of solids as a means of separating the emulsions formed in low-temperature condensates. Barnes (7D) has published design data for a 20,000-ton-per-day retorting unit producing 13,125 barrels per day of shale oil. Underground "retorting" of oil shale has been the subject of several papers. The Swedish Ljungstrom process is described again by Grindrod (MD),especially in reference to its application to the Athabasca t a r sands. Davis (170)presents a theoretical study of underground retorting, and states that necessary conditions are thick impervious overburden, 50-foot minimum bed thickness, and 5% minimum kerogen content. Electrical circuits for the heating elements are presented. Beyer ( 8 0 ) presents a brief description of the gas-flow process of retorting. Wells and Ruark (570) have compared hot shale gas, superheated steam, and hot flue gases as heating media, using a batch retort. With hot shale gas oil yield decreased with increasing inlet temperature and shale particle size, while gas yield increased in all of these cases. Superheated steam produced oil yields which were 97% of Fischer assay. Hot flue gases gave excellent results as long as the shale was closely sized. The results of a second 10-day run of the gas combustion pilot plant of the U. S. Bureau of Mines, employing 29-gallon-per-ton shale of a wide range of particle size are given in the current annual report (560). Also included therein are data from a study of shale feed rates, air rates, and recycle gas rates, the important variables for this process. The most notable new development in new retorting techniques involves the high temperature retorting of finely ground shale, a t 1200' t o 1800' F., and extremely short residence times in the hot zone ( l B 0 ) . The oil so produced is much higher in lower boiling aromatic hydrocarbons than conventional shale oils. Yields of 5 gallons of benzene per ton of 50-gallon shale are reported. Gases are rich in methane, hydrogen, ethylene, and carbon dioxide until 1800' F. is reached, whence only hydrogen and

C W R T E S Y U.S. BUREAU OF MINES

Figure 9.

Experimental Rotary Drilling Rig,

U. S. Bureau of

Mines

carbon monoxide are obtained. The process has definite promise as a source of chemicals from shale fines. The composition of the shale oil obtained is mentioned in greater detail in a subsequent section of this review. Important patents on retorts and retorting processes have been tabulated in a special section of the bibliography (IE-IIE). Included are patents on various aspects of fluidized retorting (4E7E, 9E-118) on a combination internally heated and externally heated retort (SE), on the use of recycle shale gas for heating ($E), and on thermal extraction ( I E , 8E). The reader is referred to the section mentioned for further details. PRODUCTS AND BY-PRODUCTS

Shale oil is, of course, the most important pod;ct of oil shale pyrolysis. Because of the number of papers on this subject alone, they have been grouped in a separate section on Shale Oil Properties, below. The L P gas plant of the Swedish Oil Shale Co. is described in a recent paper (5SD), together wit: the purification process for r'emoval and recovery of sulfur. Sirola (600) has isolated certain tar acid and base fractions from Serbian oil shale tar, and tested their inhibiting action in the autoxidation of gasoline. A 114' t o 123' C. fraction obtained by vacuum distillation a t 40 mm. proved most effective, while pyridine bases were least successful. The carcinogenic properties of a shale tar have been studied. Aeration, acetylation, and sulfonation reduced cancer incidence from this tar, by 57, 43, and 82%, respectively (160). Mapstone (SOD)has polymerized Australian shale tar bases with formaldehyde to yield acid-insoluble resins of the phenol-formaldehyde type. This same investigator has also successfully sulfochlorinated an olefin and aromatic-free fraction of shale oil in the presence of tungsten light, by the Reed reaction (360). According to a recent patent (100) alkyl sulfates can be pre-

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pared from shale oil olefins by first extracting with sulfur dioxide, furfural, or aniline, and thence sulfonating. Tests on 22 annual broad-leafed and grassy weeds indicate that shale oil 'can be effectively used as a contact herbicide ( 1 1 0 ) . S H A L E OIL PROPERTIES

Sherwood (49D)has reviewed the over-all status of shale oil refining to date. H e points out that the crude oil already has a carbon-hydrogen ratio similar to that of the heavy fuel oils formed in the normal cracking operations used for natural petroleum oils, and that a t present the high nitrogen content has prevented successful economic application of catalytic cracking techniques. Cost estimates are presented for producing various liquid fuels from Colorado shales. A similar review has also been presented elsewhere (400). See also the 1952 annual report of the U. s. Bureau of Mines (560). Kottes (350) discusses the refining techniques employed in Australia to produce standard petroleum products and such byproducts as cresylic acids, propane, and butane. High gasoline yields, which is the major objective sought, have been increased by use of thermally reformed retort naphtha from retort gases, Mapstone (380) has analyzed Australian shale oil naphthas and found C3 and Ca hydrocarbons, benzene, naphthalene, carbon disulfide, cyclopentadiene, indene, phenols, mercaptans, thiophenes, and pyrroles. I n a later paper (310) he reports that the discoloration of Australian cracked shale gasolines is due to the formation of quinones by oxidation, and the association of these quinones with pyridine homologs. This same author has examined the aqueous liquors from the crude oil separators at Glen Davis, and found ammonia, carbonates, sulfides, thiosulfates, ortho and meta dihydricphenols, and thiocarbamates (290). A series of studies on the continuous extraction of Manchurian shale oil and its derivatives, and polymerization of the extract has been carried out by Amagasa. The extracting agents included liquid ammonia (ID), a mixture of methanol and ammonia at 0' to 25" C. (SD), and 80 to 85% ethyl alcohol-water solutions (60). Polymerization was carried out with aluminum chloride for each of the three extracts. I n the case of the ammonia extract the polymerized product is said (WD) to be suitr able as a source of high quality lubricating oil. The methanolammonia extract was found ( 4 0 ) to yield a polymerized fraction of higher viscosity also suitable for lubricating oils. The polymerized ethyl alcohol extracts were not very promising (60). Woog (580) has patented a process for preparing lubricating oils from shale oil by fractionation to remove paraffinic constituents, addition of aromatic hydrocarbons to the residue, and polymerization with aluminum chloride. Alternately, the crude oil can be treated with hydrochloric acid, followed by addition of alkyl dichlorides prior to polymerization. The basic constituents of Manchurian shale oil have been examined in detail by Fushizaki (220), who has identified 17 homologs of alkylpyridine, and four of quinoline. Bille ( 9 0 ) has chromatographed the 200' to 325' C. fraction of Swedish shale oil. From the data obtained, as well as from ultimate analyses and further fractionations, he reports a preponderance of unsaturated highly cyclic hydrocarbons, and of oxygen- and sulfur-containing nonhydrocarbons. Attempts to identify hydrocarbon types were not successful. Dinneen and coworkers (180) have conducted a study of nineteen shale oils from seven different countries. All oils had compositions intermediate between petroleum and coal-tar distillates. Sulfur and nitrogen contents depended upon source. Sulfur ranged from 0.1 to 3%, but covered only a range of 0.26% in the case of the Colorado shales. Twice as much nitrogen was found for Colorado shales as for those from any other source. All oils produced from a given source shale by various retorting methods, as long as temperatures and residence times were similar, tended to have similar hydrocarbon compositions, Cady (IbD)examined the composition of 8 Colorado KTU oil

