INDUSTRIAL AND ENGINEERING CHEMISTRY Vogelsang, G. K. (to the Borden Co.), Ibad., 2,576,735 (Sov. 27, 1951).
Wakefield, L. B., IND.ESG. CHEJf., 43, 2363 (1951). Wakeford, L. E., and Hewitt, D. H. (to Sherwin-Williams Co.), U.S. Patent 2,556,488 (June 12, 1951). Ibid., 2,567,137 (Sept. 4, 1951). Walling, C., and Davison, J. A , , J . Am. Chem. SOC.,73, 5736 119511.
M-altei, H. A. (to Monsanto Chemical Co.), U. S. Patent 2,536,521 (Jan. 2, 1951). Varrick, E. L. (to Coining Glass Works), Ibid., 2,560,498 (July 10, 1951). Watson, W.H. (to Polymer Carp.), Ibid., 2,577,390 (Dee. 4. 1
1951).
Watts, J., Ann. Rept. Progress Rubber Technol., 14, 33 (1950). Weaver, W , I. (to Libbey-Owens-Ford Glass Co.), E. S. Patent 2,549,732 (April 17, 1951). Welch, L. M., and Wilson, H. L. (to Standard Oil Development Co.), Ibid., 2,548,415 (April 10, 1951). Wesp, G. L. (to Monsanto Chemical Co.), Ibid., 2,556,459 (June 12, 1951). Whitehill, L. N., and Shokal, E. C. (to Shell Development Co.), Ibid., 2,545,184 (March 13, 1951). Wicklatz, J. E. (to Phillips Petroleum Co.), Ibid., 2,564,632 (Aug. 14, 1951). Wicklatz, J. E., Kennedy, T. J., and Reynolds, W. B., J . Polymer Sci., 6, 45 (1951).
Wiener, H., Ibid., 7, 1 (1951). Wilder, R. S.,and Herman, D. F. (to Publicker Industries, Inc.), U. S. Patent 2,540,153 (Feb. 6, 1951). Wille, H., Brennstof-Chem., 32, 238 (1951). Winding, C. C., ISD. ENG.CHEW,43, 1997 (1951). Wingfoot Corp., Brit. Patent 655,377 (July 18, 1951).
Vol. 44, No. 9
(567) Winslou, F. H., and hlatreyek, W., IND.ENG.CHEM, 43, 1108 (1951). (568) Wittcoff, H., Modern Packaging, 24, No. 7 , 111 (1951). (569) Wittcoff, H., Peermau, D. E., Speyer, F. G., and Ronfew, M. M., I n d i a Rubber World, 124, 189 (1951). (570) Tittooff, H., and Roach, J. R. (to General Mills, Inc.), U. S. Patents 2,572,085, 2,5i2,086 (Oct. 23, 1951). (571) Wolf, R. J. (to The B. F. Goodrich Co.). Ibzd., 2,548,186 (April 10, 1951). (572) Ibid., 2,570,900 (Oct. 9, 1951). (573) Woolhouse, T. F., and Lunn, JV., Ibid., 2,568,313 (Sept. 18, 1951). (574) Wrigley, A. N., Siciliano, J., Xast, W.C., and Fisher, C. H., U . S . Dept. Agr., B u r . Agr. I n d . Chem., AIC-266, 7 (1950). (575) Yaiig, P. T., and Guile, R. L., J . Polymer Sci., 6, 881 (1951). (576) IToung, D. W. (to Standard Oil Development Co.), C . S.Patent 2,542,610 (Feb. 20, 1951). ( 5 i i ) Young, D. W., and Smyers, W.H. (to Standard Oil Development Co.), Ibid., 2,563,631 (Aug. 7 , 1951).
(578) Zenftman, H., and McGillivray, R. (to Imperial Chemical
Industries, Ltd.), Brit. Patent 653,489 (May 16, 1951). (579) Zerner, E., and Gradsten, M.A., (to Sun Oil Carp.),U. S.Patent 2,559,694 (July 10, 1951). (580) Zigeuner, G., K u n s t o f e , 41, 221 (1951). (581) Zigeuner, G., Schaden, W., Gabriel, O., and Teisenberger, E., Monatsh., 81, 1108 (1950). (582) Ibid., p. 1017 (1951). (583) Zinke, A., J . Applied C h e m ( L o n d o n ) , 1, 257 (1951). (584) Zinke, A., Zigeuner, G., \Veiss, G., Leupold-Lowenthall, W.9 and Wiesenberger, E., Monatsh., 81, 1098 (1950). (585) Zoss, -4.0. (to General Aniline & Film Carp.), U.3. Patent 2,555,179 (May 29, 1951). R E C E I V E Dfor review J u n e 25, 1952.
ACCEPTED July 8, 1952.
Pyrolysis of
'.
Coal and Shale !@g
CHARLES H. PRIEN
UNIVERSITY OF DENVER, DENVER, COLO.
Papers on coal pyrolysis during the past year have included discussions of the colloidal structure of coal, mechanism of swelling, function of the polar atoms present, and the kinetics of decomposition. The preparation of suitable blends for the oven and the effect of pulverization on coking have been noted. Fluidized bed coking and underground electrocarbonization are described, as is also pyrolysis b y dielectric means. Catalytic action of sodium compounds during low temperature carbonization and a rapid semicoking process employing superheated steam are mentioned. The substitution of calcium sulfate for acid in ammonia recovery is proposed, as is ethylene recovery b y selective solvent absorption. N e w methods of analysis for phosphorus have been devised. Underground gasification with oxygen has been suggested as a substitute for the Ljungstrom electrocarbonization of shale in Sweden. Little new research on the fundamental chemical nature of kerogen has been published. A fluidized vacuum retorting study, research on low temperature depolymerization in the presence of solvents, and an excellent paper on the role of nitrogen in shale oil hydrocarbon formation have been reported. A three-stage fluidization process of retorting has been patented. Hydrogenation studies on Colorado shale oil have been completed. A survey of methods of nitrogen determination in shale oil fractions has been conducted.
HIS is the fifth annual review of papers published in the field of coal and oil shale pyrolysis. Since the inception of this yearly summary in 1948 some 1130 references have been discussed in these pages. T h e growing list of articles which appear during each 12-month period is graphic evidence of the continued interest in this unit process and perhaps an adequate justification of the service which a review of this type can perform. Comments and criticisms as t o means by which this service can be improved and broadened are constantly sought and certainly u-elcomed.
T
I n keeping Rith previously estalilished policy all pertinent subject matter related to the general title has also been surveyed and included in the pages which follon-, T h e period covered, as usual, is primarily t h a t since June of the previous year.
