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Unit Processes Review
Pyrolysis of Coal and In the Review Year 1959 . . . I
European carbonization research continues to explore the fundamental aspects of the pyrolysis reaction. In the United States, emphasis is being given to the development of processes for the conversion of lowrank western coals to metallurgical grade coke. Intensive basic and applied oil shale research continues in the U.S.S.R.
T,Ecarbonization of coal was studied
Ih
“I
Shale
by pyrolyzing polymeric coal models and selected vitrains. Nuclear magnetic resonance, x-ray, and infrared techniques were used to follow the thermal decomposition reaction. Several investigations were reported on the thermal behavior of maceral types. Interest in low-temperature carbonization continued to be centered in those areas abundant in noncoking or weakly coking coals. The development of tar markets appears essential to the success of low-temperature carbonization. I n this country cokes suitable for use by the phosphate industry, in addition to metallurgical-grade coke, are being sought through conversion of low-rank coals. High-temperature conversion of brown coal and lignite was reported by German and Russian workers. Production of stable coke, on a laboratory scale, was achieved by briquetting brown and other noncoking coals at incipient decomposition and carbonizing the briquets at high temperatures. Studies relating the effect of the coking rate to coke quality suggest that oven width and flue temperature exert little influence on coke properties when the coking rate is constant. I n general, the strength of cokes produced from weakly coking coals could be improved by preheating the charge. Factors of blend composition, particle size, and the addition of inerts were investigated in pilot and full-scale coke oven models. Oil Shale Pyrolysis. The pyrolysis of oil shale in the U . S. continues to move closer to commercialization, as retorting costs are further reduced. Several studies of the prospects for a U. s. shale industry appeared during the year. Basic research on oil shale continues to be emphasized in the U.S.S.R. Baltic shales have been investigated with respect to the activation energy of pyrolysis, the organic nature of the cyclic structures and hetero groups present, and the flotation concentration of the organic matter. I n an interesting study of the size of the
primary inorganic particulate matter in Colorado shales, it was found that 90% of such particles had equivalent spherical diameters less than 44 microns. Some additional data on crushing of oil shale has been released, but quantitative information on the energy requirements involved is still sadly lacking. Over 1 5 U. S. patents on oil shale retorting were issued, including certain improvements in fluidized-solids retorting and in high temperature entrained retorting. A comprehensive collection of
reports on the process technology of Estonian shales was published. Research workers in the U.S.S.R. are engaged in intensive efforts to evaluate the properties and commercial potential of Russian shale oils. Included in these studies are a number of studies of the byproduct chemical potential of Estonian shale oils. A U. S. patent describes the manufacture of portland cement from oil shale. A finely divided kiln feed is prepared by impingement of two highvelocity shale slurry streams.
Pyrolysis of Coal by Manuel Gomez, Bureau of Mines, Denver, Colo.
THE
carbonization behavior of synthesized coal-like models was reported by Wolfs and others (25A). Their results show that the primary carbonization is a depolymerization reaction concurrent with a disproportionation of aliphatic hydrogen. Hydroxyl groups in the starting product induce a dehydration and condensation reaction. Aromatic hydrogen is released during secondary carbonization, but no tar is formed. Polymeric coal model pyrolysis was reported in greater detail in a series of seven papers by van Krevelen and others (17A, 72A, 26A-3OA). Smidt and van Krevelen (23A) investigated the carbonization reaction using the electron spin resonance technique. Results obtained for a series of vitrains in the 71.7 to 95.5% carbon range indicate that the number of free radicals in the tar produced is the same as in the initial material. This information suggests that the tar molecules are molecular components of the coal.