Vol. 45. No. 9

and found 39% hydrocarbons and 61% compounds of sulfur, oxygen, and nitrogen. The hydrocarbon fraction included 6% normal paraffins, 6% normal olefins, 5% isoparaffins and naphthenes, 12% isoolefins and cycloolefins, 4% monocyclic aromatic hydrocarbons, and 6% polycyclic aromatic hydrocarbons. The nonhydrocarbon portion included 36y0nitrogen compounds, 6% sulfur compounds, and 19% oxygen compounds. There appears to be a correlation between these data and the nitrogen and sulfur content of the two kerogen forms reported in the previously mentioned paper by Prien (460). Dinneen et al. (190) have reported the composition of the oils obtained by the high temperature (1200°, 1500', 1700" F.) retorting process (1.20)mentioned in a previous section of this review. All three oils were higher in aromatics. Benzene and naphthalene content increased with temperature, while toluene and methylnaphthalene reached a maximum at 1500' F. Phenol, o-cresol, and m-cresol predominated in 1500'-tar acids, while 2 , P dimethyIpyridine and symmetrical trimethylpyridine predominated in the 1500'-tar bases. The high pressure catalytic hydrogenation of Colorado (gas flow retort) shale oil has been studied by Pelipeta (380). At 900 pounds per square inch and 800' t o 900" F. an essentially sulfurand nitrogen-free product suitable for further standard petroleum processing was obtained. Some 40 to 50% of this oil is suitable for high quality Diesel oil. Hydrogen consumption, however, varied from 2000 to 2800 cubic feet per barrel of feed. The current Bureau of Mines annual report (560) contains data on the properties of gasolines prepared by hydrogenation of various aromatic shale gas oils at 1000 to 3000 pounds per square inch and 875" to 985" F. LOWsulfur and gum contents, and high lead response and stability were obtained. Current shale oil refining research a t the bureau, as summarized in the annual report (560), includes thermal reforming of naphthas, high temperature thermal cracking of NTU derived shale oil, further work on hydrotreating and acid treating of naphthas, chemical treatment of naphthas with boron trifluoride (BF3) and aluminum chloride (M&) for nitrogen removal, and catalytic cracking studies of shale oil distillates. Coking, recycle cracking, and viscosity breaking of shale oil and its distillates have been examined further by the Rifle staff. For further details the reader is referred to the 1952 annual report (660). Smith and Dinneen (510) have patented a process for removal of nitrogen from crude shale oil, by adsorptionon magnesiumsilicate, followed by elutriation of the hydrocarbons, and thence subsequent desorption of the nitrogen compounds with methanol. A N A L Y S I S AND TESTING

A modification of the standard Bureau of Mines method of analyzing crude petroleum has been devised for use in examining crude shale oil (630). About 500 ml. of sample is required. Properties obtained include gravity; aniline point: viscosity; yields of naphtha, light distillate, and heavy distillate; nitrogen content of the fractions mentioned, and tar acids and bases; nitrogen and carbon content of the residue; and hydrocarbon group analyses on neutral oils, Continuing their research on identification of thiophenes in shale oil naphthas (870), Kinney and coworkers have established a mass spectral correlation method for identification of thiophene and benzene homologs (260). The method is stated to be applicable to alkyl-substituted thiophenes of 126 to 154 molecular weight, and mono- or disubstituted benzenes of 120 to 148 molecular weight. Lake (280) has summarized the methods for nitrogen determination in shale and petroleum oils chosen by the American PetroleumInstitute cooperative project on this analysis. The Kjeldahl, Dumas, and ter Meulen methods are stated to he acceptable. Mapstone (330)reports that Mott's rapid method (340) for determining sulfate and pyritic sulfur can be applied to oil shale or torbanite. Pyrite content is calculated from extracted iron.

September 1953

INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY

2031

Organic sulfur is obhined by subtracting pyritic sulfur from total sulfur determined by the quartz tube combustion method.

(46A) Deinum, H. W., and Goedkoop, M. L., Chem. Weekblad, 48, 170-3 (1952). (47A) Delassus, M., Georgiadis, C., and Montigny, P., Compt. rend.