COAL PYROLYSIS GENERAL
X number of general reviens of the field of coal carbonization have appeared during the past y a r . Birka (26) has described retort development in the gas industry over the past 100 years and noted t h a t thermal losses in the oven have been reduced by about 50% during this period. Cooke and Hutt (48)have examined present-day types of coking coal and the cokes therefrom, and the processes of carbonization. T h e relative fuel economy of the various carbonization processes, as vel1 as the raw materials and products suitable to each, in so far as both the gas and coking industry are concerned is indicated b y Townend (275). A history of developments in gas and fuel chemistry in America has appeared (79). See alp0 general reviews by Lang
September 1952
INDUSTRIAL AND ENGINEERING CHEMISTRY
(152), Krevelen ( I @ ) , and Ferrero (76), and a new book on coal technology by Fuchs (88). A general survey of scientific research in the coking industry has been published (129), as has also a discussion of the fuel research organizations, particularly in Canada (95) and current activity there. I n commenting on the order of priority for future research in coal carbonization in Britain it is suggested (122) t h a t feasibility of commercial exploitation should be the dominating criterion. The joint efforts of the Missouri School of Mines and the Sinclair Coal Co. to pyrolyze coal in the ground by use of electric current passed between vertical steel pipes, have been described in detail by Forrester (81). See also (58). Results obtained in three plants in Norway and America where electrically heated coke ovens are being employed are said t o indicate (184) the technical feasibility of such operations. A systematic tabulation of information relative to the production of metallurgical coke has been suggested by Wright (296). Methods for controlling by-product yields are reviewed by Trefny (276). A survey of the coking industry in Poland is given by Bolewski (80). The history of beehive coking in Japan and the advantages of beehive coke for foundry use are outlined (193). The importance of the coke oven in war production is enumerated (188) in a Canadian paper. A European proposal to subject all coal with over 15% volatile matter to carbonization and to utilize portions of the coke so obtained for power production has been offered by Stief (259). M E C H A N I S M , KINETICS, THERMOCHEMISTRY
*
Three papers on the colloidal structure of coal have appeared during the period under review. In, the first of theNe (24) the evidence for t h e micellar structure of coal and changes therein during coking is reviewed. I n the second paper it is pointed out (148) that coke formation is probably a coagulation of certain of the surface active micelles in the dispersed state, because of changes in the nature of the dispersion medium during heating. The third paper (266) is concerned with the control of coke formation processes b y the use of heats of wetting and electrical conductance. Certain x-ray studies are described in detail. I n the latter connection see also (127). Quantitative measurements of the internal surface area of various coals are given by Zwietering (SOO),who claims results from the heat of wetting tests are usually much too high. This conclusion is supported by Berkowitz (25). Krevelen (144) has presented additional evidence that the pyrolytic decomposition of coal is a first-order reaction. Using polyethylene, polystyrene, and polyindene as “model” substances, this author further speculates on the nature of the chemical bonds t h a t are broken upon carbonization. A recent paper (264) advances the theory that during the coking process hot gases form from decomposing bitumen, and being prevented from escaping, cause the swelling of the coke. I n two papers on the effect of the rate of heating of coal on the dynamics of the evolution of volatile matter Vekhov points out that higher rates of coking prevent early breakdown in the liquid products so obtained (283), while increasing the plasticity of the mass, and that separation of these liquid compounds begins when the plastic stage is attained and ends when semicoke is reached (284). The effect of controlled rates of heating of coal on the products obtained is also discussed by Jones (123, 124). The theory has been advanced (192) that the thermal stability of coal is a function of the number of polar atoms (oxygen, nitrogen, sulfur) which are present. Experimental evidence in support is presented. A new hypothesis for the fusion and carbonization of caking coals is given by Gillet (94). The effects of 1 to 2% aluminum chloride on condensation reactions of coal t a r pitch are presented by Bruckner (35’).
2065
From differential thermal analysis of lignin i t is concluded (29) t h a t the basic structure of lignin is present in all low-grade coals, but disappears as higher ranks are attained. The relationship of maximum coking temperature of certain American coals to the physical properties of the cokes obtained is described by Lowry (167). The effect of partial hydrogenation of coal on coking properties has been investigated (90). A review of the chemistry of turf coking has appeared (225). Fuchs (89) has studied the behavior of sulfur in coal pyrolysis and concludes that sulfur atoms probably replace carbon atoms in the graphite lattice, forming a stable but undesirable structure. This accounts for the fact that about 50% of the total sulfur remains in the coke. Equilibrium conditions in various carbonsulfur systems are shown. Dietsch (61) has examined the distribution of nitrogeft and sulfur in the products of both high and low temperature pyrolysis of certain Chilean coals. A graphical method for correlating sulfur and nitrogen content of coals and their cokes is suggested by Schuster (239); see also (173). Duck and Himus present (68) additional evidence that arsenic in coal occurs as arsenopyrite. R A W M A T E R I A L S AND PROPERTIES
The preparation of suitable blends of raw materials for the coke oven continues to be a major subject of papers appearing during the past year. A bulletin of the British Coke Research Association (SO) surveys present practices in the United Kingdom and offers a method of calculation for the economic effect of adding coke breeze. The association has also reviewed the blending practice of some 86 American coke plants (213). Both Kinoshita (131) and Hatano (108) have described tests on Japanese coals blended with anthracite. Two other Japanese authors (12, 187) report the results of using anthracite to prepare foundry coke. See also (206) and (267). For the manufacture of Japanese foundry coke from blends of semicoke and lignite, see (112). Sabatier (231) has summarized the status of coal blending in France. A new method of blending employed in Poland, involving separation of petrographic constituents b y difference in “brittleness,” has been proposed (191). T h e use of “drift” coal in amounts up to 10% has been shown not t o be deleterious (235) A comprehensive paper describing the application of certain speaial physical tests to the preparation of coking mixtures has been published (14). Laboratory tests are divided into those applicable to the materials u p to the point of formation of semicoke and those for the finished coke. Because of the restricted distribution of the journal the reader is referred to Chemical Abstracts, 46, page 1232c, for a comprehensive summary. Factors influencing the packing density of French coals are discussed by Masson (178). Spooner has shown (265) t h a t the swelling power of coal is directly proportional to the t a r produced upon pyrolysis and inversely proportional to the porosity of the coal. The Institute of Gas Technology has presented an excellent summary of the expansion behavior of coal during carbonization ( S q ) , together with certain correlations with laboratory tests. Further relations between Young’s modulus and the caking properties of coal have been derived (118). A series of articles on the friability of coal, by Fish (8O), has appeared. It has been shown (266) t h a t cokability of certain black coals and lignites is related t o the fact that these are derived from thick wood and bark tissue closely woven together. Hinder (111 ) has examined t h e petrographic constituent vitrain from many coals in the southern hemisphere and correlated the properties thereof with the products derived upon carbonization. The effect of pulverization on t h e coking of American coals has been studied by Mandal ( 176), who concludes t h a t degree of oxidation, rather than size, is responsible for previously reported effects in German coals in this regard. A recent patent (100) 1
2066
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
describes the results of additions of a hydrogel of silica and alumina t o oven charges m-hich include noncoking coals. Coke yield has been used as a new characterization factor of the quality of peat (280). T h e usual new articles on coking coal reserves of specific locales in the Unit.ed States and abroad, arid coking tests theron, have appeared during the period under revie\v. I n t h e case of American coals, see (49,60, 66, 6 3 4 6 , 1.$5)171). Tests on Japanese coals are found in (204, 2 7 7 ) , on Indian coals in (69,91, 98),and on Purijab coals in (174). For Chilean coals see ( 1 4 2 ) ; for Venezuelan coals, see (69). French coal-: of the Sarre and Lorraine are described in ( 118). The propcrtics of a !vide variety of British Comnioiiwealth coals are set forth in reference ( 8 6 ) . For tests on certain Canadian coals see ( 3 6 ) . h general survey of the world resources of coking coal may be lourid in a paper by Rueclrcl (250). HIGH TEMPERATURE CARBONlZATlON
The coking of coal in a fluidized bed continues t o occupy the attention of investigators and l o be the subject of a number of patents. Attention is direct'ed to three further pnt,ents by ?;elson (294-196) and a supplementary patent by Ode11 (2031, which include further extensions and improvement,s not nientioned in t h e last review ($16). See also a British 1):iterit (210). The use of the Itoyster pebblc bed technique, i.c., a fixed coal bed heated bp recycled hot inert gases, has also been patented ( 2 2 9 ) . I n a series of two papers Zanlrl (208, WRS) has shown the results, bot,h in thc laboratory and the plant, of adding approximately Zyo oil of the general composition C,H2,,, t o coal prior t o carbonization. It, is claimed that' 70 tn i 5 % of t,he heuting valuc of the oil appeared in t h e resulting gas. Higher percentages of oil, it is claimed by IVurz (897),produce delcterious deposits, and are also uneconomical according t o Schenlr (236). The use of electrically heated equipiiient for pyrolysis has been investigated further. h Russian paper describes (126)the use of high-frequency dielectric heating at temperatures up to 1000" C. A Konvegian patent (201) uses an elect,ricnlly he:it,ed resist'ance furnace a t the bottoni of a coke retort. Haniilton (106, 106) has reported on the operation of eight intermittent sinall vert'ical-chamber ovens, each Lvit'h a capacity of 2.3 tons of coal. The preparation of blast furnacc coke by using a Japanese coking coal blended with semicoke ground to less t h a n 0.3 mni., is described (115),as are also coking tests n-ith such seniicoke and lignite ( 112). The manufacture of inetallurgical coke from South Aifrican coals is detailed by Morgan and others ( 186). Simek (648) has followed the course of volatile products in an experimental oven and has found that, more than 75% of these substances move toward the oven walls. Ileteiar (bb4) has studied the coking of low- ash peat briquets. The pyrolysis of a mixture of high-volatile coking coal, flotation coal, and coke breeze in a hoppers-type oven is mentioned ( 6 7 ) . Spasov (26.54) has studied coal pyrolysis a t high pressures up to 25 tons per square centimeter and found t h a t t,he effect, of pressure is t o stabilize the organic materials and reduce carbonization. Additional data on 30 coals carbonized under the G. S. Bureau of Mines survey of American coking coals have been reported ( 5 5 ) , LOW TEMPERATURE CARBONIZATION
TM-obooks on low teniperature carbonization have appeal et< (205, 27.2). I n the latter of these the properties and utilization of low temperature coke from brown and bituminous are outr lined. A number of low temperature reviews have been published. Pound (612) surveyed various retorts and the produet. therefrom. W-etzel (600) reported on the history of low temperature pyi olysk in Europe and America. Recent progre-c in
Vol. 44, No. 9
this field has been reviewed (97, 123, 164). For a description of recent German developments, see (for). Lorenzen (163) claims that it is more economical t o convert bit,uininous coals to liquid fuels by low temperature carbonization then by hydrogenation. The Disco low temperature retorting process has been described in detail by Lesher (166). A new Bureau of Mines process einployiiig a modified low temperature distillation has been reported (40). A Russian paper mentions a "high speed semicoking process" employing superheated steam (198). For a paper on the pyi,olysis of peat in the presence of steam, see ( 8 7 ) ,and for a discu.ision of the coking of peat briquets, see ( $ 2 4 ) . In the latter connection, also note a careful study oil the theriiial decomposition of ileat,, by Kasakov (226). Rarich (222j investigat,ed the catalytic actmionof sodium conipounds on l o x temperature carbonization. -4lberti (8) reviex-ed t h e behavior of sulfur in the low temperature pyrolysis of lignit,e. Sulfur recovery from high sulfur-containing brown coals has heen investigated ( 1 6 0 ) . The use of vaste pyrolysis gases for hro.ivn coal carbonization is featured in a paper by Jilek (131). Specific lo^ temperature carbonization studies have been niade oii the coals of \I-ashington ( 4 7 ) :Japan (246), Russia (28$),and the Balkans (147). For patents oil new low temperature processing t,echniques, attention is called to (168, 262, 693). OVEN OPERATION
lkqmience gained during 30 years of operation of horizoiit :il retorts has been reviewed (5;). A book on horizontal retorh aiid their operation has appeared (113). Lewis (257) has suniinarized the results of performance tests performed during the paet 27 years on vertical retoi American and Norwegian experiments in heating coke ovens electrically have been reported (183).