Nuclear magnetic resonance (NMR) spectra obtained from solutions of products derived from vacuum coal carbonization were used by Brown and others (2A) to estimate the relative proportions of aromatic hydrogen, hydrogen on CYcarbon atoms, and hydrogen on other saturated carbon atoms. The N M R results for aromaticity, degree of aromatic substitution, and ring size (for different assumed values of the average composition of nonaromatic structures) paralleled those obtained by infrared and x-ray analysis of the parent coals ( 3 A ) . A significant observation made by these authors is that there is no N M R evidence to indicate that hydrogen exists, to any appreciable extent, as methylene bridge structures. This information disagrees with the mechanism of carbonization discussed by Wolfs and others (25A) through the use of model polymers and with the coal model postulated by Given (6A). Both Wolfs and Given found it necessary to use methylene VOL. 52, NO. 8
AUGUST 1960
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bridges to obtain a model consistent with their data. The carbonization of coals of 82 to 94y0 carbon was investigated by Holden and Robb (8d)by means of mass spectrometry. I n the 80' to 450' C. range, the evolution of alkyl-substituted benzenes, naphthalenes, and phenols was temperature dependent. The appearance of alkyl-substituted aromatics below 300" C. was interpreted to be the result of vaporization from the micropore structure of the coal and not of thermal decomposition. Dilatometric studies of vitrinite and exinite concentrates and blends of softening and nonsoftening coals were reported by van Krevelen and others ( 7 3 A ) . The researchers believe that a definite relationship exists between the percentage dilatation and the content of inert constituents. The dilatation of mixtures of several coals can be calculated if the dilatations of the separate components are known. Kroeger reported (15A) that carbonization yields of coke, tar, and gas depend on the volatile content and elemental composition of the charge, rather than on maceral type. Ergun and others (5A) investigated maceral thermal behavior by determining fusion and resolidification times (at constant temperatures) in the 450" to 500" C. range. Qualitative results showed that exinites and vitrinites, when heated a t slow rates, behaved differently from those heated instantaneously. With slow heating rates, the high-temperature coefficients of time required for fusion suggested that depolymerization or cracking is the initial step of thermal decomposition. From a study of weight loss curves, Berkowitz ( 7 4 concluded that these curves did not show a protracted thermal decomposition of coal but rather that the decomposition reaction must be relatively fast. Corrales and van Krevelen ( 4 4 examined coal decomposition thermogravimetrically and concluded that it is essential to account for the rate of diffusion within grains and the desorption of the volatiles. The rate of weight loss was rank dependent and largely controlled by chemical decomposition. The reactive groups in coal were studied by Iyengar and Lahiri (70A). They observed that the structural units of coking coals are probably held by van der Waals forces. Increase in temperature weakens these forces until the coal becomes plastic at 350" to 450' C. T h e relationship between the heat of combustion and the structure of gas coal and the solid products of carbonization was investigated by Urazovskii ( H A ) . T h e structural index obtained, when
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plotted against temperature of carbonization, rose to a peak value at 540" C., corresponding to the structure of coke formed at that temperature. Studies relating the alicyclicity of coal and tar formation, based on the dehydrogenation of coal by sulfur, were reported by Mazumdar and others (78A). Dehydrogenation resulted in the inhibition of tar formation because of the apparent aromatization of the alicyclic part of coal. However, van Krevelen and others (74A) refuted Mazumdar's results on the basis that several completely aromatic compounds yielded hydrogen sulfide when heated with sulfur at 200' to 300" C. Results confirming the view of van Krevelen were reported by Iyengar and others (94. By dehydrogenating coal with iodine, Mazumdar and others (79A) obtained results paralleling those reported for sulfur. The iodine dehydrogenation reaction may be complex in that iodine probably reacts with alicyclic and aromatic hydrogen. Low- and High-Temperature Carbonization
The potential of low-temperature carbonization of bituminous coal was discussed by Glenn and Jacoby (7B). Chief deterrent is the lack of markets for low-temperature tar. Two large industrial firms announced development of processes for converting western United States low-rank coals to metallurgical-grade coke (4B). U. S. Fuel Co.'s process employs an integrated pelletizer-carbonizer unit. Utah subbituminous coal is pelletized with an inert binder and carbonized a t 1220" C. in a stream of natural gas. T a r and a gas high in hydrogen are collected as byproducts. Food Machinery and Chemical Corp.'s process uses a two-stage technique. The first stage reduces the coal to a friable semicoke. The semicoke is briquetted mechanically without a binder and is carbonized. No byproducts are collected. Pilot plant tests a t Montana State College's externally heated, vertical-shaft retort were reported by Berg and Miscellaneous Reports on Mechanism, Kinetics, and Thermochemistry of Coal