ACKNOWLEDGMENT

congr. ind. gaz (Assoc. tech. i n d . gaz France), 66th Congr. L y o n , 1949,597-611. (48A) Dept. Sei. Ind. Research (Brit.), Report for Year 1951,

The author is greatly indebted to Edgar Millaway for aid in collecting the more than 640 references which were screened for this review, and for arranging the literature citations. Appreciation is also expressed to Dorothy Talbott for typing the rnanuscript.

BIBLIOGRAPHY COAL PYROLYSIS

(1A) Ackeren, J. van, and Koppers Co., Inc., Brit. Patent 669,425 (1952). (2A) Allain, J., Compt. rend. congr. ind. gaz (Assoc. tech. i n d . gar France), 66th Congr. L y o n , 1949,495-507. (3A) Amemiya, T., Coal T a r ( J a p a n ) ,3 , 5 3 4 (1951). (4A) Andrews, R. S., Natl. Gas Bull. (AustTalia), 16, 4-10 (Jan.Feb. 1952). (5A) Aono, T., and Yamauchi, G., J . Electrochem. SOC.J a p a n , 20, 114-16 (1952). (6A) Aranda, V. G., and Arbunibs, J. A., Combustibles (Zaragoza), 11,319-23 (1951). (7A) Barlet, C., Compt. rend. congr. ind. gaz (Assoc. tech. i n d . gaz France), 66th Coagr. Paris, 1948,325-32. (SA) Barr, F. T., and Martin, H. Z. (to Standard Oil Development Co.), U. S. Patent, 2,592,377 (April 8, 1952). (9A) Barritt, R. J., Cokeand Gas, 14,180-2 (1952). (10A) Bastick, M., Bull. soc. chim. France, 1952,308-9. (11A) Belcher, R., A n a l . Chim. Acta, 8, 16-21 (1953) (in English). (12A) Berl, E., U. S. Patent 2,591,496 (April 1, 1952). (13A) Bhagat, H. P., Indian Patent 41,328 (Aug. 13, 1952). (14A) Blanzat and Barbe, Bull. soc. chim. Frame, 1952,569-73. (15A) Breck, C. R., Gas, 28, No. 5 , 4 4 4 (1952). (16A) Brender Brandis, G. A., and Felsbourg, J., Gas World, 135, 689-90 (1952). (17A) Bresler, A. E., and Zakolodkina, Y . I., Imest. A k a d . N a u k S. S. S. R.,Otdel. T e k h , N a u k , 1951, 1841-48. (MA) British Coke Research Association, Coke and Gas, 14, 280-4 (1952). (19A) British Coke Research Association, London, “Cooling and Quenching of Coke,” No. 9; “Removal and Recovery of Sulphur from Fuel Gases,” September 1952. (20A) Brit, Standards Inst., Brit. Standards, No. 1796 (1952). (21A) Brown, R. L., Caldwell, R. L., and Fereday, F., Fue2, 31, 261-73 (1952). (22A) Brown, R. L., and Carman, E. P., U.S. B u r . Mines, Inform. Circ. 7647 (1952). (23A) Burrough, E. J., Can. M i n i n g J., 73,63-73 (September 1952). (24A) Burstlein, E. M., and Societ6 des Aci6ries de Longwy, Brit. Patent 680,451 (1952). (25A) Campbell, R. W., Blast Furnace Steel Plant, 40, 643-50, 779436,800 (1952). (26A) C h a . Age (London), 67, 219-26, 357-61 (1952). (=A) C h a . Eag., 59,244-5 (March 1952). (28A) Chem. Eag. News, 31,2182-3 (1953). (29A) Chem. Trade J., 130,518 (1952). (30A) Chukhanov, Z. F., Doklady Akad. N a u k S.S.S.R., 81, 821-4 (1951). (31A) Claxton, G., Gas World, 135, No. 3538, Coking Sect., 68-70 (1952). (32A) Cleary, E. J., and Kinney, 3. E., Proc. Znd. Waste Cmf., 6th Cmzf., 1951; Purdue Univ. Eng. Bull., Extension Ser., No. 76,158-70 (1951). (33A) Coke and Gas, 14,273-9 (1952). (34A) Colson, M., Industrie chim. belge, 17, 369-72 (1952). (35A) Coppens, L., and Venter, J., I n s t . natl. ind. charbonnikre, Bull. tech.-Houzlle et &T~vBs. Mens., No. 4,58-117 (1951). (36A) Ibid., No. 5,11848 (1951). (37A) Ibid., NO.6,149-77 (1952). (38A) Cramp, G. B., U. S. Patent 2,581,517 (Jan. 8, 1952). (39A) Crawford, A,, Trans. Inst. M i n i n g Engrs. (London), 111, 204-18 (1951-52). (40A) Creelman, G. D. (to Pittsburgh Consolidation Coal Co.), U. S. Patent 2,595,338 (May 6, 1952). (41A) IbicE., 2,606,145 (Aug. 5, 1952). (42A) Cumming, A. P. C., and Morton, F., J . A p p l . Chem. (London), 2,314-23 (1952). (43A) Cunnah, J. E., Colliery Eng., 29,205-8 (1952). (44A) Damm, P., Er&l u. Kohle, 4,765-70 (1951). (45A) Davies, C., J . Fuel SOC. J a p a n , 30,259-76 (1951).

