INDUSTRIAL AND ENGINEERING CHEMISTRY
2006
(324) Stober, K. E., and Amos, J. L. (to Dow Chemical Co.), Ibid., 2,530,409 (Nov. 21, 1950). (325) Sully, B. T. D., J. Chem. SOC.,1950, 1498. (326) Sully, B. T. D. (to A. Boake Roberts and Co., Ltd.), U. S. Patent 2,498,226 (Feb. 21, 1950). (327) Surmatis, J. D. (to Chemical Development Corp.), Zbid., 2,499,7943 (March 7, 1950). (328) Susameyer, L., Chim. peintures, 13, 71 (1950). (329) Sward, A. F., I n d i a Rubber World, 121, 681 (1950). (330) Swern, D. (to U. S. A., Secy. Agr.), U. S. Patent 2,516,928 (Aug. 1, 1950). (331) Taft, W. K., and Goldsmith, H., IND.ENG.CHEM.,42, 2542 (1950). (332) Tasdur, R., K i m y a ve Sanayi, 5,50 (1950). (333) Tawney, P. 0. (to United States Rubber Co.), U. S. Patent 2,505,844 (May 2, 1950). (334) Ibid., 2,507.871 (htay 16, 1950). (335) Ibid., 2,524,684, 2,524,685 (Oct. 3, 1950). (336) Ibid., 2,526,434 (Oct. 17, 1950). i337) Tegge, B. R. (to Standard Oil Development Co.), Ibid., 2,529,318 (Kov. 7, 1950). (338) Thurmond, C. D., Paint Vurnish Production Mgr., 30, No. 5, 10 (1950). (339) Tkachenko, G. V., and Khomiskvskii, P. N., Doklady A k a d . N a u k S . S . S . R . , 72, 543 (1950). (340) Toy, D. F. (to I-iotor Chemical Works), U. S. Patent 2,497,637. 2,497,638 (Feb. 14, 1950). (341) Trommsdorf, E., Chem-Ztg., 74, 217 (1950). (342) Troyan, J. E. (to Phillips Petroleum Co.), U. S. Patent 2,508,734 (Mav 23. 1950). (343) Tyran,'L. k: (to E.'I. du Pont de Nemours & Co.), Zbid., 2,532,583 (Dee. 5, 1950). (344) Upson, R. R . (to E. I. du Pont de Nemours & Co.), Zbid., 2,511,310 (June 13, 1950). (345) Ibid., 2,517,944 (-4ug. 8. 1950). (346) Ibid., 2,517,945 (Aug. 8 , 1950). (347) Van Berg, C:. F. (to Standard Oil Development Co.), Ibid., 2,523,168 (Sept. 19, 1950). (348) Vanderbilt, R . M., and Bascom, F. (to Standard Oil Development Co.), Ibid., 2,527,162 (Oct. 24, 1950). (349) Vaughan, ,% F., Chemistry I. & Industrv, 1950,76. (350) Vystrcil, A., and Bohdaneck9, M., Chem. L i s t y , 43,97 (1949). (351) Wagner, H. P., U. S. Patent 2,514,734 (July 11, 1950). (352) Wakefield, L. B., and Bcbb, R. L., IND.ENG.CHEM.,42, 838 (1 950).
Vol. 43, No. 9
(353) Wakeford, L. E., Hammond, W. T. C., and Lewis Berger and Sone, Ltd., Brit. Patents 640,832, 640,836 (July 26, 1950). (354) Wall, F. T., Florin. R. E., and Delbecq, C. J.. J . Am. ChrfrL. Sac.. 72. , 4769 (19501. . (355) Walling, C., Briggs, E. R., Cummings, \V.,and Mayo. 1,'. R.. Ibid., 72, 48 (1950). (356) Walling, C., and Snyder, R. H. (to Cnited States Rubber C'o.). U. S. Patent 2,500,265 (March 14, 1950). (357) Walsh, D. C., and Schutse, H. C. (to Standard Oil De1,elopment Co.), Ibid., 2,521,431, 2,521,432 (Sept. 5, 1950). (358) Weber, K. H. (to Armstrong Cork Co.), Ibid.. 2,497,107 (Feb. 14, 1950). (359) Weber, K. H., and Powera, P. 0. (to Armstrong Cork C O . ) , Zbid., 2,518,509 (Aug. 15, 1950). (360) Weigand, F. G., Am. Po,int J.,35,S o . 5, 62 (1950). (361) Whitby, G. S., Wellman, N., Flouts, V. W., and Stephens, N . L., IND. ENG.CHEM.,42, 445 (1950). (362) Whitmore, W. F., and Gei,echt, J. F., J . A m . Chem. Soc., 72, 790 (1950). (363) Wilde, M. C. de, and Smets, G., J . P o l ~ wSci., 5 , 283 (1950). (364) Wiley, R. H., and Hobson, P. H., Zbid., 5 , 483 (1950). (365) Williams, E. G. (to Imperial Chemical Industries, Ltd.), V. S. Patent 2,500,728 (March 14, 1950). (366) Williamson, L., ,J. Oil and Colour Chemists' Assoe., 32, 579 (1949). (367) Wilson, W. K. (to Shawinigan.Resins Corp.), U. S. Patents 2,508,341, 2,508,342, 2,508,343 (May 16, 1950). (368) Winding, C. C., IXD. ENG.CHEX.,42, 1724 (1950). (369) Wingfoot Corp., Brit. Patent G42,423 (Sept. 6, 1950). (370) Yarsley, V. E., and Unsworth, A. K., Brit. Plastics, 23, 23 (1950). (371) Young, D. W. (to Standard Oil Development Co.), U. S. Patent 2,534,095 (Dee. 12, 1950). (372) Young, J. H. (to E. I. du Pont de Xiemours & Co.), Ibid., 2,497,828 (Feb. 14, 1950). (373) Yurzhenko, T. I., Puchin, V. A . , and Grigor'eva, K. S., Doklady A k a d . N a u k S.S.S.R., 75, 547 (1950). (374) Ziegler, K., Brennstof-Chem., 30, 181 (1949). (375) Ziegler, K., Eirners, E., Hochelhanimer, W., and Wilms, H., Ann., 567, 43 (1950). (376) Zinke, A., and Ziegler, E., Fette u. Seifen, 52, 588 (1950). (377) Zwicker. B. M. G.. India Rubber World, 121, 431 (1950). I
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RECEIVED June 10, 1051.
Pyrolysis of Coal and Shale E
CHARLES H. PRlEN
UNIVERSITY OF DENVER, DENVER, COLO.
I
S CONFORMANCE with previously established policy, this
fourth annual review, although principally concerned with coal and shale pyrolysis, their mechanism and their application, is extended to include all pertinent subject matter related to this unit operation. The period covered is primarily t h a t since June 1950, except for previous omissions growing out of the normal lag in the publication of papers and abstracts. The author would welcome pertinent comments, criticisms, and suggestions for improvemen ts.