The problem of better heat utilization in the coke oven coiitiiiues to be the subject of investigation. Jenkins (120)measured heat losses on a modern battery of 76 ovene supplied by blast furnaces gas, wit,h special attention to radiation losse?. Laming (150) has conducted a temperature survey on a continuous 1-ertical retort,. The general thernyal efficiency of coal distillation :ind gasification processes was considered by Dent (60); see itlso (76). A process for preheating t'he coal fed t o an oven has been patented (227). For a discussion of direct heat'ed low carlmnixation ovens, see (18f). The recirculat'ion of combustion products t o the coke oven is mentioned by Gubergrits ( 1 0 1 ) . The mixing of rich anti leiin gases for heating the oven is the subject of two patent8 (9, ( 5 4 ) ~ n of d a paper by hgroskin (4). Price (214) gives a detailed description of the cooling of 311 idle batt,ery of ovens a t the Colorado Fuel and Iron Co. A reries of six papers describing coke oven battery maintenance cluriiiy periods of steel plant idleness has been summarized (83). The relation between the carbonizing temperature, carbonizing time, and the width of the coke oven is treated by Terada (26!1), who derives a mathematical formula correlating these variables. The influence of coking conditions on tar yields and quality from Ruhr coals is stressed by Damin ( 6 2 ) ,and the importance of the c.onipensating main by Trefny (276). Leakage into the ovens lroni the flues and prevention thereof by control of hydraulic main pressure has been st~udied(7). The control of density of t>heoven charge by careful addition of oil aiid water is discussed, and it is stated (657) that about one pint of oil per ton of coal results in smoother operation. .% metshod of quickly repairing coke oven floors is mentioned (88). Forsans (86) describes a process for coking fines. The Bureau of Mines has compiled data on the rate of 01),solescence of coke ovens in 6lie C . S. (41). T h e application of ?tatist,ical analysis to process data from t'he coke ovens i. drmonatrated by Thomas ( 2 7 3 ) .
September 1952
INDUSTRIAL AND ENGINEERING CHEMISTRY
PRODUCTS AND B Y - P R O D U C E
A brief history of t h e by-products coking industry in Australia
2061
The paper by Pound (211) also sets forth methods for the dephenolization of the ammoniacal waste liquors from low temperature carbonization. More detail is given in ( l l ? ) ,which describes the use of butyl acetate for phenol extraction. Plant experience with the Phenosolvan process, which uses a mixture of esters boiling in the range 110" to 130" C. (predominantly butyl acetate), is related by Munderloh (190). A process of dephenolization based on the use of two straw-oil fractions as solvent, is said to remove 9570 of the phenols present in low temperature plant effluent (166). Pulicek (218) states that filtration with brown coal and pressure oxidation are successful methods of treatment,
and future developments in by-product recovery there has been published (73). Shaw (249) reviewed German practice with respect t o tar, ammonia, benzene, sulfur, gas, and phenol production from coal. Recent literature on the physical and thermal properties of coal hydrocarbons and their mixtures has been reviewed by Lochmann (162). A number of patents concerned with ammonium sulfate recovery are worthy of mention. Otto (207)describes an improved saturator for producing sulfate of larger crystal size. The Koppers Co. (138) has patented a process for contacting coke oven gas with the surface of an acid solution, a t liquor velociEOUIPMENT ties such as to "bring to I n keeping with past precewithin 4 inches of the surface dent the references mena t least 16.5 gallons of liquor tioned in this section are per pound of ammonia conlimited to only the more pertacted." A later patent by tinent patents and papers the same company (137) diswhich have appeared. The closes a two-stage process for listings are therefore necessimultaneous ammonia and sarily incomplete. pyridine recovery, I n the Brown (32) has designed a latter connection see also refnew small coke oven with B erence (256). Klempt (134) space 11 feet long b y 9 feet has studied the equilibria inhigh and a width tapering volved in the production of from 3 3 / ~ to 4l/2 inches. ammonium bicarbonate from Lorenzen (16giJ reviews brick coke oven gas. I n a paper and steel ovens for low tempublished at the same time, p e r a t u r e carbonization of Klempt (133) presents the renoncaking coals. The new sults of experiments on the Simon-Carves batteries of the substitution of calcium sulNantgarw plant in Britain, fate for sulfuric acid in amand their accessories, have Drilling and Logging a Test Core of Colorado oil Shale Deposits monia recovery. The new been described (46), Lampolyacrylonitrile fibers have ing (151) outlines a series of stimulated research on hvlaboratory experiments on scurf deposition and flaking of refracdrogen cyanide recovery from coke oven gas. Kastens (128) tories in continuous vertical retorts. gives details on the process of the Koppeis c'o. itt Kearny, N. J. Among new oven patents which have been issued are those for The use of ammoniacal by-product liquors as a nitrogen source a new horizontal oven with a vertical channel in each door to in soil fertilization is said t o be successful (253). carry away gases evolved at the bottom of the bed (908) and with The effects of the world sulfur shortage on ammonium sulfate alternate high and low burner nozzles in the flues (9, 10); a production in Britain are shown (44). T2eonet (156) presents a narrow retort for promoting carbonization in thin beds (292); an report on sulfur recovery in the Belgian Carbonization industry. electrical resistance-type furnace (200); a retort heated by comA new type of German sulfur recovery plant has been mentioned bustion gases from the devolatilized material discharged there(39)b u t no details are given. from (51); and a peat oven equipped with a screw conveyBr for A study on the recovery of ethylene from coke oven gas by the moving the charge (119). use of solvents has been set forth by Klenipt (135). It is stated Ackeren (3)has patented a new means of gas recirculation from that toluene and xylene are the most selective absorbents. The horizontal oven batteries and an improved method of cooling the use of coke oven gas as a glass furnace fuel and the design of basement air in underjet-fired ovens ( 2 ) . Wethly has patented burners therefor is the subject of a paper by Gunther (102). a new design of vertically flued oven (289). The influence of pressure and temperature on the yield of Recent patents on accessories include a new regenerator design benzene from coal pyrolysis in Polish plants is shown (287). for horizontal ovens (249), a leveller bar for introducing coke The refining of coal-derived benzene by catalytic hydrogenation breeze (138) and a bar with reduced sag a t the coke side of the of unsaturated impurities, patented originally in 1925, is now oven (199), and a sturdier buckstay and door frame structure for claimed to be commercially successful (278). For a book on ovens (182). benzene recovery, see (197). I n dry-cooling plants heat losses from the gas-recirculation I n a recent paper (84) it is argued that greater yields of useful system can be reduced, i t is claimed ( 1 1 4 ) , by jacketing the lines products from coal tar are technically and economically feasible. and preheating the primary air fed to the producers in the reThe origin of the phenols in low temperature tars has been studied sulting double-pipe exchanger. For a discussion of coke screen by Vahrman (279). The continuous fractionation of tar acid cloth, see (181). fractions to recover phenols, cresols, and xylenols, as practiced a t British Diesel Oil and Petrol Co., is described (116). See also a paper by Pound (211). The phenols and cresols in two samples C O K E PROPERTIES of high temperature tars from American coals have been deterThe commonly held opinion that size is the single most immined (92). A comparison of low temperature tars from ovens portant characteristic of metallurgical coke is the subject of a with steel or ceramic surfaces and from the direct Lurgi process in recent report (31). T h e microstrength and wet-oxidation tests which hot gas contact is secured has been made (70). For a new have been examined as substitutes for the usual tests for the book on coal tar, see (294).