Command Paper 8494, London, Her Majesty’s Stationery Office. 1952. (49A) Directie‘ van de Staatsmijnen in Limburg, Dutch Patent 68,656 (Sept. 15,1951). (50A) Ibid., 69,186 (Dec. 15, 1951). (51A) Ibid., 70,816 (Sept. 15, 1952). (52A) Dudderar, F. A., Steel, 129, 98, 101, 104, 106 (November 1951). (53A) Ellis, C., Proc. Roy. SOC.(London), B139,449-63 (1952). (54A) Elphick, J. O., and Gerson, T., Fuel, 31, 43844 (1952). (55A) Ershov, V. N., and Pomerantsev, V. V., J . Gen. Chem. (U.S.S.R.), 21, 596-76 (1951) (English translation). (56A) Ewart, T. G., Can. M i n i n g M e t . Bull. 465, 264, 265 (1952). (57A) Farafonow, W., Australasian Engr., March 1951, 70-3. (58A) Fies, M. H., Gasification and Liquefaction of Coal Symposium, Ann. Meeting Am. Inst. M i n i n g Met. Engrs., New Yorlc, N . Y., Feb.20-1,1952, pp. 122-72. (59A) Firkin, T. M., Natl. Gas B u l l . (Australia), 15, 19-23 (MarchApril 1951). (60A) Forsdike, R., Gas World, 136,350 (1952). (61A) Francombe, K. W., Ibid., 135, No. 3533, Coking Sect., 53-7, 62 (1952). (62A) Franklin, R. E., Proc. Roy. SOC.(London), A209, 196-218 (1951). (63A) Fraser, T., Crentz, W. L., and Bailey, A. L., U.S. B u r . M i n e s , Bull. 483 (1950). (64A) Freebury, L. S., Gas World, 135,210-23 (1952). (65A) Fuchs, W., Industrie chim. belge, 17, 944-8 (1952). (66A) Fuchs, W., and Hamacher, K. A., Erddl u. Kohle, 5, 561-3 fIRh2). \ - - - - I .

(67A) Fuel, 31,33-6 (1952). (68A) Funasaka, W., et al., Bull. Inst. Chem. Research, Kuoto Univ.. 27,16-21 (1951). (69A) Gayle, J. B., U.S. B u r . M i n e s , Rept. Invest. 4933 (1952). (70A) Gayle, J. B., and Auvil, H. S., Ibid., 4923 (1952). (71A) Georgiadis, C., Compt. rend. congr. i n d . gaz (Assoc. tech. ind. gaz France), 66th Congr. Paris, 1948,389-97. (72A) Georgiadis, C., J. usines gaz, 76, 133-90 (1952). (73A) Gessner, H., and Zbinden, H. R., Schweiz. Ver. Gas-u. Wasserfach. Monats-Bull., 32,45-7 (1952). (74A) Given, P. H., et ai., Bull. Brit. Coal Utilization Research Assoc., 16,247-70 (1952). (75A) Golcsewski, S., H u t n i k , 18,481-4 (1951). (76A) Goodman, J. B., Gomez, M., and Parry, V. F., U.S. B u r . Mines, Rept.Invest. 4969 (1953). (77A) Goswami, M. N., and Roy, M., J . Sci. Znd. Research ( I n d i a ) , 11B,23941 (1952). (78A) Graham, J. P., Hall, G. E., and Lee, G. W., J . I n s t . Fuel, 25, 333-7 (1953). ENG.CHEM.,44,1011-14 (1952). (79A) Griffith, R.H., IND. (80A) Grosskinsky, O., Umbach, H., and Bergwerksverbrand zur verwertung von Schultzrechten der Kohlentechnik, G.m.b.H., Brit. Patent 670,847 (1952). (MA) GuBrin, H., and Bastick, M., Compt. rend., 234, 218-20 (1952). (82A) GuBrin, H., Bastick, M., and Marcel, P., Chaleur & ind., 33, 177-80 (1952). (83A) GuBrin, H., and MarceI, P., Bull. SOC. chim. France, 1952, 310-1 1. (84A) Gutzeit, G., Petroleum Processing, 7,828-32 (1952). (85A) Haarmann, A., Brennstofl-Chem., 33,321-7 (1952). (86A) Hadzi, D., Fuel, 32,112-13 (1953). (87A) Haringhuizen, P. J. (to Directie van de Staatsmijnen in Limburg), U. S. Patent 2,591,658 (April 1,1952). ( S A ) Hemminger, C. E. (to Standard Oil Development Co.), Ibid., 2,610,944 (1952). (89A) Hersche, W., Gas WorZd, 135,673 (1952). (9OA) Hess, H. V., and Arnold, G. B. (to Texas Co.), U. 5.Patents 2,618,664; 2,618,665; 2,618,666 (Nov. 18, 1952). (9lA) Hollings, H., Inst. Gas Engrs., Copyright Publ. No. 407 (1952). (92A) Howard, F. A. (to Standard Oil Development Co.), U. S. Patent 2,582,712 (Jan. 15,1952). (93A) Howard, H. C., IND.ENQ.,CHEM., 44,1083-8 (1952). (94A) Hurysz, J., Przeglad G6rniczy, 7,439-44 (1951). (95A) Igoe, J. W., and Rose, H. J., M i n i n g . Congr. J., 39, 72-8 (Feb. 1953). (96A) Intern. Chem. Eng. & Process Znds., 33, 120 (March 1952).