COAL PYROLYSIS GENERAL
One of the outstanding events of the past year, in so far as the coal carbonizing industries are concerned, was the Fourth World Power Conference, held in London in July 1950. Papers presented at this conference (46)pointed out the need for conservation of depleting reserves of coking coals in the worId, discussed carbonization of low-rank coals, and compared merits of coke
ovens ( 2 1 )and gas retorts (217)for gas production, see particularly ('71). Specific papers dealing with individual areas of coal carbonization are noted under their appropriate headings in the sections t o follow. Several reviews on coal pyrolysis have appeared during the past year. Attention is called t o a summary of pyrolysis in the gas industry for the past 30 years by Foxton (70); a progress report on all phases of coke oven practice, including raw materials, oven equipment and operation, and by-products by Barritt ( I O ) ; and a thorough well-annotated German review by Umbach (263). For reviews on gas coke, see (47, 66). The U. S. Bureau of Mines surveyed the influence of increased use of natural gas on coal and coke production and concluded (62) that about 2% of annual coke capacity will be lost through such competition in the next 5 years. The importance of the coke industry t o the present U. s. emergency economy is stressed in a paper by Morris (172). The present-day position of the coal carbonization industries in
September 1951
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
A l t h o u g h no radically new developments in coal pyrolysis were reported during the past year, substantial contributions to a more detailed understanding of all facets of this unit operation continue to be made. Increased attention is being given to processes for coking low-rank coals, because of the steady depletion of more workable reserves. Better control of the coking process through the use of fluidized beds was suggested. The role of various petrographic constituents and ash during carbonization is under further study, as are the causes of swelling. Reasons for the failure of most existing low temperature carbonization processes to live up to expectations have been reviewed; better heat economy in oven operation is still being sought. Because of current sulfur and benzene shortages improved production methods have become popular research goals. M i n o r constituents of coal and coke ash are becoming of interest in the coking process, and hence new analytical procedures are appearing. Research activity in oil shale pyrolysis i s increasing sharply, and is reflected in the large number of papers published during the current year. Additional evidence of a benzenoid structure for certain kerogens has been obtained. The kinetics of kerogen decomposition were re-examined, and a thorough study of the nitrogen compounds was completed. N e w retorting processes include both a gas combustion retort, a ball-mill type with heated pebbles, and a radiant retort to yield aromatics. N e w data on shale oil refining were acquired.
various forpign countries has been the subject of a number of papers. Barritt (11) outlined the factors governing the economic size and location of coke ovens for British steel mills. Burstlein surveyed ( 2 7 ) the technical and economic aspects of various processes for coking of the French coals of Lorraine. A new battery of Simon-Carves ovens u as constructed a t Hirapur, India (45), as xvvas the first coke oven plant in Jugoslavia (38). Several papers from Russian sources were noted, including a description of the supply and demand for coke in western Germany (167). M E C H A N I S M , KINETlCS, T H E R M O C H E M I S T R Y
An excellent summary of present-day theories of the physical and chemical changes occurring during coal pyrolysis, irrespective of the equipment employed, was prepared by Jones (113). This paper points out the advantages of controlled heating of coal either in thin beds or by the fluidized solids t,echnique, as a means for obtaining increased yields of gaseous and liquid products. Multistage heating is suggested as a prefractioniition process for volatiles. Separation of various petrographic constituents from bright and dull coals, because of their different coking characteristics, in order t o modify product properties, is mentioned. The influence of the petrographic constituents of bright and dull coals on the coking process is analyzed in even grrater detail in an article by Terres (2b4) who discusses their relntionship t o shrinking and sivelling, heat of carbonizatim, and cokc~strength. Reference is also made to a study on the mechanism of hydrogenation and pyrolysis of the anthraxylon fraction of bituminous coal, by the U. S. Bureau of Mines ( 195). McKee published a worth-while study on the function of the inert material of coal during the Carbonization process. He concluded (160) t h a t inerts maintain the porous structure of the matrix during pyrolysis. The greater swelling of high-ash coals is believed due to loss of rigidity of the coal structure as a result of the quantity of inert filler present. The role of inerts in slow and rapid carbonization is postulated. The effect of maximum carbonization temperature on coke properties, including elemental analysis and various physical properties, has been described by Lowry (145). The paper states that a t temperatures below 800” C. the ash content of the coal used has no bearing on the mean size or spread of the coke, a s determined in standard drop-shatter tests. A graphical-statistical method, in which the atomic ratio of hydrogen t o carbon is plotted against the atomic oxygen to carbon ratio, has been used (127) to study the carbonization process in coals. Final product is said to have the composition (CsH200.is),. These data, together with the results of oxidation, hydrogenation, and solvent extraction studies, using the same diagram, confirm the conclusion t h a t coal is not a homogeneous macromolecule. From research on the humic acids from oxidized bitumi-
2007
nous coal it is concluded ( 1 ) th:tt. neither fusion nor evolution of volatile aromatic fragrnentv occurs when t h e w substances are pyrolyzed. The distribution of carbon, hjdrogcn, oxygen, arid nitrogen in the products of pyrolysis was reportc,tl l)y Kustov ( 1 3 1 ) ; however, little nelv information is not,ed. For a s u m marized discussion of the vwiotls physico-chemical steps occurring tiuring coal pyrolysis the reader is rctforretl t,o :in article by Iciphng ( 11 8 ) . R A W M A T E R I A L S AND PROPERTIES
Foxwell and Johnson ( 7 2 )presented a revicv of coal requirements for carbonization in Great Britain, and trends therein during rcctxnt years. These requirements have been related particulnrly to gas manufacture by Burns (26). Papers on pretreatment of coal, in preparation for p y r o l j ~ i s , continue to appear in the technical literature. No attempt ha5 been made t o report such data here in any detail. Refcrcncc is made, however, to an improvement interpretation (218) of conventional float and sink diagrams over t’hat originally suggested by Chapman and Mott. The blending of coals for carbonization was the subject of a recent conference of the British Coke Research Association. The papers presented there included descriptions of the association’s own research in this field ( Z f d ) , of work by related Britibh agencies (If$, 1 76, 191 ), and of current French (262) and .Imcrican (204)practices. Continued research 011 the swelling characteristies of coal h a s been reported. Carlile claims ( 9 3 ) t h a t the bulk density of the hollow spherical ‘Lcenospheres,”formed n.her, finely pulvc~iizcd coal is heated for short intervals in an inert atmosphere, in I)(’ used as a sensitive test for swelling power. neuter intlicatts (212) some success on Ruhr co:tls by using the calorific v:~Iu(,of the residual coal from laboratory carbonization tests, as tlr~fincvl by a heat balance. Lambris (134) studied the problem from the point of view of plastic zone characteristics and delineates carefully between expansion pressure and swelling. Kozina and coworkers ( 123) use a relatively complicated plasticity measurcment test t o determine vertical expansion characteristics and volume changes with time, simultaneously. The interrelationship of caking and coking properties of coals has been reviewed by Yoshida (276), who concludes that caking tests are not a reliable criterion of cokability. Sakai proposes (224) t h a t an “ash index,’’ when used in conjunction with cxking, washing, and other tests, can be used t o evaluate the suitttbility of a coal for the production of metallurgical coke. Further results of the carbonization properties of spccific American coals, as carried out by the Bureau of Mines, Anit’rioan Gas Association testing method, have been reported. Reforenre is made particularly t o results obtained on coals from P c m i sylvania (56, 57) and West Virginia (61)and to a comparison between the American Gas Association test and studies in the Illinois Geological Survey slot-type oven (50, 6 7 ) . A discussiori of American coking coals imported into Japan was prcscmtcd by Maeda ( 163). Among the carbonization tests reported on foreign coals is a survey of 260 British and Commonwealth coals ( 1 9 ) , in which it is concluded that coking properties are determined primarily by colloidal structure and not by chemical constitut.ion. For coking data on Indian (61, 7 9 ) , Brazilian ( 1 9 7 ) , and Australian (109) coals, the reader is referred to the respective papers n o t d ihl c:lch case.