2068
INDUSTRIAL AND ENGINEERING CHEMISTRY
suitability of coke for the blast furnace (109). Methods for the estimation of the pore size of metallurgical coke are reviewed by Gilchrist (93). A porosity test (resistance to gas flow) is discussed in a recent Russian paper (263). A review of x-ray and petrographic studies on the structure of coke has been published (266).
A new method for testing the reactivity of coke by controlled combustion a t 1300” C. is described by Banerjee (15). A review on the utilization of coke breeze has appeared ( I S % ) , covering steam raising, carbonization, briquetting, and other uses. The effect of coke breeze additions on metallurgical cokes from Silesian coals is discussed by Byrtus (56). Romwalter (228) claims that coke stability can be deduced from the stability of the microcrystalline units which are present and shows statistical evidence in support of his conclusion. The relationship of moisture content to coke size has been examined (120). Except for small sizes the moisture present was found to be inversely proportional to particle dimensions. I n a Russian paper the drum test and other physical tests, as applied to blast furnace practice there (140), are critically analyzed, Lownie (166) gives data in support of his contention, which has been noted before, that a stronger foundry coke will increase the capacity of the cupola. The properties of cokes prepared in the Kiel Gas Works from American coals are described by Siebel (246). Characteristics of dry-quenched coke are reviewed (199). The distribution of by-product and beehive coke in 1950 in the United States is given in the usual Bureau of Mines report (68). A N A L Y S I S AND TESTING
The U. S. Bureau of Mines has issued a report (78) describing its methods of analysis for coal and coke. An adaptation of the British Standard method is used for free swelling index and silicon carbide is employed as a diluent in determining agglutinating values. An information circular from the same source ( 1 7 ) has collected the opinions of 13 experienced fuel engineers as to the significance of BSTM laboratory tests of coal and coke for combustion. I n a preliminary report by the ASTM (11) it is recomniended that the Hardgrove machine grindability test for coal be adopted and the old ball mill test withdrawn. A comprehensive discussion of the significance of various laboratory coal tests has been published by Francois (86). I n (86) it is pointed out that attention must be paid to the atmosphere in which moisture determinations on coal are made. Belcher (19) notes that the ordinary desiccator is ineffective in preventing moisture absorption by dried coal. A discussion of the significance of moisture tests is given by Ward ($86)and Francois (86). A number of papers are concerned with elemental analyses on coal and coke. A new, small (40-ml.) bomb for sulfur determination is described by Siegfriedt (247). A rapid method for determination of total sulfur as barium sulfate is proposed (268). Davies (55) compares the Eschka and Strambi (262) methods for total sulfur and shows that the latter tests gives lower values. A new method of phosphorus determination, in which a solution of the inorganic constituents of coal is obtained by wet oxidation, from which solution phosphorus is determined colorimetrically, is described ( 7 1 ) . For an alternate colorimetric method, employing p-methylaminophenol, see (219). I n a review of methods for phosphorus determination (695) a modified Kjeldahl method is proposed. Radmacher ($31) reviews the Kjeldahl, Mantel and Schreiber, and the Dumas methods for nitrogen determination in solid fuels. Wildenstein (291) presents a direct method of oxygen determination, based on pyrolysis in a current of hydrogen. Laboratory assay methods of low temperature carbonization are discussed by Gomez Aranda (96) and a survey of laboratory coking tests is given by Ferrero (77). The determination of caking, smelling, and expansion tendencies of coal in a single
Vol. 44, No. 9
“dish” test, in which thin layer coking is essentially employed with the crucible method, is suggested by Gehle (92). Swelling and agglutination tests are compared and discussed by Pire (209). The correlation of various laboratory tests on coke with blast furnace practice is reviewed by Weed ($88),who emphasizes the need for rapid tests requiring the minimum of special equipment. I n the first of two papers on aqueous wastes from coke plant Shaw presents a test for phenol, which is said to measure concentrations as low as 20 parts per billion (244). The second paper (243) is devoted to tests for the estimation of the oxygenconsuming value of these wastes.
OIL SHALE PYROLYSIS Interest, in oil shale research continues to mount, as evidenced by the 70-odd papers on this subject which have appeared during the current 12 months under review. The more important of these references are listed in the sections to folloa~. GE NE R A L
The collected papers of the Second Oil Shale and Cannel Coal Conference held at Glasgow, Scotland, in 1950, have been published in book form (242). These papers were individually discussed in detail in the previous year’s review ($15). A number of new reviews on shale have appeared, including a brief literature review of the period 1939 to 1950 (72), a summation by Grand Ry (99), and one by Baranski (16). For a general report on fuels from shale by hydrogenation and other synthetic processes, see
(104). Guthrie and Klosky (105) present a comprehensive picture of the oil shale industries of Scotland, France, STYeden, Spain, and Germany from personal observation, together nith notes on Estonia. The Swedish shale oil industry is described in a recent paper by Schjanberg (240). I n view of the lack of water power in Sweden for the underground electrothermal Ljungstrom process, the inventor (161) suggests applying coal gasification processes t o the shales there, An account of the retorting plant and processes formerly in operation a t Glen Davis, New South Wales, Australia, is given by Kraemer and Thorne (141). Developments in Brazilian oil shale technology are mentioned by Abreu (1) and Rabin (620). Developments in American oil shale processing are reviewed by Mull (189), Sherwood (244, Berg (23), and Storch (261). Storch urges the continued support of long-range research and development work on all American synthetic fuel sources. The application of new techniques and equipment developed for mining the shales of the Green River formation a t Rifle, Colo., to other industries, is proposed by Sipprelle and Ballinger (250). The geology, occurrence, and processing of the low-grade Devonian shales of Ohio are examined in further detail by Krumin (145). A report of developments in the U. S. Bureau of Mines research program on shale is not possible a t this writing, because of the delayed publication of the usual annual report. 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
There has been relatively little n e v information published during the current year on the fundamental chemical characteristics of oil shale. Pringle and Barrick (216) have employed a fluidized bed to retort Colorado shale in vacuo a t pressures of 5 to 600 mm. This work is similar to investigations conducted 30 years ago by McKee and Goodwin (169), who used a mercury retort on Colorado shale a t 8 mm. of pressure; by Blackburn (27) who retorted a t 22 to 180 mm. of pressure, followed by highvacuum fractionation of the resulting primary bitumen; and by Luts (168) and Lindenhein (169) a t 7 to 20 mm. of pressure, working with Estonian kukersite and vacuum distilling the re-
September 1952
.INDUSTRIAL AND ENGINEERING CHEMISTRY
sultant oil. The present authors conclude that the heavy oil produced by fluidized vacuum retorting a t low temperature is "olefinic and cyclic in character." This is also true of the heavy shale oil fractions produced by the usual atmospheric retorting processes. Little further analytical data are given. Robinson and Hubbard (226) have presented an interesting study in which Colorado shale was carefully heated a t subretorting temperatures of 175' t o 300" C., using gases of composition similar to retort off-gases. Oil yield was shown to decrease with increase in temperature of the heating gas and with time and to decrease with shale particle size. Reducing atmospheres had no effect on oil or water yield but the presence of oxygen decreased the oil yield and increased the amount of water produced. Schnackenberg (237) and Prien have completed a study of the effect of solvent molecular configuration on the depolymerization of oil shale kerogen at very low pyrolysis temperatures (200" to 300' C.). Low internal pressure and the absence of hydrogen bonding were found to favor solubility, as did also high molar volume and large resonance energy for the solvent. An extremely low activation energy, of the order of 2000 calories per gram mole, for the decompositioon appears t o suggest a desorption mechanism for the initial "depolymerization" of kerogen. For a comprehensive discussion of the mechanism of decomposition of kerogen, in so far as the formation of is0 and cyclic compounds in the resulting shale oil is concerned, see an excellent paper b y Cady (37). Nitrogen compounds are stated to be the key factors in the sequence of degradation. R A W M A T E R I A L S AND PROPERTIES
Belser (21) has compiled an excellent report on the oil shale reserves of the Green River formation of northwestern Colorado, including logs of the more important core holes and surface samplings. Krumin (145) discusses the characteristics of the Devonian shales of Ohio. A detailed analysis of the inorganic matter in two series of oil shale samples of the Mahogany ledge near Rifle, Colo., is given b y Stanfield and coworkers (268). An analysis of the French lignitic schists of Vagnas has been made by Barlot (18), who also investigated their retorting characteristics. T h e occurrence of torbanites in the Union of South Africa is reviewed by Stelling (260), together with geological and historical d a t a on these deposits. Brazilian oil shales are described ( 1 , 220). Tertil (271) presents a classification system for bituminous shales. The electrical resistance of shale in the range 200' to 900' C. has been measured (6). A patent on a method of removing water from oil shale concentrates, involving flotation, filtration, an oil wash, and heating, has been issued (153). See also a patent for purification of raw oil shale by digestion with a 482" F. hydrocarbon oil at about 350" F. (62). RETORTS AND RETORTING PROCESSES
Ljungstrom has given a detailed discussion (161) of his wellknown method for electrothermal production of oil shale underground. It is stated t h a t two thirds of the energy input is required to heat the shale to the distilling temperature of 300" to 360" C., the remaining third being consumed by the pyrolysis. Underground gasification with oxygen is now being proposed as an alternate process, advantage being taken of the fact that Swedish shale foliates when subjected to pressure by pumped-in gas. Attention is called to a number of patents on retorting processes. Fluidization continues t o be the most popular new technique, as evidenced by recent patents by Thompson (274) and Atwell ( I S ) . See also a patent by Clark (42), which is concerned with combining fresh shale feed with hot shale from the combustion zone of the retort. Leffer (154) describes a threestage process of fluidization, which avoids dilution of the product gases and vapors from pyrolysis, with combustion gases.