2032

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~(97A)I r o n Age, 169,51,52 (March 1952). (98A) Iyengar, M. S., J . Sei. I n d . Research ( I n d i a ) , 11B, 14-27 (1952). (99A) Iyengar, M. S., Rept. Proc. Symposia o n Fuels, Fats & Oils, and Research & I n d . ( I n d i a ) ,1950, 13-29. (100A) Jarry, R. M., French Patent 973,567 (Feb. 12,1951). (101A) Jerger, E. W., and May, J. R., Proc. Midwest Power Conf., 13, 78-85 (1951). (102A) Johnson, V. H., M i n i n g Eng., 4,391-5 (1962). (103-4)Jones, W. I., and Pontypridd Test Plant Committee, Brit. Coke Research Assoc., London, Tech. Paper, No. 5 (1952). (104A) Joumier, E., and Millereux, L., Compt. rend., 234, 2277-9 (1952). (105A) Kazakov, E. I., and Grigor’eva, K. V., Zhur. Priklad. Khim., 25,997-1000 (1952). (106A) Kec, J., I n s t . Gas Engrs. Communs. Repts., No. 404 (May 1962)(107A) Kimberly, R. L., Univ. Kentucky Eng. E x p t . Sta. Bull., S o . 21 (1951). (108A)King, J. G., Coke and Gas, 14, 363-7 (1952). (lO9A) Kirkby, W. A., and Sarjant, R. J., Xature, 170, 597-9 (1952). (llOA) Kitazaki, U., Yagishita, H., and Araki, H., Mise. Repts. Research I n s t . N u t . Resources ( J a p a n ) , No. 25, 51-60 (19523. (111A) Kitazaki, C., et al., Ibid., No. 22, 42-54 (1951); No. 26,52-9 (1952). (112A) Kiuchi, S., Tetsu-to-Hagane, 37,140-4 (1951). (113A) Kleinert, T., Austrian Patent 164,257 (Oct. 25, 1949). Brennstog-Chem., 33, 114-19 (1952). (114-4) Klempt, W., (1158) Koppers Co. Inc., U. S. Patent 2,581,409 (Jan. 8 , 1952). (116A) Kozakevich, P. P., Vilisvo, L. A, and Kononenko, A. F., Zhur. Obshch. Khim., 3, No. 7,808-18 (1933); Translation: Tech. I n f o r m . Circ., Battelle Memorial Institute, Columbus, Ohio, 9, 191-208 (February 1952). (117A) Krevelen, D. TV. van, Chem. Weekblad, 48, 202-8 (1952). (118A) Lahiri. A.. J . Sci. I n d . Research ( I n d i a ) , 11A. 146-58 (1952). (119A) Lang, W. A,, Can. Mzning N e t . Bull., No. 479, 148-52 (1952). (120A4)Leidi, G., Riv. Combustabili, 6,316-20 (1952). (1218) Le Paslier, R., Compt. rend. congr. ind. gaz (Assoc. tech. ind. gat France), 66th Congr. L y o n , 1949,219-43. (122.4) Lesher. C. E. (to Pittsburgh Consolidation Coal Co.), Brit. Patent 665,681 (Jan. 30, 1952). (123.4) Lesher. C. E. (to Pittsburgh Consolidation Coal Co.). U.3.

(126,4) Locke, C. R., Am. Gas Assoc., Proc., 33, 670-82 ( (127A) Lowenstein-Lom, V., Petroleunt (London), 15, 154-6, 160 (1952). (128A) hIcKee, J. H., Bull. Brit. Coal Utilisation Research Assoc., 16, 41-51 (1952). (129A) Mains, H . , Brennstof-Chem., 33,124-9 (1952). (130A) Mantel, W., andHansen, H., Ibid., 33,69-75 (1952). (131A) Ibid., pp. 75-80. [13224)Ibid., pp. 80-9. (133-4) Martinez de la Escalera, LI., D y n a , 26,265-68 (October 1951). (134A) Matheson, G. L., (to Standard Oil Development Co.), U. S. Patent 2,614,069 (1952). (13.54) Matsuyama, E., J . Fuel SOC. J a p a n , 31,262-6 (1952). (1366) ll-azov, A. V., T r u d y Vsesoyuz. Nauch.-Issledomtel Inst. Iskusst. Zhidkogo Topliva i Gaza V S I G I . ? 1950, S o . 2, 86-103. (137A) Meissner, H. P., and Hyde, R. W.(to Republic Steel Corp.), U. S. Patent 2,584,280 (Feb. 5, 1952). (138-4) Melan. H., Gas, Wasser, W a r m e , 6 , 169-71 (August 1952). (139A) LIichel, J., Compt. rend. congr. i n d . gaz (Assoc. tech. z n d . g a t France), 66th Congr. L y o n , 1949,647-54. (140A) Xidland Tar Distillers, Ltd. (Roland Scott and Eric 1%..Joscelvne. inventors), Ger. Patent 804,559 (April 26, 1951). (141A) Morgan, R. E., and Barkley, J. F., U . S . B U T .Mznes, Bull 512 (1952). (142.4) Morris, W. R., Am. Gas Assoc., Proc., 32, 1950, 374-94. (143A) Rlortimei, K. R., Cas World, 137, 581-2 (1953). (144A) LIulcahy, B. P., Blast Furnace, Coke Oven, and Raw Materials Proc. Conf. Am. I n s t . M z n m g X e t . E n g r s , 10, 54-89 (1951). (145A) RIuller-Neugluck, H. H., Brennstoff-Chem., 33, 119-24 (1952). (146A) RIyhill, A. R., Gas Times, 71,109,110 (1952). (147A) Ibid., 72, 47-51 (1952). (148A) Ibzd., 73,424,426,429 (1952). (149A) Nadmakiewicz, J., and Pampuch, R., Prace Glo’wnego I n s t . G6rnictzua (Ratowzce), Iiomun., KO. 79 (1951) (English summary). (150A) Nakagawa, S., J . PuelSoc. J a p a n , 29, 293-301 (1950).