2008
INDUSTRIAL AND ENGINEERING CHEMISTRY
HIGH TEMPERATURE C A R B O N l Z A T l O N
I n a previous review (207) attention was called to a correlation of laboratory high temperature coke yields with plant processing results, by Mantel. Two additional papers have been published by this same author during the past year. I n the first of these (156), laboratory and plant results over a 10-year period are compared and evaluated as t o their significance in oven operation and on coke properties. I n the second article (156) the author discusses the results of systematic chemical, physical, and petrographical studies conducted over a similar period on the coals used and their influence on the coke and by-products obtained. For a general review of recent work on high temperature carbonization see (215).
COURTESY JOHN SAVAOE
Scottish Oils’ Westwood Shale Oil Works General view of retorts and its auxiliaries
Watanabe (268) subjected Bojuntan, a mixture of coal dust and tar blended a t 300”C. (7),to high temperature carbonization a t 900” C. and obtained a 70% yield of metallurgical quality coke. Three new papers involving briquetting of coal for carbonization have appear6d. The first of these (231) describes a prooeaa b y which noncoking bituminous coal is briquetted under high pressure or with sulfite liquor as binder and then is carbonized in a shaft kiln at 800”to 1OOO” C. The descending kiln charge first passes through a n upward current of hot, recirculate then enters a lower, electrically heated section. Ste at the base of the shaft. I n the second paper Kurchatov (130) has examined the influence of charcoal addition, with and without briquetting, on the carbonization of Balkan coals. He concludes t h a t only the mechanical properties of the resultant coke were improved. T h e last paper is concerned with the production of spheroidal coke briquets from carbonizable materials, b y direct pyrolysis in a rotary retort (90). Kramers and others (124) suggest that weakly caking coals may be converted t o suitable gas coke by rapid high temperature carbonization in thin layers or beds, Sabatier (923) and Pray (205) claim satisfzytory experiments to obtain metallurgical coke from Lorraine gas coals, by using proper blends of these coals with coke dust, coking coal, and/or semicoke. The satisfactory coking of a mixture of high volatile coal, “flotation” coal, and coke breeze is mentioned b y Dubois ( 5 8 ) . Carbonization of somewhat similar mixtures containing coke breeze is noted by Pluckthun (201). The use of deashed anthracite and a pitch binder as a pyrolysis mixture is said to be successful (122). A number of patents involving carbonization processes are of interest. Included are the addition of iron oxide to coal (240)and the coking of expanding coals by adding small quantities of pitch to the charge (120,196). Patents involving the use of a fluidized
Vol. 43, No. 9
carbonization bed (183) and a vertical retort in which a miutuw of the carbonizable material and a recirculated “fluent mass of solid, heat-transfer material” flows downward (8),have also been issued. LOW TEMPERATURE C A R B O N I Z A T I O N
I n a review of low temperature carbonization during the past 50 years, Pound (203) points out t h a t although most processes have failed t o justify their proponents’ claims, increasing use of such methods for smokeless fuels and liquid products can be foreseen in the years ahead. Further reports of his research on the fractional pyrolysis of peat, including work on the tars (40, 42, 43), on the low-boiling products ( , $ I ) , and on various constituents of a Carex peat ( 4 2 ) have been published by Christiansson. See also a paper on pcat coke by Frank ( 7 3 ) . Three Japanese papers describe experiments on the use of various blends of semicoke with domestic cads (129, 152) and with both American coals and petroleum coke (Im),for the manufaeture of blast furnace coke. Operations with semicoke in the Lurgi Spulgas retort in New Zealand are detailed by Jones ( 1 1 1 ) . The use of vertical retorts and noncoking Silesian coals for blast furnace coke production is outlined by Thau (265). The coking characteristjcs of the constituents of coal t a r pitch have been examined ( 2 6 ) . The Brennstoff-Technik process for low temperature carbonization, in which iron retorts with movable walls are used, is claimed (87) to yield a tar of low pitch content. The production of gaseous olefins by low temperature pyrolysis of British cannel coals is concluded not to be feasible economically (87’3). A number of process patents are worthy of mention. Further applications of t h e fluidized bed for low temperature carbonization have been disclosed by Nelson (181, 182). The addition of residues from coal hydrogenation to a coke oven charge has been s has low temperature thermal solution in patented (103, 104), a the presence of unsaturated hydrocarbons (192) and metallic oxides or sulfides ( 193). The latter are employed t o reduce phcno1 and sulfur content. Saha patented a process (233) in which partial combustion of coal a t the bottom of a chamber furnishes hot gases which convert the remaining charge t o a soft coke. O V E N OPERATION
The general problem of waste-heat recovery in coke plants is still of high interest. A review of various Swiss methods at the Basel gasworks is given by Thoma (256). The factors involved in a heat balance on a coke oven battery are discussed by Taylor (253). See also a paper by Widmer (271). A summary of systems devised during the past 25 years t o recover the sensible heat in the coke discharged from the ovens has been written (80). Hersche published a series of two papers on the dry cooling of coke by the Sulzer process (91, 92),including a discussion of the heat transfer mechanisms involved. The economy and efficiency of the quenching plant at f i e 1 and a comparison with the Sulzer system has been shown (236). Ryska has proposed (221 ) a new infrared-sensitive pyrometer for measurement of oven charge temperatures and also thc temperature of pushed coke; see also (220). A method for calculating temperature gradients in a coke bed has been suggested (356). The general problems associated with starting, shutdown, and maintenance of coke plants, particularly as a result of interrupted production, have been set forth (77, 78). Experiences in this regard, owing to war damage to Japanese plants, have been described by Nishio (185)and Shoya (83.4). Corrosion problems encountered throughout by-product coke plants, including t h r ovens, have been notcd in a n escellcnt resume by Pogacar and Tice (202,261), including the best met:ils to employ for various plant equipment. Repairs to refnrctories
September 1951
INDUSTRIAL AND ENGINEERING CHEMISTRY
2009
2010
INDUSTRIAL A N D ENGINEERING CHEMISTRY
(206) and end flues (168) and the spraying of leaking ovens (219) have been noted. Duxbury (62) indicated the relationship of refractory properties to start-up heating rates in vertical retorts. A summary of the causes of expansion pressure of the charge during coking and ways to reduce them has been prepared by Russell (119). Attention is also called to the proposed use of the back pressure of the gas found in the interior of a fused mass of coal, &s a criterion of coal swelling during pyrolysis (97). PRODUCTS AND BY-PRODUCTS