Subject Ref. Third Conference on Carbon, ( Z 7 A ) Univ. of Buffalo Mechanisms of coal pyrolysis (7'4) Degasification of brown coal (76A) Acidic structural groups in Illinois ( 7 7 A ) coals
Effect of catalysts on destructive distillation and plasticity of coal Irradiation studies on coal and its by-products
INDUSTRIALAND ENGINEERINGCHEMISTRY
(2OA)
(22A)
Atkinson (3B). Their report included a discussion of the commercial plant at Red Lodge, Mont. The Red Lodge unit processed 40 tons of Montana coal per 24-hour day and produced about 20 tons of low-temperature char and 18 to 20 gallons of crude tar per ton of coal charged. Pound (12B-14B) discussed low-temperature carbonization and products derived from the Coalite commercial process. High-temperature carbonization of brown coal by the Bilkenroth-Rammler process was reported by Gerlach (6B). Screened, dried brown coal is briquetted and carbonized in vertical ovens. Compressive strength of the product is satisfactory, but abradability is inferior. High ash, sand, or clay contaminants and xylite deteriorate the quality of the carbonized briquets. Allied Chemical Corp. (7B) patented a three-stage process. The raw coal is dried and is preheated in a fluidized bed at 660 " F. ('in an atmosphere of combustion gases generated by burning fuel gas with air); 1% residual fuel oil is added to the preheated coal before it is charged to the coke oven. Owners assert that coking time is decreased from 30 to 20 hours. A carbonization process applicable to processing coal, lignite, and briquetted solid fuels was patented by Ode11 (9B). Fine-size char or coke is heated to incandescence in a fluidized bed. The hot solids are introduced to the carbonizer along with raw coal. The hot solids supply some of their sensible heat to the coal and raise its temperature. Char temperatures are controlled by the quantity of raw coal supplied to the carbonizer. A study of the heating of Moscow lignite alone and the rapid heating of airdried lignite by mixing with hot coke was made by Solyakov (76B). Final temperatures of 400' to 750' C. were achieved by rapid heating. The yield of tar was highest for final temperatures of 500' to 600" C. obtained by rapid heating. Taits and Andreeva (78B) described experiments in which brown coal or noncoking coals were placed in a press form and heated at a rate of 3' C. per minute. The coal mass was pressed at incipient coal decomposition, heated to 950" C. in a muffle, and cooled. Stable coke was produced by this technique. The effect of different scavenging gases on the yields of products at low temperatures of carbonization was studied by Steinbrecher and Novotny (77B). The rate of flow of gas, along with the chemical reactions that may occur between the gas and the distillation products, had a significant effect. Hydrogen decreased both the tar and phenol yields relative to yields obtained
anr4 with an inert gas. Steam also increased both tar and phenol yields. T h e Bureau of Mines reviewed work in coal research for 1957 (19B). A series of carbonization tests was made on a dried Texas lignite in the Bureau's Denver, Colo., coal research laboratory in a n &inch fluidized bed reactor (shown), heated both internally and externally, varying the air-lignite ratio. T h e principal effects of increasing this ratio were a decrease in char and tar yields and an increased yield of combustible gas per pound of moisture- and ash-free lignite charged. Thermal stabilization of anthracite by calcination was achieved in a pilot-scale, verticalshaft reactor (p. 720) by the Bureau's
Unit Processes Review
Dainton and Kaye (5B). Their data suggest that maceral composition largely determines the swelling or contraction in the plastic zone. At carbonization temSubject Ref. peratures above 600" C., briquets Desulfurizinglow-temperature char (2B) contract in a manner independent of Low-temperature carbonization of ( 7 7B) carbonaceous materials their previous history. Parks and others Coke manufacture from coke breeze ( 75B) (70B) found no relationship between and coal petrographic composition and yields of Expanding properties of American (ZOB) carbonizing products for Hernshaw seam coals tested in a sole-heated oven Carbonization of briquets (27~) coal. Reactivity of residues from low-temperature carbonization of low- and highrank coals was investigated by Nandi and Anthracite Experiment station, Schuylothers (8B). T h e greater reactivity was kill Haven, Pa. observed for residues from low rank Expansion and contraction of briquets coals at 500" to 600" C. because of the during carbonization was reported by greater content of active oxygen groups.