2069
The preheating studies of Robinson and Clark (226),mentioned previously, are of interest in postulating the processes of decomposition which occur during retorting. For patents on thermal solution processes see a previously mentioned patent by Dongen (62) which employs a hydrocarbon oil a t 350" F. and a French (234) and a British patent (233), which propose the use of dichloroethylene a t 10" to 43" C. and normal pressure, for 11/4 to 11/2 hours. PRODUCTS AND BY-PRODUCTS
The principal product of the pyrolysis of shale is, of course, 'shale oil. Because of the number of papers on this subject it has been thought advisable to discuss shale oil properties in a separate section, t o follow. Schroeder (838) has discussed the potential synthesis of chemicals from oil shale and claims t h a t a shale plant producing chemicals could "pay for itself in 2 to 3 years." Spent shale is suggested (285) as a neutralizer for soil acidity, where it is said t o increase the availability of phosphorus. The extraction of low temperature oil shale tars with sulfur dioxide and other selective solvents has been carried out by Terres (870). Detailed criteria explaining t h e effect of temperature on t a r quality, hydrogen on phenol production, the influence of carbon dioxide on pyrolysis, and the effect of calcium carbonate on gas and phenol production in the thermal decomposition of a French oil shale has been presented by Barlot (18). Reichert (223) has examined a number of sulfonation products of sulfur-containing shale oils. Ahlborg (6) mentions six cases of hydrogen sulfide poisoning in the Swedish shale oil industry. S H A L E OIL PROPERTIES
Willcox (292) summarized present methods of producing and refining shale oil. Rocha (227)describes the oil obtained from a Brazilian shale, together with proposed methods of analysis. A French patent is concerned with the refining of the oil from the bituminous schists of t h a t country (46). The hydrogenation of a Colorado shale oil from a n N T U retort at 3000 pounds per square inch and 700' F. has been investigated by Smith and coworkers ( M I ) , using fixed bed, undiluted metal sulfide catalysts. Sulfur removal of 90% or more is reported and nitrogen was eliminated to less than 1% concentration. Hydrogenation of a shale oil coker distillate has been shown by Clark and coworkers (43) to be a feasible means of producing j e t and Diesel fuel. Reforming of the light hydrocarbon gases produced in the process, with steam, is said t o furnish the hydrogen required. I n the first of two papers Mapstone (179) states t h a t the hydrolysis of acid sludge produced in the acid treatment of shale gasoline from the Glen Davis refinery in Australia, is independent of the proportion of water used. I n a later paper (202) Mapstone gives the results of a n analysis of hydrocarbon types in the gas oil fraction of a shale oil from the same source. Cady and Seelig (37)have studied the composition of Colorado N T U shale oil. From their studies they conclude the following with respect to kerogen degradation during retorting: T h e yield of is0 and cyclic compounds depends primarily upon the denitrogenation of nitrogen compounds. The sequence is nitrogen compounds t o isoparaffins plus naphthenes, t o iso-olefins plus cyclo-olefins, to aromatics. The oxygen and nitrogen compounds in a Colorado shale oil naphtha have been identified by Van Meter, Ball, and coworkers (288). Pyridines, pyrroles, nitriles, and phenols are shown to be present, and the individual homologs in these classes are postulated. Kinney, Smith, and Ball (130)have identified some 17 individual thiophenes in Colorado shale oil naphtha. These compounds represent about 80% of the total sulfur compounds in this oil fraction.
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INDUSTRIAL AND ENGINEERING CHEMISTRY.
I n a recent patent McKinnis claims (170) that nitrogen bases can be extracted from shale oil by "an aqueous solution of an acid ammonium or amino salt of a etrong, nonvolatile inorganic acid, which forms a normal salt with the baqe." ANALYSIS AND TESTING
An escellent four-paper symposium on the determination of nitrogen in shale oil, in which the Dumas and Kjeldahl procedures on a micro-, semimicro- , and macroscale, were compared by 17 different laboratories, has been published. Crude shale oil, shale oil naphtha, and a shale oil Diesel fuel fraction were employed. I n the first paper Ball and Van Meter ( 1 4 )indicate that the macio-Kjeldahl method yields the most satisfactory result. The second paper in the series ( 1 4 9 )is devoted t o a n examination of the effect of digestion temperature on the Kjeldahl analyses, while the third paper, by Van Meter, Bailey, and Brodie ( M I ) , evaluates the Dumas procedure against results obtained by mass spectrometry. The last paper, b y Moore et al. (185), is devoted t o a perchloric acid titration procedure for distinguishing between basic and nonbasic nitrogen compounds. Continuing his excellent series of papers on nitrogen in oil shale and shale oil, as noted in detail in the previous review (216), Mapstone has added two additional articles t o the group. I n the first of these (17'6) he describes a volumetric method for determination of basic nitrogen in shale oil, employing xylene cyano1 a F a screening agent. The second paper (thirteenth in the series) iq concerned with an approximate method for determining pyridine nitrogen (17'7). hletcalf states (180) that p, p'-osydipropionitrile is a selective solvent for aromatic hydrocarbons in the presence of paraffins. This suggest8 the use of this compound in a liquid-liquid extraction method as a n analytical tool for hydrocarbon identification in shale oil fractions.
ACKNOWLEDGMENT The author desires to espress his appreciation t o M'erner Schnackenberg and Edward Mllaway for aid in the collection of the 700-odd references which were screened for this review and to Lora Keck for typing of the manuscript.