Three general papers dealing with developments in product and by-product recovery (22, 263, 264) appeared during the period under review. Little new information is contained therein. Graham (84) has surveyed the more important trends in the quality of metallurgical coke, particularly in so far as western Europe is concerned. The literature on coke utilization has been reviewed (180), as have specifical methods of using coke breeze more profitably (235). Kustov (182)argues for a more efficient utilization of coke oven gas in the U.S.S.R., particularly as a raw material for synthetic fuels. Design and operating data on the production of water gas in tall horizontal ovens have been published (188). The oil washing of coke-oven gas under pressure, in order to recover light oil and to reduce the organic sulfur content, has been described for a British plant by Illingworth (106). Haynes patented ( 8 9 ) a six-stage process for the separation of olefins from oven gases. A “barrier” process for enriching coke-oven gas has also been patented (121). In discussing light oil recovery processes Hoffert ( 9 6 ) states that adsorption is a more advantageous process for small plants than absorption. Fuel oil is suggested as being just as efficient for absorption as the usual wash oil now employed (171). For a review of recent developments in wash oil recovery methods see (269). Technical and economic factors controlling ammonia recovery and the production of concentrated ammonia liquors are discussed by Bell (15). For a comparison of the relative merits of various ammonia recovery processes, see a recent paper (16)by the same author, and a review by Lorenzen (143). Lorenzen has examined various sulfur recovery processes also. A somewhat complex process of producing sulfur from brown coals, involving impregnation with magnesium chloride and low temperature carbonization in a stream of “hydrogen-containing gas” (149) is of interest in the light of the current sulfur shortage. The recovery of phenol from by-product coke plant wastes oontinues t o receive increasing attention. Wilks describes a process
Vol. 43, No. 9
used a t Armco Steel Co. ( 2 7 2 ) that involves stripping the ammonia liquor with hot gases and absorption in base. Carbone ( 3 2 ) has outlined a liquid-liquid extraction process employed a t Allied Chemical and Dye Corp. See also a reference to a similar process of the National Tube Co. (257). The use of isopropyl ether and certain commercial ketones m liquid extraction solvents for phenol has been investigated (144). i5n economic survey of the Pehnosolvan process has appeared ( 5 3 ) . EQUIPMENT
As has bcen the practice in past reviews the items noted in this section are restricted t o the more significant articles and patents which have been publbhed. The listings are therefore admittedly incomplete. A brief review of the advantages of various types of ovens has beea compiled (277). Construction details of certain new vertical, inclined, and horizontal retorts, as well as operating data, are compared by Funk (75). For a discussion of horizontal retort settings particularly, see reference ( 5 ) . Among the subjects of more recent British patents on carbonization retorts are the following: vertical retorts discharged by rams operated by pulley-controlled weights (146); a low temperature retort consisting of chambers arranged vertically on a rotating central shaft (247); a continuous vertical retort with a revolving helical coke-discharging device (270); a n oven battery arranged with a cooling fan in the gas collecting main (274); and a coke oven door self-sealed by the deposition of pitch or tar from the charge (140). Recent U. S. patents include a continuous carbonization chamber with an inclined grate arranged with pusher feed and downward flow of hot combustion gases (267); a vertical oven with horizontal regenerators at the end of a series of superimposed heating flues (189); and a new type of coke car (190). See also patents (34,100,251). A variety of refractories recommended for different types of coke ovens have been evaluated by Heuer (93). The causes of refractory spalling in continuous vertical retorts are reported by Laming (135). Reasons for the failure of Dinas brick in coke ovens was examined by Bron (24), who states that deposition of pitch in the jointsis a major factor. COKE PROPERTIES
A new “coke index” has been developed in order to express the suitability of metallurgical coke for the blast furnace (227). The characteristics of coke produced for domestic consumption are dealt with in detail by Mott (174) and a standard method for
INDUSTRIAL AND ENGINEERING CHEMISTRY
Spteerber 1951
testing domestic lignite coke, by Kato (116). A statistical analysis of the size distribution of coke, as discharged from the oven, is given by HancOck (86). A number of investigators have presented added data on the reactivity of coke. Relationships between fuel bed temperatures and reactivity a t low rates of combustion have been postulated ( 6 0 ) . Tests on ore reduction with 950" and 1650" F. low temperature cokes were conducted by Lesher (141). Further comments on the reaction between coke, carbon dioxide, and steam have been made (2666),in reference particularly to the 1948 work of the British Gas Research Board ( 1 1 7 ) . See also a paper by Pierot (184). An Indian article ( 3 7 ) mentions a laboratory study of methods for reducing the sulfur content of a coke, employing alkali chlorides or hydrogen. A British patent states that coke-oven gas cracked previously by passage through hot coke, can be used t o remove sulfur, if sodium carbonate or water vapor is present as a catalyst (266). For a paper on the grinding of coke t o ultrafine particle sizes using a ball mill, see (177). ANALYSIS A N D TESTING
An attempt has been made to correlate the standard GrayKing carbonization assay with swelling number and with the carbon-hydrogen content of certain British coals ( 1 1 5 ) . The Hessler assay apparatus has been modified, in order to yield improved results ( b t l ) , as has the low temperature assay method of the Coal Research Institute of Prague (257). New methods for determination of coking power of coals include an apparatus constructed on the Ramsbottom principle (158)and a dilatometer working on a compressed bar of raw coal ( 166). The rapid determination of sulfur in coals has been modified, by titrating the silver sulfate from the combustion train with potassium isothiocyanate solution ( 1 4 ) . A new procedure of analysis for pyritic and sulfate sulfur is outlined by Mott (175, 175). See alm ( 1 2 ) . An extraction method for free sulfur in coke and semicoke has bwn proposed (258). In a recent review Myhill states ( 1 7 9 ) that minor constituents of coal and coke ashes, previously thought to be of lesser industrial importance, are now receiving increased attention. Among these constituents is phosphorus, for which two new colorimetric methods of analysis have been devised ( 1 3 , 2 1 0 ) . Hodgson (96)offers some sound arguments for using a thermal test in place of the usual standard ignition analysis for the volatile matter content of coke. The British standard swelling index for coking coals and its method of determination have been critically examined by Forch ( 6 8 ) and Kreulen (125). Fiirch claims better results with the .4msterdam scale for swelling index, and the latter investigator discredits the utility of the British index completely. In discussing various tests on cupola coke, Mott ( 178) emphasizes the need for correct assessment of the size of coke. A statistical analysis of size testing, made on h e l v e American and Canadian coals, is presented by huvil (6). An improved method of thermal fractionation of the gases from coal pyrolysis (159) is said to reduce the analytical time to half the present requirements. A new modified adsorption analysis of the benzene content of coke-oven gas has been devised ( 2 0 9 ) .