Vol. 45, No. 9

(151A) National Coal Board, London, “Coal Carbonization Coke and By-products of Coal,” undated. (1526) Naugle, B. W., Davis, J. D., and Wilson, J. E., IND.EXG. CHEM., 43,2916-22 (1951). (153d) Nelson, K. J. (to Standard Oil Development Co.), U. S. Patent 2,582,711 (Jan. 15, 1952). (154d) Nickling, T., and Redman, M.,Gas World, 135,385-8,418-22 (1952). (155d) O’Connor, J. A., Chem. Eng., 58, 219, 222 (September 1951). (156-1) Odell, W. W. (to Standard Oil Development Co.), C. S. Patent 2,631,921 (March 17, 1953). (l57A) Odell, W. T.V., and Matheson, G. L. (to Standard Oil Development Co.), Ibid., 2,595,365; 2,595,366 (May 6, 1952). (158A) Oele, A. P., Brennstof-Chem., 33, 231-8 (1952). (159A) Oka, h-., et al., J . Fuel SOC.J a p a n , 29,302-4 (1950). (160-4) Onusartis, B. A., and Yur’evskaya, N. P., Zavodskaua Lab., 15,955-6 (1949). (161A) Orchin, AI., et al., U . S.Bur. Mznes, Bull. 505 (1951). (l62A) Oreshko, V. F., and Tislin, T. S., Z ~ Z LPriklad. T Khim., 25, 373-83 (1952). (163A) Otto, C., U. S. Patent 2,599,067 (1952). (164-4) Ibid., 2,611,739 (1952). (165A) Owen, L., Proc. Australasian I n s t . M i n i n g & Met., No. 15051,3-31 (1948). (l66A) Pamart, C., Compt. rend. congr. i n d . gaz (Assoc. tech. i n d . gaz France), 65th Congr. Paris, 1948, 156-70. (1678) Ibid., 66th Congr. L y o n , 1949,368-78. (168A) Paoloni, A., J . j o u r e‘lec., 61,83-103 (1952). (169-4) Petroleum Processing, 7,45 (1952). (170-4) Peytavy, A. A., and Lahouste, J., Compt. rend., 234, 934-5 (1952). (171A) Picon, AI.,Ibid., 231,1491-3 (1950). (172A) Pieper, P., Bergbau Arch., 13,50-61 (1952). (173A) Poncins, P. de. Compt. rend. congr. ind. gaz (Assoc. tech. ind. oaz France). 66th Connr. Lvon. 1949. 590-6. (174.2) Pound, G. S.;Coke and Gas, i4, 355-62, 401-7 (1952). (175A) Prax, Y., Chemistry & I n d u s t r y , 1952, S o . 22, 490. (176-4) Rademacher, W., Bergakademie, Die., Freiberg. Forch., hTo. 3; A . Bernbau, No. 1, 3-22 (1951). (177d) Rademacher, W.,Brennstof-Chem., 33, 129-35 (1952). (178A) Rao. G. R.. Rent. Proc. Svmvosia on Fuels. Fats & Oils and Research R. I i d . (IndiaK 1950, 44-7. (179d) Reed, F. H., et al., Blast Furnace Steel Plant, 40, 305-311, 344 (1952). (180A) Reerink, IT.,Brennstoff-Chem., 33,101-51 (1952). (181-4) Reid, A. H., Il’atl. Gas Bull. (Australia), 14, 21-3 (Nov-Dec. 1950). (1828) Reim, E. P., J . Chem. Met. M i n i n g SOC.S. A f r i c a , 52, 15660 (1952). (1836) Rex, W. A: (to Standard Oil Development Co.), E. S. Patent 2,608,526 (Aug. 26, 1952). 15, No. 167, 36-42; (184d) Reyes, H. G., Metalurgia y elec. (Spain), NO.168,38-44; NO.170,40-46 (1951). (185A) Robson. T. D.. Coke and Gas. 14,241-6 (1952). (1869) Rogan, J., Gas World, 136, No. 3546, Coking Sect., 25-6 (1952). (187A) Rosendahl, F., Chem. A g e (London),66,466 (1952). (188A) Sawai, L., et al., J . Chem. SOC.J a p a n , I n d . Chem. Sect., 54, 301-3 (1951). (lS9A) Schoberl, H., Brennstof-Chem., 33,241-4 (1952). (190-1) Schulte-Mattler, W., GlUckauf, 88,13-21 (1952). (191A) Scott, R., and Joscelyne, E. H. (to Midland Tar Distillers, Ltd.). U. S. Patent 2,598,449 (May 27. 1952). (1926) Sen, B. L., and Banerjee, T., J . Pro;. Inst. Chemists (Pndza), 24,7?-95 (1952). (193A) Seyler, C. A,. P ~ e l31, , 159-70 (1952). (194d) Shaw, J. A., A n a l . Chem., 23, 1788-92 (1951). (195A) Shiro, H. (to Nippon Iron hlfg. Co.), Japan. Patent 509 (Feb. 24, 1950). (196A) Shotts, R. Q., Fuel, 31,448-61 (1952). (197-&)Simek, B. G., Tejnicky, B., and Charvat, V., Palzm, 32, KO. 2,40-3; NO.3 , 6 4 4 (1952). and Brown, R. L., Prof. Paper No. PC-52-15, (198A) Smith, F. W., Am. Gas Assoc. Conf.. Los Angeles, May, 1952. (199A) SociBt6 des Btablissements Barbet, Brit. Patent 683,322 (Sov. 26, 1952). (200A) SociBtB de technique industrielle, French Patent 970,752 (Jan. 9, 1951). (201-4) SodBtB Technique de Provence, French Patent 989,186 (1961). (202-4) Spaulding, W. D., and Wassorkrug, B. K. (to National Steel Corp.), U.S. Patent 2,626,285 (Jan. 20,1953). (203d) Stephens, H. A., J . Inst. Australian Foundrymen, 2, 139-59 (1950). (204d) Stilcok Co., Coke and Gas, 14,272 (1952).