LITERATURE CITED (1) Abreu, S. F., Rev. qzriin. i n d . ( R i o de Janeiro), 20 (227), 12-16
(1951). (2) Xckeren, J. van (taKoppers Co., loc.), U. S. Pat?nt 2,537,197 (1951). (3) Ibid., 2,541,794 (1951). (4) Agroskin, A. A , , and Guhergriqs, hi. Ya., Izvest. A k a d . W a d 6 S.S.S.R., Otdd. T e k k . A-auk, 1949, 1626-41. (5) Agroskin, A. A., and Petrenko. I. G., Ibid., 1950,89-100. (6) Ahlborg, Gunner, Arch. I n d . Hug. Occupational Med., 3, 247-66 (1951). (7) Ahlers, W., Gas-u. Wassevfach, 92, 54-56 (1951). (8) Alberti, H. J. von, Bergbau 16. Energiewirt, 3, 159-64 (1950). (9) Allied Chemical & Dye Corp., Brit. Patent 660,175 (1951). (10) Allied Chemical & Dye Corp., U. S. Patent 2,564,141 (1951). (11) .4merican Society for Testing Materials, Report of Committee D-5 on Coal and Coke, Preplint 66, Philadelphia, 1951. (12) Arakawa, Y., J . Fuel SOC.J a p a n , 29,306 (1950). (13) At,well, H. V. (to Texas Co.), U. S. Patent 2,544,912 (March 13, 1951). (14) Ball, J. S., and Van Met,er, R., Anal. Chem., 23, 1632-4 (1951). (15) Banerjee, S., and Sarjant, R. J., Fuel, 30, 130-9 (1951). (16) Baranski, K., Przeglad Gwniczy, 7, 110-19 (1951). (17) Barkley, J. F., U.S. B u r . Mines, Inform. Circ. 7619 (1951). (18) Barlot, J., B u l l . soc. chim. France, 1951,736-9. (19) Belcher, R., and hiott, R. A., J . A p p l . Chem. ( L o n d o n ) , 1, 204-209 (1951). (20) Bolewski, A., H u f n i k , 18, 1-6 (1951). (21) Belser, C., U . S. Bur. Mines, Repts. Invest. 4769 (1951). (22) Bengtason, E., Ibid., 4755 (1950). (23) Berg, C., Petroleum Engr., 24, X o . 1, A37-43 (1952). (24) Berkowitz, N., Brennstof-C'hern., 32, 225-32 (1951). (25) Berkowitz, N., and Schein, H. G., Fuel, 31, 190-2 (1952).
Vol. 44, No. 9
(26) Birks, F. M., Gas J . , 267,520, 525 (1951). (27) Blaokburn, C. O., Quart. C o b . School M i n e s , 19, No. 2, 9 (1424).
(28) Bl&i>~;?mce Steel Plant, 39, 1127-8 (1951). (29) Breger, I. A., and Whitehead, W. L., Fuel, 30, 247-53 (1951). (30) British Coke Research A4ssociation, Coal Blending for Carbonization in Coke Ovens, Tech. Paper 4 (1950). (31) British Coke Research Association, Size Grading of Coke for Blast Furnaces, 1st Rept. Res. Comm. (1951). (32) Brown, C. O.,IND.ENG.CHEM.,43,No. 5,5711,588,60A (1951). (33) Brtlckner, H., and Huber, G., Gas-u. Wusserfaclc, 92, No. 5, (Gas', 53-4 11951). (34) Brysch: 0. P., and Ball, W. E., I n s t . Gas Tech. (Chicago), Res. Bull., 11 (1950). (35) Byrtus, F., P m c e Glownego I n s t . M e t , 3,85-95 (1951). (36) Burrough, E. J., Can. M i n i n g Met. Bul?., No. 470, 412-14 (1951). (37) Cady, W. E., and Seelig, H. S., preprint, Division of Petroleum Chemistry, 121st Meeting, AMERICAN CHmmxi, SOCIETY, hiilwaukee, 1952. (38) Cheasley, T. C., Utilization, 4, 27-8 (1950). (39) Chem. Eng. Yews, 29, 1662 (1951). (40) Ibid., p. 3462. (41) Ibid., p. 3576. (42) Clark, A., and Sailors, H. R. (to Phillips Petroleum Co.), U. 8. Patent 2,474,345 (June 28, 1949). (43) Clark, E. L., Hiteshue, R, W., Kandiner, H. J., and Morris, Bovd. IND. Ero. CHEM..43. 2173-8 119513. (44) Cokeand Gas, 13,53-4 (1951). (45) Ibid., pp. 303-15. (46) Compagnie F1 ancaise de Raffinage, Fiench Patent 973,167 (1951). (47) Conradi. L. .1..l'niv. Washington, Engr. E.zpt. SLa. Rept. 6 (1950). (48) Cooke, J. O., and Hutt, A. C., Smokeless A i r , 21, 116-22 (1951). (49) Crents, V.L., Bailey, A. L., and Miller, J. W., U . S. B u r . Mines, Repts. Invest. 4823 (1951). (50) Crentz, W. L., Steele, Fern, and Bailey, A . L., Ibid., 4763 (1951) . (51) Dalin, David, Hedbiick, T. J., Gejrot, C. J., and Johansson, A. TI'., U.S. Patent 2,550,677 (1951). (52) Damm, Erddl-u. Kohle, 4, 765-70 (1951). (53) Davies, I., and Jackson, P. J., J . A p p l . Chem. (London), 1951, SUPPI. 1, 54-57. (54) Davis, G. -4.(to Allied Chemical 8: Dye Corp.), U. 8. Patent 2,554,818 (1951). (55) Davis, J. D., .4m.Gas Assoc. Proc., 32, 402-9 (1950). (56) Davis, J. D.. Reynolds, D. A,, Brewer, R. E., Wolfson, D. E., Xaugle, B. IT., and Birge, G. W., U.S. B u r . Mines, B u l l . 496 (1951). (57) Davis, J. E., and Stott, C., Inst. Gas Engvs., Concmuns. and Repts. 387 (1951). (58) DeCarlo, J. A , , and Ryan, E. E., U . S . Dept. I n t e r i m , Mineral I n d . Surceys, iMineral Market Rept. 2034 (1951). (59) Delicado del Valle, .J. M., Rea. S O C . venenolnna quim., 10, No. 22,29-35 (1950). (60) Dent, F. J., Gas J . , 267,230-2,240 (1951). (61) Dietsch, J . , Anal. I o congr. pan-amer. ing. mines y g e o l . Santiago, Chile, 4, 1376-90 (1942). (62) Dongen, L. F. K. van (to Foster-Wheeler Corp.), U. 8 . Patent 2,524,859 (Oct. 10, 1950). (63) Dowd, J. J., Turnbull, L. A . , Toenges, A. L., dbernathy, R. F., and Reynolds, D. A., U . S . Bur. M i n e s , Repts. Invest. 4801 (1951). 164) Ibid.. 4803 (19511. (65) Ibid.] 4807 i1951). (66) Dowd. J. J., Turnbull, L. A., Toenges, A. L., Cooper, H. M., Abernathv. R. F.. Revnolds. D. A.. and Crents. W. L.. Ibid., 4757 (1950). " (67) Dubois, Josef, Milaszewicz. Olpierd, and Kahane, Saymon, Przeglad Gorniczy, 6, 339-46 (1950). (68) Duck, N. IT., and Himus, G. W., Fuel, 30,267-71 (1951). (69) Duttn Roy, R. K., Records Geol. Survey I n d i a 75, Prof.Papers, NO. 3, 1-27 (1940). (TO) Eisenlohr, H , and Obenaus, IT., Erdbl-u. Rohle, 4, 557-61 (1951). (71) Ellington, E'., and Adams, W. S . ,Fuel, 30,272-4 (1951). (72) Erdol-u. Rohle, 3,495-7 (1950). (73) Farafonow, W.,Australasian Engr., 1951, 70-73 (March 7, 1951); cf. J . I r o n Steel Inst., 169, 284 (1951). (74) Fe, F. P., Combustibles (Zaragoza), 10,304-34 (1950). (75) Ferrara. E., Termotecnica, 4, 547-51 (1950). (76) Ferrero, P., Schweiz. V e r . Gas-u. Wasserfnch, Monats-Bull., 30, 275-86 (1950). (77) Ibid., 31, 45-57 (1951) ~~
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September 1952
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