OIL SHALE PYROLYSIS GENERAL
Ample evidence of the constantly increasing interest in oil shale may be found in the fact that Yome 100 papers on this subject have appeared during the past year. This is a greater number than has been published in any single 12-month period for the past 20 years. A great stimulation to this interest in oil shale andwithout doubt
201 1
the most significant event of the period under review, was the Second Oil Shale and Cannel Coal Conference held in Glasgow, Scotland, in July 1950 (108, 199). From personal attendance there this reviewer can attest to the high quality of the work presented on all phases of oil shale science and technology. Reprints of the various papers, which are to appear later in book form under auspices of the Institute of Petroleum, are noted under their proper headings below. A number of new reviews on shale have been published during the year. Among these are a survey of the history, Occurrence, geologic origin, chemical constitution, and retorting of shales throughout the world (208); a review of the Estonian oil shale industry (1668); an account of an American shale engineer's observations of the Swedish shale oil industry, by Savage (128); and discussions of the development of the Australian industry in New South Wales (39, 2%). The last-named country has recently abandoned its shale efforts,by government edict (187). Western Germany has begun the production of shale oil once more; 137,000 barrels were manufactured in 1949 from a mine northeast of Darmstad'c ( 2 7 5 ) . The greatest activity in oil shale continues to be centered, however, in the Cnited States. The status of U. S. governmentsponsored research to date may be found in the latest report on synthetic fuels by the Secretary of the Interior (266) and in a survey by Hull and others (108). For a more technical discussion of the Green River shales and their products, see two excellent papers by Thorne, Murphy e l al. (259)and Stanfield ($&), all of the . U. S. Bureau of Mines. The most economically feasible locations for synthetic fuel plants in the United States, including oil shale plants, has been and the role of the various synexamined by the Bureau (44), thetic processes in future fuels production is reported by Boyd ($3). Mciillister suggests (148) that western U. S. shales represent the best potential source for alleviating future fuel shortages on the Pacific Coast. M E C H A N I S M , KINETICS, THERMOCHEMISTRY
From microscopic examinations and extraction studies, Ferris (65) has concluded that oil shales, contrary to some belief, have not been a geologically significant source of the world's petroleum. The geologic origin of the Australian torbanites has been postulated by Dulhunty (59). Reporting on the results of 12 years of research on krrogencontaining rocks and on the chemical constitution thereof, Himus suggests (&) that kerogen originated from two source materials, one humic in character and the other planctonic or sapropelic-i.e. aquatic -in nature. Definite evidence of a benzenoid structure, of a weaker type than that of coal, is found in some shales, whereas in others-e.g. Estonian kukersite-it is totally absent. Xothing suggests that animal remains played any important role in kerogen formation. Dancy and Giedroyc (49) confirm the presence of such a benzenoid structure in both a South African torbanite and in a French oil shale. Various separation processes for kerogen are reviewed critically by these authors. Cane ( S I ) has studied the mechanism of decomposition of iiustralian torbanite in greater detail. IIe postulates a four-stage process, the initial stages being unimolecular in so far as rate is concerned, with an activation energy of 48,500 gram-calories per gram-mole. A similar conclusion as to moleculaiity was reached a number of years ago by Maier and Zimmerley working with Green River shale. In a more recent study on Colorado shales, Hubbard and Robinson (101) have' reported specific reaction rates for kerogen, over the range 350" to 525" C. For a list of compounds obtained on controlled oxidation of Colorado shale, see ( 2 6 6 ) . The thermophysics of torbanite decomposition was also examined by Cane (31), who gives values of 530 to 810 calories per gram of torbanite. Sohns and coworkers (244)have examined the
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
2012
COURTESY JOHN SAVAGE
Scottish
Oils’ Broxburn Candle Factory, Moulding Machines for Paraffin W a x Candles
over-all heat requirements for retorting Colorado shale and report values of 207 to 378 B.t.u. per pound, depending on temperature firid richness of the raw material. For a report on the reactivity :ind kinetics of the ovidation of fixed carbon in spent shale, see a pnper by Givaudon (82). An outstanding series of eleven papers has been published by >lapstone (157) on nitrogen in oil shale and shale oil. For a more condensed version see (167). Included are studies on the nitrogcn compounds present in kerogen and their distribution on pyrolysis; the organic nitrogen compounds in shale oil and ref i n d products therefrom; analytical methods for nitrogen in oil shale and shale oil; and studies on the pyrolysis of porphyrins and proteins. For analytical methods for the nitrogen in &loratio shales sce (266). R A W M A T E R I A L S AND PROPERTIES
The mining methods employed for the various shales throughout the world have been the subject of a number of articles during the period under review. Caldwell (28) gives a historical resume of the underground modified stoop and room methods employed in Scotland and the mechanical improvements therain made throughout the past 90 years; these include the use of the longnall method ( 2 9 ) of mining. Similar methods, analogous to standard coal mining procedures, are used in South Africa (20). The open-pit working of certain Scottish deposits, using modern evcavating machinery, has been described (30). Details of the room-and-pillar mining of American shales a t Rifle, Colo., are given by Gardner (76). See also (966). For the mining procedures adapted to the French shales of Autun, see ( 3 ) . Survcys of the characteristics of the shales of individual countries have been compiled by a number of authorx. Reference is made to papers on the South African torhanites by Stelling (248, 349); on the geology of the mid-lothian shales of Scotland by Simpson (239); on the Kimnieridge shales of England by MacDougall (149); and on the oil shales of Spain by Thorne (258). The properties of the Wittenberg shales of Germany have been well noted by Couderc (48). Brief reviews of the Australian shales (186) and of the beds in Brazil (154) are also available. Thorne (26‘60) and Frost ( 7 4 ) have discussed the characteristics, properties, and utilization of the U. S. shales. Schopf (950) recapitulates the close relationship between oil shales, torbanites, and boghead and cannel coals. R E T O R T I N G PROCESSES
A review of the work to date of the C . S. Bureau of Mines on the retorting of Colorado oil shale may be found in a preprint from the recent shale conference ( 3 6 ) . A new “gas combustion re-
Vol. 43, No. 9
tort” is described in the organization’s annual report (266),as are the effects of tempemture and heating time on the quantity and quality of the products obtained. A new high temperature radiant retort, which is stated to produce commercially attractive quantities of benzene and other aromatics, is also presented here (266). A recapitulation of the operating characteristics of the Union Oil Co. internally heated retort has appeared (18,198). Details of the Swedish process for pyrolysis of shale in situ, by a system of underground electrical heaters, have been explained by Salomonsson (226). The Holzheimer process for underground gasification of lean shales, employing a system of shafts, is said t o result in carbonization of 80% of the deposit (229). The wartime production of N.T.U. shale oil a t Marangaroo, New South Wales, has been recounted by Mapstone (168). The continuous flow Renco retort and its proposed use on Australian shales is described by Moate (170). See also (59). Recent changes in the design and operation of the Pumpherston retort used on Scotch shales are given by Smith (241). The horizontal, low temperature carbonization retorts (Salermo) used on South African torbanites are the subject of a paper by Forbea (69). For a description of another low temperature carbonizatior pilot plant, see (85). An interesting, novel retort for the pyrolysis of oil shale has been proposed by a Swedish engineer ( 4 ) . Briefly, the apparatus consists of a revolving drum supplied continuously with heated metal or ceramic pebbles of graded size. These pebbles flow countercurrently to a feed of pea-sized shale; the sensible heat of the pebbles furnish the heat of retorting. It is said that there is no lower limit t o the fineness of the shale which may be so treated. The retorting of French shales so as to obtain a spent shale which could be used as a raw material for cement or lime production has been described (81), as has a means for using the fixed carbon of shale fines, for power production (153). The boilers used for the burning of spent shale coke in Sweden have water tubes imbedded directly in the burning fuel bed (110). Reference is made to an article on the thermal evtraction of shale by Marecaux (166) and to a survey of the electrical services in the Scottish shale oil industry by MacLennan (151).