September 1953

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INDUSTRIAL AND ENGINEERING CHEMISTRY

(205A) Stillman, A. L. (to Fuel Research Corp.), U. S. Patent 2,590,733 (March25,1952). (206A) Suzuki, K., Kitaaaki, U., and Yagishita, H., Japan. J . Geol., 22,241-56 (1952). (207A) Szadecaks-Kardoss. E., Acta Tech. Acad. Sei. Hung.. 1, No. 2,125-32 (1951). (208A) Tawada, K., J . Fuel SOC.J a p a n , 31, 340-8 (1952). (209A) Terbeck, H., and Brutcher, H., Gliickauf, 81-84, 327-30 (1948). (210A) Terres, E., and Schultze, K., Brennstoz-Chem., 33, 353-61 (1952). (211A) Thau, A., Braunkohle, 5,12-20 (1953). (212A) Thibaut, C. G., Compt. rend. congr. ind. gaz (Assoc. tech. ind. gaz France), 68th Congr., Jude 1951,797-827. (213A) Thompson, R. J. S.,Gas World, 135, No. 3529, Coking Sect., 37-41 (1952). (214A) Tixier, C., J . usinesgaz, 76,183-7 (1952). (215A) Todd, T., Gas World, 135, No. 3529, Coking Sect., 42-8 (1952). (216A) Tomkbw, K., Prace Badawcze Gldwnego I n s t . Gdrnictwa (Katowice), Komun., No. 68 (1950). (217A) Trefny, F., Brennstog-Chem., 33, 104-14 (1952). (218A) Ibid., pp. 257-60. (219A) U.S. Geol. Survey, Circ. 90 (1951). (220A) Vahrman, M., J. A p p l . Chem. (London),2, 532-46 (1952). (221A) Waeser, B., Erdol u. Kohle, 5, 575-7 (1952). (222A) Warmuainski, J., Przeglad G6rniczy, 7,413-18 (1951). (223A) Weingaertner, E., E r d d l u . Kohle, 5,711-18 (1952). (2248) Weisa, H. L., and Orning, A. A,, Fuel, 31, 288-301 (1952). (225A) Wnekowska, L., and Caubek, S., Prace Gldwnego Inst. Gdrnictwa, Komun., No. 83 (1951) (English summary). (226A) Yagishita, H ., Mise. Repts. Research I n s t . N a t . Resources (Japan), No. 26,40-7 (1952). (227A) Ibid., NO.27, 69-79 (1952). (228A) Yagishita, H., and Araki, H., Ibid., No. 23, 28-38 (1951). COKE O V E N PATENTS

(1B) Allied Chemical and Dye Corp., Brit. Patent 664,352 (1952). (2B) Forsans, P. E. H., Ibid., 667,563 (1952). (3B) Horner, H. R., and Woodward, W. K. (to Reilly Tar and Chemical Corp.), U. S. Patent 2,622,361 (1952). (4B) Jones, W. D., and Otto, C. and Co., G.m.b.H., Brit. Patent 670,301 (1952). (5B) Kuhl, E., and Brennstoff-Technik, G.m.b.H., Ger. Patent 829,588 (1951). (6B) Kuhl, E., Sehrt, R., and Brennstoff-Technik, G.m.b.H., Ibid., 825,988 (1951). (7B) Les Fours Lecocq, S.A., Brit. Patent 667,566 (1952). (8B) Martin, H. Z . (to Standard Oil Development Co.), U. S. Patent 2,607,666 (1952). (9B) Nash, C. W. (to Woodall-Duckham Co. Ltd.), Ibid., 2,580,121 (1951). (10B) Otto, C., Brit. Patent 667,547 (1952). (11B) Otto, C. and Co., G.m.b.H. (Hellmut Temme and Wilhelm Schuchert, inventors), Ger. Patent 801,632 (Jan. 18, 1951). (12B) Poindexter, F. E. and Lowe, F. Mi., U. S. Patent 2,615,834 (Oct. 28, 1952). (13B) Records, E. H., Ibid., 2,586,862 (Feb. 26, 1952). (14B) Regie des Mines de la Sarre, Brit. Patent 672,168 (1952). (15B) Sievert, G., French Patent 986,623 (1951). (16B) Soci6t6 de Technique Industrielle, Brit. Patent 668,062 (1952). (17B) Soci6t6 Technique de Provence, French Patent 989,187 (1951). (18B) Takahashi, K., Japan. Patent 853 (March 31, 1950). (19B) Taylor, A , , and Woodall-Duckham Co., Ltd., Brit. Patent 673,112 (1952). (20B) Totzek, F., and Koppers, H., G.m.b.H., Ibid., 675,909 (1952). (21B) Woodall-Duckham Co., Ltd.,Ibid., 666,279 (1952). O V E N ACCESSORIES AND REFRACTORIES

(IC) Baker, E. W., and Koppers Co., Inc., Brit. Patent 676,754 (1952). (2C) Bamag-Meguin A.-G. (WilIy Franke, inventor), Ger. Patent 804,696 (April 26, 1952). (3C) Cokeand Gas, 14,107,108 (1952). (4C) Dobson, F. W. (to Woodall-Duckham Co., Ltd.), U. S. Patent 2,582,238 (1952). (5C) Drake, J. W. (to Koppers Co., Inc.), Ibid., 2,589,231 (1952). (6C) Gas Times, 71,366 (1952). (7C) Koppers Co., Inc., Brit. Patent 676,741 (1952). (SC) Ibid., 681,073 (1952). (9C) Ibid., 685,328 (1952). (1OC) Koppers, H., G.m.b.H., Brit. Patent 674,509 (1952).