(78) Fieldner, A. C., and Selvig, W. A., U . S. Bur. M i n e s , Bull. 492 (1951). (79) Fieldner, A,‘ C., Gauger, A. W., and Yoke, G. R., IND.ENG. CHEM.,43, 1039-49 (1951). (80) Fish, B. G., Colliery Eng., 28,317-19 (1951). (81) Forrester, J. D., and Sarapuun, E., Univ. Missouri School M i n e s and Met., Bull. 78 (1952). (82) Forsans, P. E. H., French Patent 965,802(1950). (83) Fort, G. A.,et al., Am. Inst. M i n i n g Met. Engrs., Blast Furnace, Proc. 9,162-83 (1950). (84) Fowler-Williams, A., Intern. Chem. Engr. Process Znd., 32, 159-64 (1951). (85) Francis, W., Inst. Fuel (London),Preprint, March 6,1951. (86) Francois, J., Chaleur & I d . . 31,301-5 (1950). (87) Fridman, G. E.,DokEady A k a d . N a u k S.S.S.R., 77, 875-7 (1951). (88) Fuchs, P., “Kurzgefasste Technolopie,” Berlin, Kammer der Technik, 1950. (89) Fuchs, W.,Brennsbff-Chem., 32,274-6 (1951). (90) Garcia-Conde, J. R., Combustibles (Zaragozu), 10, No. 51, 10-14 (1950). (91)Gee, E. R., Recorda Geol. Survey I n d i a , 75, Prof. Paper 11, 1-46 (1940). (Si) GeNe, H., Gas-u. Wasserfuch, 92, No.7 (Gas) 73-7 (1951). and Taylor, J., J . Znst. Fuel, 24,207-11 (1951). (93) Gilchrist, J. D,, (94) Gillet, A.,Nature, 167,406-7 (1951). (95) Gilmore, R. E., and Cameron, A. E., Can. M i n i n g M e t . Bull., 44,145-54 (1951). (96) Gomez Aranda, V. and Martinez Cordon, J. L., Combustibles ( Z a m g o z a ) , 10,No. 51,3-9 (1950). (97) Gomez Aranda, V.,Martinez Cordon, J. L., and Auria Albunies, J., I b d . , NO. 52, pp. 93-108 (1950). (98) a s h , S. S.,et d.,Brennstoff-Chm., 32,368-74 (1951). (99) Grand Ry, G. de, Ann. mines, 49,592-611 (1950). (100) Green, William, Brit. Patent 660,374(Nov. 7, 1951). (101) Gubergrits, M. Ya., Zzvest. A k a d . N a u k . S.S.S.R., Otdel. Tekh. NuuIC, 1950,1016-23. (102) Gunther, R., Gas-u. Wasserfach, 92,No.15 (Gas) 201-2 (1951). (103)Guthrie, B., and Klosky, S., U. 5. B u r . M i n e s , Repts. Invest. 4776 (1951). (104) Hall, C. C.,Inst. Petroleum Rev., Petroleum Technol., 10,244-63 (1951). (105) Hamilton, G., Gas J., 266,306-8,315 (1951). (106) Hamilton, G., and Whitehead, C., Gas W o r l d , 134, 278-80 (1951). (107) Hansen, C. J., Brennstoff-Chem., 32, 97-104 (1951). (108) Hatano, M., J. Fuel SOC.J a p a n , 29,306 (1950). (109) Hewitt, F. J., Gas World, 135, No. 3524, Coking Sect., 21-32 (1952). (110) Hills, D.C., and Holmes, C. R., TND. ENQ.CKEM.,43, 1635-8 (1951). (111) Hinder, N., J . R o y . Sac. N . S. Wales, 83, 195-209 (1950). (112) Hisada, S., J . Fuel SOC.J a p a n , 29, 194 (in English, 198-9) (1950). (113) Hock, H.,“Horirontalkammerofen,” Munich, R. Oldenbourg, 1951. (114) Hofmann, E., Schweiz. Yw. Gas-u. Wasserfach, Monats-Bull., 31, 42-5 (1951). (115) Imai, K., J . FueZSoc. J a p a n , 29, 1934 (1950). (116)I n d . Chemist, 27,497-501 (1951). (117)Ibid., pp. 545-50 (1951). (118) Inouye, K.,J . Colloid Sci., 6, 190-210 (1951). (119) Jarty, A. A. B., French Patent 972,449(1951). (120)Jenkins, D., Gas World, 133, No. 3481, Coking Sect., 46-50 (1951). (121) Jilek, J., Paliva a voda, 31,14-19,36-46 (1951). (122) Jones, W.I.,Gas J., 268,488-93 (1951). (123) Jones, W. I., Gas W o r l d , 135, No. 3520, Coking Sect., 15-18 (1952). (124) Jones, W. I.,J . Znst. Fuel, 24,69-75 (1951). (125) Karavaev, N. M., Sevast’yanov, Yu. L., Dolgopolov, N. N., and Bur’yan, Yu. L., Doklady A k a d . N a u k . S.S.S.R., 77, 871-4 (1951). (126) Kasakov, E.I.,Izvest. A k a d . N a u k S.S.S.R., Otdel. Tekh. N a u k , 1949,1219-30. (127) Kasatochkin, V.I., Ibid., 1951,1321-34. (128) Kastens. M. L.. and Barraclough, R.. IND.ENG.CHEM..43, 1882-92 (1951). (129) Kellett, S., Gas World, 135, No. 3520, Coking Sect., 13-14 (1952). (130) Kinney, I. W.,Smith, J. R., and Ball, J. S., preprint, Division of Petroleum Chemistry, 121st Meeting, AMERICAN CHEMICAL SOCIETY, Milwaukee, 1952. (131)Kinoshita, H., J . Fuel SOC.J a p a n , 29,305 (1950). (132)Kirov, N. Y.,Bull. Brit. Coal Utilisation Research Assoc., 15, 37-44 (1951).
207 1
(133) Klempt, W.,Ber. Ges. Kohlentech, 5,401-13 (1950). (134) Ibid., pp. 414-420. (135) Ibid., pp. 460-72. (136) Koppers Co., Inc., Brit. Patent 651,282(1951). (137) Ibid., 653,325(May 16,1951). (138)Ibid., 659,381 (1951). (139) Zbid., 660,773(1951). (140)Kozlowski, T., and Nadriakiewicr, J., H u t n i k , 16, 297-310 (1949); cf. J . I r o n Steel Inst., 165,463 (1950). U . S. B u r . M i n e s , Repfs. (141) Kraemer, A. J., and Thorne, H. -M., Invest. 4796 (1951). (142)Krassa, P., Chait, Enrique, and Thumm, Carlos, Anales Io congr pan-amer. ing., minus y geol., Santiago, Chile, 4,1391-3 (1942). (143) Krevelen, D.W. van, Chem. Weekblad, 46,233-53(1950). (144) Krevelen, D. W.van, Fuel, 30,253-9 (1951). (145) Krumin, P. O.,Ohio State Univ. Studies, E n g . E x p t . Sta. Bull. 143,1-29 (1951). (146)Kunii, S.,J . Fuel SOC.J a p a n , 29,196,200-1 (1950). (147) Kurchatov, M. S.,Annuaite univ. Sofia, Faculte Sci., Livre 2, 45,l-27,summary in Russian, 28-30 (1948-9). (148)Lahiri, A.,Fuel, 30, 241-7 (1951). (149) Lake, G. R., McCutchan, Philip, Van Meter, Robert, and Neel, J. C., A n a l , Chem., 23,1634-8 (1951). (150) Laming, J., Gas J . , 265,235-7 (1951). (151)Laming, J., and Rigby, G. R., Gas J., 265, 419-20, 425-6, 431-2 (1951). (152) Lang, W. A., Can. M i n i n o M e t . Bull., 471,472-7 (1951). (153) Larsson, M. (to Liljenroth, F. G . ) , Canadian Patent 468,282 (1950). (154) Leffer, F. W. (to Universal Oil Products Co.), U. S. Patent 2,544,843(March 13, 1951). (155) Leonet, G., Coke and Gas, 13,326-7 (1951). (156) Lesher, C. E.,Trans. Ant. Znst. M i n i n g M e t . Engrs., Tech. P u b . 