COURTESY JOHN b A V A a E
Seottioh Oils’ Westwood Shale
Oil Works, Naphtha Plant
PRODUCTS AND BY-PRODUCTS
The principal product from the pyrolysis of oil shale is shale oil. Reviews on progress t o date in the refining of the oils from Colorado shales have been published by Lankford ( 236, 157) and by Guthrie (85), including data on atmospheric distillation, visbreaking, recycle cracking, and the production of Diesel fuel. Further details of current refining research, including the hydro-
September 1951
INDUSTRIAL A N D ENGINEERING CHEMISTRY
genation of crude shale oil and the production of jet fuels, may be found in (266). Reports specifically on the hydrogenation of N.T.U. shale oil include a paper by Smith (942), a Shale Conference report by Hoog of Shell Oil (go),and a preprint of the Kansas City meeting of the American Institute of Chemical Engineers (194). A detailed description of the hydrogenation of Fushun shale oil is given by hlizoshita (169). Cracking studies on oils derived from Green River shales pyrolyzed in the N.T.U. retort and in the Parry coal carbonization retort are reported by Egloff ( 6 4 ) . The cracking of Australian crude shale oil and the unique properties thereof are noted by Mapstone ( 1 6 4 ) . A discussion of the carbon disulfide content of shale naphtha has been presented by the same author (160). Robertson (216) states t h a t the major products from the refining of the torbanite oil of South Africa are gasoline stock and bitumen for road asphalt. Details of the refining processes used there are given by this author. Egloff ( 6 3 ) reports a study on the refining of both South African and Australian torbanite oils. Lundquist ( 1 4 7 ) compares the refining processes necessary for the Swedish oils produced by the three oven retorting methods now in operation a t Kvarntorp, and by Ljungstrom underground pyrolysis. For a description of the refining of French shale oil, see (166). The waxes obtained from Colorado shale oil were examined as t o physical and chemical properties by Tisot and Horne (96'9). Peutherer (200) reviews the various steps in the processing of paraffin wax from Scottish shale oil. Emulsion problems arising during the refining of Australian torbanite oil and their solution are mentioned by Mapstone (159). The properties of the asphalts obtained by vacuum distillation, cracking, air blowing, and pi opane precipitation from Green River shales have been examined by Kommes and Stanfield (119). Utilization of the Clo t o CZo olefinic const;tuents of Scottish shale for the commercial production of synthetic detergents is desciibed ($50). See also (943). Anderson ( 2 ) outlines the manufacture of shale lime bricks from spent shale in Scotland. The chemical composition of various Scottish shale oil distillates, including the hydrocarbons present, has been determined (88), as has the analysis of a crude gasoline from the Swedish oil works at Kiniie-Kleva (98). The olefins contained in ten different shale oil naphthas and nine petroleum naphthas were identified and compared by Dinneen, Smith, and Ball (56). A process for the cat:ilytic conversion of a shale oil fraction to butadiene has been patented (245). Dinneen conducted accelerated gum formation studies on a n N.T.V. naphtha and noted the nitrogen present in the gums so obtained (64). Benzie ( 1 7 ) identified the pyridine bases in a basic tar obtained from Scotch shale oil. The nitriles present in Manchurian shale oil have been analyzed (105). For a n excellent and comprehensive survey of the nitrogen compounds present in Australian torbanite oils and methods for their determination see reference (157). A N A L Y S I S AND TESTINQ
Salomonsson proposed (226) a new assay apparatus for determining the oil yield from shales, which is said to be superior to the standard Fischer or Gray-King methods. hlapstone ( 1 6 3 ) modified the Gray-King method for use on Australian torbanite and compared the oils from this new procedure with those obtained by both the Fischer assay and the standard Gray-King assay. Specific heat determinations on a sample of Brazilian oil shale have yielded, it is stated ( Z l d ) , an average value of 0.221. The density-temperature relationships of various shale oil fractions have been plotted (161). See also (157),which deals specifically with these relationships for the bases in shale tar. Analytical methods for the nitrogen compounds in oil shale and shale oil have been outlined by lMapstone (157)and the U. S. Bureau of Mines (266). A study of the sulfur compounds present in
2013
petroleum, by Ball (9),is certain to be useful in future shale oil research.
ACKNOWLEDGMENT The author wishes to express his gratitude to Louis Herzog, Department of Chemical Engineering, University of Denver, for his aid in the collection of the numerous references for the current review. The assistance of Virginia Cofer in the cataloguing of the literature citations is also &-atefully acknowledged.