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(11C) Ibid., 684,789 (1952). (12C) Lavely, P. H. (to Koppers Co., Inc.), U. S. Patent 2,576,126 (1951). (13C) Ibid., 2,589,266 (1952). (14C) Ogoraaly, H. J., and Rex, W. A. (to Standard Oil Development Co.), U. S. Patent 2,613,832 (Oct. 14, 1952). (15C) Plant, C . R., and Simon-Carves, Ltd., Brit. Patent 664,561 (1952). O I L S H A L E PYROLYSIS

(1D) Amagasa, M., et al., J . Chem. Soc. J a p a n , I n d . Chem. Sect. 52,319-23 (1949). (2D) Ibid., pp. 321-3. (3D) Ibid., 53,12-13 (1950). (4D) Ibid., pp. 65-6. (5D) Ibid., pp. 116-18. (6D) Ibid., pp. 156-7. (7D) Barnes, K. B., Oil Gas J . , 51, No. 21, 142-3 (1952). (8D) Beyer, H. A,, Erd6Z u. Kohle, 5, 630-2 (1952). (9D) Bille, R., Svensk K e m . Tidskr., 64, 113-21 (1952) (in English), (10D) Birch, S. F., Dean, R. A., and Anglo-Iranian Oil Co., Ltd., Brit. Patent 661,364 (Nov. 21, 1951). (11D) Bohmont, D. W., Farm Chemicals, 115, No. 3, 12-15 (1952). (12D) Brantley, F. E., et al., IND.ENG.CHEX.,44, 2641-7 (1952). (13D) Cady, W. E., and Seelig, H. S., Ibid., pp. 2636-41. (14D) Charrin, V., Chimie & industrie, 67,825-31 (1952). (15D) Cheney, L. K. (to Sinclair Refining Co.), U. S.Patent 2,609,331 (Sept. 2, 1952). (16D) Danetskaya, 0. L., Gigiena i Sunit., 1952, No. 10, 23-61. (17D) Davis. C. M., and Sleaak, J. M., Petroleum Times. 56, 306, 307 (1952). (18D) Dinneen, G. V., Ball, J. S., and Thorne, H. M., IND.ENG. CHEM., 44,2632-5 (1952). (19D) Dinneen, G. V., Smith, J. R., and Bailey, C. W., Ibid., 44, 2647-50 (1952). (20D) Ertl, T., Trans. Am. I n s t . Mining Met. Engm., Tech. Pub., No. 3316-A; M i n i n g E n g . , 4 , 6 0 1 4 (1952). (21D) Faber, G., Inst. Grand-Ducal Luxembourg, Sec. Sei. nat., phys. etmath., Arch., 19,265-82 (1950). (22D) Fushizaki, Y., Technol. Repts. Osaka Univ., No. 1, 309-17 !1951) (in German). (23D) Grindrod, J., Petroleum Times, 56,963-5 (1952). (24D) Hubbard, A. B., et al., U . S. B u r . M i n e s , Rept. Invest, 4872 (1952). (25D) Jukkola, E. E., et al., “Thermal Decomposition Rates of Carbonates in Green River Oil Shale,” preprint, Division of Industrial and Engineering Chemistry, 123rd Meeting, AMERICAN CHEMICAL SOCIETY, Los Angeles, 1953. (26D) Kinney, I. W., Jr., and Cook, G. L., A n a l . Chem., 24, 1391-6 (1952). (27D) Kinney, I. W., Jr., Smith, J. R., and Ball, J. S., Ibid., 24, 1749-54 (1952). (28D) Lake, G. R., Ibid., 24,1806-11 (1952). (29D) Mapstone, G. E., J. I n s t . Petroleum, 38, 98-107 (1952). (30D) Ibid., pp. 180-91. (31D) Ibid., p. 192. (32D) Mapstone, G. E., Durham, J. S.,and Taskis, E.D., J. Inst. Petroteum, 38,172-8 (1952). (33D) Mapstone, G. E., and Nartisissov, B., J . A p p l . Chem. (Lond o n ) , 2,405-8 (1952). (34D) Mott, R. A., Gas World, 132, No. 3237, Coking Sect., 66-7 (1950). (35D) Nottes, G., Petroleum Engr., 24, No. 13, C22-30 (1952). (36D) Nottes, G., and Mapstone, G. E., J. I n s t . Petroleum, 38, 178-9 - . - - fl9.52). >----,(37D) Organisation for European Economic Cooperation, Swedish Shale Oil, O.E.E.C., TAR-93 (52), 1, Paris, Oct. 1952. (38D) Pelipetz, M. G., et al., Chem. Eng. Progr., 48, 353-6 (1952). (39D) Petroleum (London),15,92-5,158-60 (1952). (40D) Petroleum Processing, 7, 1624-7 (1952). (41D) Rembashevskii, A. G., and Proskuryakov, V. A., Econ. Topliva, Za, 8,14-20 (Dec. 1951). (42D) Richards, S. H., Revs. Petroleum Technol. (London), 12, 380-92 ~~. .- (1952). --,(43D) Robinson, W. E., Heady, H. H., and Hubbard, A. B., IND. ENG.CHEM.,45,788-91 (1953). (44D) Runnels, Russel, et al., State Geol. Survey Kansas, Bull. 96,157-84 (1952). (45D) Savage, J. W., Savage Oil Shale Development Co., Debeque, Colo., 1952, private communication. (46D) Schnackenberg, W. D., and Prien, C. H., IND. ENG.CHEM., 45,313-22 (1953). (47D) Sherwood, P. W., Petroleum Refiner, 31, 97-101 (February 1952). (48D) Ibid., pp. 134-8 (March 1952). \ - -

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(49D)