3264-P;Mining Eng., 4,287-99 (1952). Gas J., 265,223-4,229-32(1951). (157)Lewis, C. H., (158) Linberg, T., German Patent 762,217(1951). (159) Lindenhein, H. A. R., Arch. sci. phys. et nut., 3,379 (1921). (160)Lissner, A , , Bergbau u. Energiewirtsch, 3, 188-9 (1950). (161) Ljungstrom, F., Tek. Tid., 81,33-40 (1951). (162)Lochmann, C., Brennstoff-Chem., 32,301-9 (1951). (163) Lorenzen, G., Zbid., pp. 324-31. (164)Low Temperature Coal Distillers of Great Britain, “Progress with Low Temperatuie Carbonization Fuel,” National Smoke Abatement SOC.,Proc. Harrogate Conf., 1949,26-7. (165) Lowenstein-Lom, V.,Petroleum (London), 14,33-5 (1951). Foundry, 79, K O .7,72-6 (1951). (166)Lownie, H.W., (167)Lowry, H. H., Chemistry and I n d u s t w , 1950,619-25. (168) Luts, K., “Der estlandische Brennschiefer-Kukersit, seine Chemie, Technologie und .4nalyse,” Tartu, Estonia, 1934. (169) McKee, R. H.,Quart. Colo. School M i n e s , 18, No. 1, Suppl. A (1923): (170) McKinnis, A. C. (to Union 011 Co., Calif.), W. S. Patent 2,518,353(Aug. 8, 1950). (171) Maeda, K., and Sanada, hI., J . Fuel Sac. J a p a n , 29, 193 (1950). (172) Maillard, P., Rev. Franc. Energie, 3, No. 16,149-58 (1951). (173) Mainr, H., Gliickauf, 87, 1045-53 (1951). (174) Majid, A,, and Ahmad, B., P a k i s t a n J . Sci., 1,72-6 (1949). (175) Mandal, A. K.,and Orning, A. 4.,Fuel, 31,33-6 (1952). (176)Mapstone, G. E., J. Proc. Roy. SOC.N. S. W a l e s , 84, 30-3 (1950). (177) Zbid., pp. 34-7. (178) Masson, R., Compt. rend. congr. ind. gaz, Assoc. tech. ind. gaz. France, 66,254-69 (1949). (179) Mathews. R. C.,and Mapstone. G. E., J . Inst. Petroleum. 37,147-57 (1951). (180) Metcalf, E. C.,et al., Petroleum Refiner, 30, No. 7, 97-100 (1951). (181) MGkie, A. A,, Blast Furnace Steel Plant, 39, 1091-3 (1951). (182) Millard, R. K., U. S. Patent 2,571,597(1951). (183) Minchin, L. T., Elect. T i m e s , 169,168 (1951). (184)Minchin, L.T., Gas W o r l d , 134,297-91 (1951). (185) Moore, R. T.. McCutchan, P., and Young, - D. A,. A n a l . Chem.. 23,1639-41 (1951). (186) Morgan, T. D.,Bossert, J. P., Harris, J. F., and La Grange, C. C.. J . Chem. Met. M i n i n n SOC. S. Africa. 51.219-38 .(19.51). - .- - , (187) Norihana, Y.,J . Fuel SOC.J a p a n , 29, $06 (1950). (188) Morris, W. R.,Can. Chem. and Process Inds., 35,118-22 (1951). (189) Mull, J. B., J . Petroleum Technol., 2, Sect. 1, 14-16 (1950). (190) Munderloh, H., ErdaLu. Kohle, 4, 177-80 (1951). (191) Nadziakiewica, Julian, Przeglad Gorniczy, 7,73-5 (1951). (192) Nadziakiewicz, Julian, and Pampach, R., “Thermal Decomposition Temperature of Coals,” Prace Glownego Znst. G‘orniczy, Kommunilc No. 79 (1951). (193)Nakagawa, S.,J . Fuel Soc. Japan, 29,301 (1950).
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(194) Kelson, K. I., and Howard, F. A. (to Standard Oil Development Co.), French Patent 963,986 (1950). (195) Nelson, K. J. (to Standard Oil Development Co.), U. S. Patent 2,549,117 (1951). (196) Ibid., 2,554,263 (May 22, 1951). (197) rewall, H. E., Inst. Petroleum Rec., Petroleum Technol., 10, 284-95 ~.~ . (19513. (198) Nickolaev,’ A. ’M., and Chukhanov, 8. F., Doklady Akad. ~ V a u kS.S.S.R., . 78, 267-70 (1951). (199) Nitskovich, E. A., Ekon. Topliva, Za., 7,21-25 (1950). (200) Norsk Hydro-Electrisk Kvaelstofaklieselskab, Norwegian Patent 75,000 (June 18, 1951). (201) Ibid., 77,415 (1950). (202) Nottes, G., and Mapstone, G. E., J . I n s t . Petroleum, 37,259-64 (1951). (203) Odell, W. W. (to Standard Oil Development Corp.), U. S. Patent 2,557,680 (June 19, 1951). (204) Oka, N.,J. Fuel SOC.Japan, 29,304 (1950). (205) Olden, >I. J. F.. I n s t . Petroleum Rev., Petroleum Technol., 10, 264-83 (1951). (206) Ono, Y., J . Fuel SOC.Japan, 29,305 (1950). (207) Otto, Carl, Brit. Patent 655,171 (1951). (208) Ibid., 658,661 (1951). (209) Pire, L. R., Combicstibl~s(Zaragoza), 11, 71-82 (1951). (210) Pittsburgh Consolidated Coal Co. (to Safford, R. V.), Brit. Patent 658,542 (1951). (211) Pound, G. S., Chem. Trade J., 128,901-3 (1951). (212) Pound, G. S., J . Inst. Fuel, 24, 61-8 (1951). (213) Powell, A. R., and Russell, C. C., “Coal Blending in American Coking Industry,” British Coke Research Association, Proceedings 4th Conf., London, 1950. (214) Price, J. D., Blast Furnace Steel Plant, 39,203-13 (1951). (215) Prien, C. H., IND.ENQ.C ~ ~ i ~ . , 4 3 , 2 0 0 6 -(1951). 15 (216) Pringle, J. W., Barrick, P. L., and Wigton, H. F., IND. ENG. CHEM,,44, 1489-91 (1952). (217) Puening, F., U. S. Patent 2,552,014 (1951). (218) Pulicek, J., Paliva a voda, 30,308-19 (1950). (219) Puri, R. P., and Benerjee, 8. P., J . Sci. I n d . Research ( I n d i a ) , 10B, 86-8 (1951). (220) Rabin, J., Rev. quim. i n d . (Rio de Janeiro), 19, No. 221, 22-3 (1950). (221) Radmacher, W., and Lange, W., GZ.Lickauf,87,739-46 (1951). (222) Ravich, M. B., J. Applied Chem. (U.S.S.R.), 24,970-5 (1951). (223) Reichert, B., and Schwebs, U., Pharmazie, 3,493-5 (1948). (224) Reteiar, Arpld, Magyar Kem. Folydirat, 57, 97-100 (1951). (225) Retehar, Arphd, Magyar Kem. L a p j a , 5, 242-7 (1950). (226) Robinson, W. E., and Hubbard, A. B., U.S. Bur. Mines, Repts. Invest. 4787 (1951). (227) Rocha, E. F., Rev. quim.i n d . (Rio de Janeiro), 19, No. 224, 1215 (1950). (228) Romwalter, Alfred, Acta Tech. Acad. Sci. Hung., 1, No. 2, 75-82 (1951) (in German). (229) Royster, P. H., U. S. Patent 2,536,098 (1951). (230) Rueokel, W. C., Blast Furnace Steel Plant, 39, 195-9, 327-32, 426-38, 540-8 (1951). (231) Sabatier, J. L., “Coal Preparation and Blending in French Coking Industry and Present Practice and Research,” British Coke Research Assoc., Proo. 4th Conf., London, 1950. (232) Sainte-Fare, XI. de, French Patent 981,527 (1951). (233) Schabelitz, E. J., Brit. Patent 654,753 (1951). (234) Schabelitz, E. J.,,French Patent 974,759 (1951). (235) Schenk, P., Gas-u. Wasserfach, 91 (Gas) 308 (Dec. 1950). (236) Ibid., 92, No. 17 (Gas), 233-7 (1951). (237) Schnackenberg, TT. D., Master of Science thesis, University of Denver, 1952. (238) Schroeder, W. C., preprint, Xat. Capitol Sect. Meeting, Am. Inst. Chem. Engrs., 1951; cf. Chem. Eng. News, 29, 1830 (1951). (239) Schuster, F., Gas-u. Wasserfach, 92 (Gas) 30-33 (Feb. 15, 1951). (240) Schjanberg, Edmund, Abhandl. brauschweig. wissenschaftl. Ges., 3, 216-38 (1951). (241) Sell, G. F. (editor), “Oil Shale and Cannel Coal”, Vol. 11, London, Institute of Petroleum, 1951. (242) Shaw, H. P., Coke Ouen Managers’ Assoc. Yearbook, 1951,
__
2.17-5.1
(243) (244) (245) (246) (247)
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Vol. 44, No. 9
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ACCEPTEDJuly 28, 1962.