LITERATURE CITED Ahmed. M., and Kinney, C. R., J . Am. Chem. SOC.,72, 556-9 (1950). Anderson, A.,and McCallum, J., preprint No. B21, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Arthand, M., preprint No. A3, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Aspegren, O., private communication. Athinson, R. K., Gas J., 265,43.34, 437-8 (1951). huvil, H. S.,and Gayle, J. B., U . S. BUF.M i n e s , Repts. Invest. 4735 (1950). Baba. A , . J . Fuel SOC..J a m n . 28,22532 11949). Bailey, E. G. (to Babcock and' Wilcox bo.),'U. S. Patent 2,519,340(Aug. 22, 1950). Ball, J. S., et al., preprint, Division of Petroleum Chemistry, 119th Meeting, AMERICANCHEMICAL SOCIETY, Cleveland, Ohio. Barritt, D. T., and Kennaway, T., J . Inst. Fuel, 23, 308-12 (1950). Barritt, R. J., Coke Oven Mjgrs. Assoc. Yearbook, 1950, 110124. Barton, K., and Strizova, S.,Paliua a voda, 30,73-6 (1950). Belcher, R., Fuel, 29, 232-5 (1950). Belcher, R., and Spooner, C. E., Ihid., No. 8, 188-192 (1950). Bell, J., Coke and Cas, 12,2 0 6 9 (1950). Ihid,, pp. 253-60. Benzie, R. J., et al., preprint No. B23, Second Shale Oil and Cannel Coal Conf., Glasgow (1950). Berg, C., Ibid , preprint No. B3. Berkowitz, N.,Fuel, 29, No. 6 , 138-43 (1950). Blore, G. B., and Somerville, W.B., preprint No. A9, Second Oil Shale and Cannel Coal Conf., Glasgow, 1950. Boulin, W., and Verret, P., preprint Trans. World Power Conj., 4th Conj., London, Sect. D2, Paper No. 2 (1950). Bowman, R. O., Yearbook Am. I r o n Steel Inst., Tech. C m m . Activities, 1949,328-39. Boyd, James, Petroleum Refiner, 29,No. 12,77-85 (1950). Bron, V. A., Ogneupory, 15, No. 1, 19-28 (19.30). Bruckner. H..and Huber. G.. Gas- u. Wasserfach, 91, No. 9 (Gas), i04-7 (1950). Burns, J., Gas World, 132,80-2 (1950). Burstlein, E.,Chaleur & I d . , 31, 215-32 (1950). Caldwell, J. M., e t al., preprint No. All,Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Ihid., preprint No. A12. IbM.. m e m i n t No. A16. Cane','R..F., Ibid., preprint No. B25. Carbone, W.E.,Seuage and I n d . Wastes, 22,200-5 (1950). Carlile, J. H.G., J . I n d i a n SOC.Enpa., 13, 117-19 (1948). Cartmight, J., U.S.Patent No. 2,526,459(Oot. 17,1950). (35) Cassan. H..Chaleur & I d . , 31,No. 296,76-8 (1950). (36) Cattell, R.'A., et al., preprint No. E l , Second Oil Shale and Cannel Coal Conf., Glasgow (1950). (37) Chatterjec, N . N., Geol. Mining M e t . SOC.I n d i a , Bull. 5, 1-8 (1943). (38) Chemie-Ing.-Tech., 22, 249 (1950). (39) Chemistry & I n d u x f i ? ~1950, . 438. (40) Christiansson, B.,Ing. Vetenukaps Aknd., Peat Lab. Communic. 10 (Aug. 15, 1949). (41)Ibid., 14. (42) Ibid., 15. (43) Ihid., I V U 20, , 164-75 (1949). (44) Coal Age, 54, 172 (1949). (45) Coke and GUS,12,229-36 (1950). (46) Ibid., pp. 242-44, 272-76. (47) Cornefert, J.,J . .i~sinesgaz, 73, 105-6 (1949). (48) Couderc, J., preprint No. h4, Second Oil Shale and Cannel Coal Conf., Glzsgow (1950). (49) . . Dancv. T. E.,and Giedroyc, V., J . Inst. Petroleum, 36,593-603, 607-23 (1950). (50) Davis. J. D., el al,, U . S. Bur. M i n e s , Bull. 480 (1950). (51)Ihid., 493. ~
.
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I
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 DeCarlo, J. A., and Corgan, J. A., U . S. Bur. M i n e s , Inform. Circ. 7579 (1950). Dierichs, A., Chem. Tech. (Berlin), 2, 224-30 (1950). Dinneen, G. U., and Bickel, W. D., preprint, Division Petroleum Chemistry, 118th Meeting, AMERICANCHEMICAL SOCIETY, Chicago, Ill. Dinneen, G. U., et al., Petroleurn Refiner, 29, No. 5, 129-34 (1950). Dowd, J. J., et al., U . S. B u r . M i n e s , Rept. Invest. 4734 (1950). Tbid., 4757 (1950). Dubois, J., et al., Przeglad Gorniczy, 6 , 339-46 (1950). Dulhunty, J. A,, preprint No. 8 7 , Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Dunningham, A. C., J . Inst. Fuel, 23,242-6 (1950). Dutta Roy, R. K., Records Geol. Survey India, 75, Prof. Paper NO.3, 1-27 (1940). Duxbury, -4. D., Gas J . , 262, 956-8, 963-4 (1950). Egloff, G., et al., preprint No. B11, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Ibid., preprint No. B26 (1950). Ferris, B. J., World Oil, 131, No. 3, 80, 82, 84, 88; NO. 5, 85-86, 89-90 (1950). Fitz, W., Stah2 'u. Eisen, 70, 1122 (1950). Flickinger, C. H., and Graham, J. P., U . S.Bur. M i n e s , Tech. Paper 726, 51-5 (1949). Forch, J . H., Hct Gas, 70, 79-82 (1950). Forbes, C. E., and Somerville, W. B., preprint No. B4, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Foxton, J., Gas World, 133, 82-4 (1951). Foxwell, G. E., et al., preprint, Trans. World Power Conl., 4th C m f . , London, Sect. D2, Paper No. 4 (1950). Foxwell, G. E., and Johnson, C., Gas World, 132, 76-80 (1950). Frank, F., Peat, 1, 11-4 (1950). Frost, I. C., et al., preprint, Division Petroleum Chemistry, AMERICAN CHEMICAL SOCIETY, 118th meeting. Chicago, 111. Funk, Viktor, Gas- I L . Wasserfach, 91, No. 13 (Gas), 172-6 (1950). Gardner, E. D., and Sipprelle, E. M., preprint No. A8. Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Gas World, 132, Coking See., 82-3 (1950). Ibid., pp. 91-3. Gee, E. R., Records Geol. Survey India, 75, Prof. Paper No. 11, 1-46 (1940). Giordano, I., Calore Il., 21, 211-20 (1950). Givaudon, J., and Dumoutet, P., preprint No. B6. Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Givaudon, J., and Nessler, A., Ibid., preprint No. B7, 1950. Graf-Ignis, U. S. Dept. Commerce, Washington 25, D. C., OTS Rept.. PB 98744 (1946). Graham, J. P., et al., preprint, Trans. World Power Conf., 4th Conf., London, Sect. B3, Paper No. 1 (1950). Guthrie, B., and Schramm, L., Mech. Eng., 72, 707-11, 732 (1950). Hancock, R. T., Coke and Gas, 12, 60-1 (1950). Hansen, C. J., Brennstofl-Chem., 31, 308-17 (1950). Harmnape, D.. and Lowry, R. A., preprint No. B20, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Haynes, P. E., (to Koppers Co., Inc.), I?.S. Patent 2,503,265 (April 11. 1950). Hemminger, C. E. (to Std. Oil Development Co.), U. S. Patent 2,511,709 (1950). Hersche, W., Schweiz Ver. Gas- u. Wasserfach Monats-Bull., 30, 182-91 (1950). Ibid., PP. 147-53, 182-91. Heuer, R. P., and Grigsby, C. E., Steel, 126, No. 22, 65-8; NO. 23, 98-104 (1950). Himus, G. W., preprint No. A6, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Hodgmn, R., Gas J., 261, 786, 791 (1950). Hoffert, W. H., and Claxton, G., preprint, Trans. World Power Cmf.., 4th Conf., London, Sect. C2, Paper No. 6 (1950). Hofssss, M., Bergb. u. Energiewirtsch, 3, 118-22; Glilckauf, 86, 581 (1950). Holmberg, B., Finska Kemistrramfundets Medd., 54, 111-15 (1945). Hoop, H., et al., preprint No. B28, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Horner, H. R., and Hennessy, R. J., U. S. Patent 2,537,670 (Jan. 9, 1951). Hubbard, A. B., and Robinson, W. E., U . S. Bur. M i n e s , Rept. Invest. 4744 (1950). Hull, Wm. Q., et aZ., INU. ENG.CHEM.,43, 2-15 (1951). I. G. Farbenindustrie, A.-G., Ger. Patent Appl. 163,353, class VI/lOa.
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(104) I. G. Farbenindustrie, .4.-G., Ger. Patent Appl. 165,129, class
VIb/lOa. (105) Iida, T., and Tanaka, SI.,J . Pharm. Sac. J a p a n , 64,No. 9-4, 33-4 (1944). (106) Illingworth, H.S., Gas W o r W , 131, No. 3424, Coking Section, 37-41 (1950). (107) Inahara, T., J . Fuel SOC.J a p a n , 29, 196 (1950). (108) Inst. Petroleum Rev., 4, 275-83 (1950). (109) de Jersey, N. J., Univ.Queensland Papers, Dept. Geol., 3, No. 7, (1949). (110) Johansson, A., and Hedback, T. J., preprint T r a m . World Power Conf., 4th Con/.,'London, Sect. C 2 , Paper No. 4 (1950). (111) Jones, A. B., Coke and Gas, 12, 287-90 (1950). (112) Jones, W. I., J . Inst. Fuel, 24, 21-2 (1950). (113) Ibid., pp. 69-75 (1951). (114) Jordan, I., A n a i s assoc. gwim. Brasil, 8 , 1 5 H 5 (1949). (115) Jowett, G. H., and Sarjant, R . J., J . Inst. Fuel, 23, 304-7, 332 (1950). (116) Kato, Ichijiro. J . Fuel Soc. J a p a n , 29, 1 3 7 4 0 (1950). (117) Key, Art.hur, Gas Reseurch Bourd, Copyright Pub., C o m m u w No. 40 (1948). (118) Kipling, J. J., Science Progresa, 37, 657-69 (1949). (119) Kommes, W. C., and St,anfield, K. E., preprint, Proc. Assoc. Asphalt Paving Techn.ol., -4nnual Meeting, Denver (1951). (120) Koppers Co., Inc., Brit. Patent 638,335 (1950). (121) Koppers Go., Inc., and Harlow, E. V., Brit. Patent 633,372 (1949). (122) Kosaka, Y., et al., J . Fuel Sac. J a p a n , 28, 200-2 (1949). (123) Kozina, A., et al., Paliva a voda, 30, 209-14 (1950). (124) Kramers, W. J., e f a l . , Fuel, 29, No. 8, 184-7 (1950). (125) Kreulen, D. J., Ibid., KO. 5, 112-17 (1950). (126) Kreulen, van Selms, F. G.. Chem. en Pharm. Tech. (Dordrecht), 5, 181-6 (1950). (127) van Krevelen, D. W., F u e l , 29, 269-84 (1950). (128) Krumin, P. O., Ohio Stal. Univ. Eng. Erpt. Sta. Circ. 50 (1949). (129) Kunii, S., J . Fuel SOC.J a p a n , 29, 196 (1950). (130) Knrchatov, M. S.. Annuaire univ. S o f a , Facult6 sci., Livre 2, 45, 1-27, summary in Russian, 28-30 (1948-49). (131) Kustov, B. I., Zhur. Priklod. K h i m . ( J . Applied Chem.), 21, 421-3 (1948). (132) Kustov, B. I., and Vaisberg, 0. P., E k u n . Topliva, Z a , 5 , 5-9 (1950). (133) Labourel, M., preprint S o . B19, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). (134) Lambris, G., and LeMarie, H., B r e n n s t o f - C h a . . 32, 50-6 (1951) . (135) Laming, J.;and Rigby, G. R., Gas Research Board, Copyright Pub., Commun. G R B 53 (1949); 40th Rep. Refract. Mat. Joint Comm., 6-26, 1948-49. (136) Lankford, J. D., and Ellis, C. F., IND. ENG.CHEM..43, 27-32 (1951). (137) Lankford, J . D., and Morris, B., preprint No. B9, Pccond Oil Shale and Cannel Coal Conf., Glasgow (1950). (138) Lanyi, B., A l u m i n u m ( B u d u p m t ) , 1, 121-5 (1949). (139) Lebeau. P., and Picon. A f . , Compt. rend., 231, 259-61 11950). Brit. Patent 647,610 (1950). (140) Les Fours Lecocq, S.-4.. (141) Lesher, C. E., Trans. -4m. Inst. M i n i n g Met. Engrs., 187. Tech. Pub. No. 2874-I: (also in M i n i r q Eng.. 187, 805-10) (1950). (142) Lissner, A., Bergbau u. Energiewirt., 3, 188-91 (1950). (143) Lorenzen, G., Chem. Tech. (Berlin), 2, 297-305 (19.50). (144) Lowenstein-Lom, V., el a l . , Gaz i Woda,. 24, 94-9 (1950). (145) Lowry, H. H., Chemistry B. Indw..stry, 1950, 619-25. 1146) Low-Temperature Carbonization, Ltd., et ul. Brit. Patent 644,023 (1950). (147) Lundqnist,, L., preprint KO.B12, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). (148) McAllister, 8. H., Pctroleuunr Processing, 5 , 1067-9 (1950). (149) MacDougall, D., and Cawley, C. M., preprint No. R5, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). Fuel, 29, S o . 8, 195-6 (1950). (150) McKee, J . H., (151) MacLennan, G. A , . preprint No. A13, Second Oil Shale and Cannel Coal Conf., Glasgow (1950). (152) Maeda, K., J . Fuel SOC.J o p a n , 29, 195 (1950). (153) Maeda, K., and Sanada, M., Ibid., p. 193. (154) Malzahn, E., Erd6l z1. Kohle, 3, 592-8 (1950). (155) Mantel, Walthcr, Brennstofl-Chcm., 31, 161-72 (1950). (156) Ibid., pp. 265-78. (157) Mapstone, G. E., Proc. R o g . SOC.N. S. Wales, 82, 79-106, 12S149; 83,4&63, 114-16 (1950). (158) Mapstone, G. E., preprint S o . B8, Second Oil Shale and Carinel Coal Conf., Glasgow (1950). (159) Ibid., preprint No. B13. (160) Ibid., preprint No. B15.
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Ibid., preprint No. €318. Ibid., preprint No. B24. Ibid., preprint No. R30. hlapstone, G. E., and IIogiLn, K. J., Ibid., preprint No. B27. Marecaux, M., Ibid., preprint KO. -416. Ibid., preprint S o . €316. Martin, K. W.,Stahl 11. Eiscn, 69,839-40 (1949). Mayfield, P. C., Blast Fiwnoce, Coke Oven, and Raw Maferiols (Proc. Conf. Am. Inst. Zliiiiiig AIet. Engrs.), 8, 97--100 (1949).
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