Additional Publications on Low- and High-Ternperature Carbonization
Oven Operation, Products, By-products
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Bureau of Mines' Denver coal research laboratory uses 8-inch-diameter, fluidizedbed reactor for low-temperature carbonization of lignite and noncoking coals
The effect of heating rate on coke quality was studied by Kalinowski and others (742). Two blends were tested a t heating rates of 0.895" C. per minute to 1.43" C. per minute. At the higher rate, the coke strength and the >2.75inch coke decreased. Gayle and Eddy (9C) examined factors of oven width, flue temperature, and coking rate. They concluded that coking times vary as the 1.49 power of oven width ; oven width exerts little influence on coke properties when coking rates are constant; and moderate changes in flue temperature have little influence on coke properties when coking rates are constant. Preheat effects on coke quality were investigated by Erkin and others (8C). T h e strength of cokes derived from weakly coking coals increased materially following preheat of the charge a t 250" C. Dmitriev and Enik (6C) treated weakly coking coals with vapors from coke ovens. Carbonization of the treated coal resulted in coke of improved quality. A laboratory study on the effects of high-carbon additives on the carbonizing properties of Illinois coals was reported by Harrison (72C). His data showed that the quantity, particle size, and nature of the additive affect the composition of the coke. Partington and Sidebottom (27C) investigated the effect of inorganic additives on the carbonizing properties of coal briquets. The use of additives and carbonization under reduced pressure decreased the distortion and sticking tendencies of the briquets and produced a more compact coke product. A 17-inch movable wall oven was used by Jackman and others (73C) to test blends of Illinois coals with six medium-volatile coals. The factors of coal size and blend composition were examined by Brisse and Price (2C) in a full-scale coke oven model. Durand VOL. 52, NO. 8
AUGUST 1960
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and Lahouste (7C) described a laboratory scale coke oven of 20-kg. capacity. Results from the laboratory unit agreed with those obtained from the 400-kg. oven. Wet- and dry-coke quenching techniques were examined by Gayle and others (70C). Dry quenching yields a coke that is slightly larger and more resistant to degradation by impact forces. According to Cameron and Stacy (3C), chars contain two distinct pore systems similar to coke. Fine-grinding does not alter the density of coke and char but does increase their surface areas, as the pores are made accessible to adsorbate molecules by grinding. Studies made by Terres and Raven (23C) on the relationship of coke reactivity and strength to coke structure showed that dense coke with heavy cell walls and a fine pore structure has both maximum strength and maximum reactivity. Moutach and Guerin (20C) reported that coke reactivity is related to microporosity.
Other Studies o f Oven Operation, Products, and By-products
Subject Ref. Delayed coking of lignite tar (5C) Handbook of the coking industry ( 77C) (Vol. 11) Prediction of coke quality from ( 1 % ) composition of coking coal blends of medium- and low-volatile coals Electrical conductivity of coke ( 76C) Coke and pitch from low-tempera- ( 77C) ture tar Production of blast-furnace coke ( 2 2 C ) from noncoking coals
A statistical examination of BM-AGA 800°, 900°, and 1000" C. carbonization results was made by Walters and Birge (24C). They compared these values with industrial practice. The physical properties of BM-AGA cokes agree closely with industrial coke, except for the 2-inch shatter index and the apparent specific gravity. Dahme (4C) evaluated the micum drum test at 100, 600, and 800 revolutions. The data permitted an estimate of the fissure strength and structural strength of coke. The conversion of organic sulfur in coal to sulfide sulfur by coking in the presence of calcium hydride was investigated by Angelova and Syskov ( I C ) . They concluded that under coking conditions it is difficult to transform all organic sulfur of coals to sulfide sulfur. Medvedev and others (79C) reported that the residual sulfur in the coke generally did not decrease when several inorganic and organic compounds were added during carbonization. Iron(I1) sulfide added to the coal reduced the evolution of sulfide sulfur (7%').
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Vertical shaft pilot plant for calcining anthracite is located at Bureau of Mines Anthracite Experiment Station, Schuylkill Haven, Pa.
Oil Shale Pyrolysis by Charles
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H. Prien, Denver Research Institute, Denver, Colo.
N THIS twelfth review of research on oil shale pyrolysis, over 100 reports have again been screened ; the most significant have been selected and are reported in the sections which follow.
INDUSTRIAL AND ENGINEERING CHEMISTRY
General Savage and Hough ( 7 0 ) have examined the present status of a potential U. S. shale oil industry, including re-
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cent advances in reducing mining and retorting costs. An excellent up-to-date map of private shale land holdings is presented. In an article analyzing when a U. S. shale industry might begin, Welles (6D)noted the effect of such factors as the depletion allowance, capital availability, and the foreign and domestic surplus of petroleum. H e concluded that the evidence points to favorable conditions within the present decade. A comprehensive study of current prospects for a U. S. shale industry was made by Cornel1 (20) in the light of current technology, the future demand for liquid hydrocarbons, and rising petroleum production costs. H e concluded that shale oil is already competitive with domestic crude petroleum production a t current petroleum prices; and that it is more than competitive with new petroleum production because of the latter’s increasing high finding and production costs. American Gilsonite disclosed details of its plant for treating the solid hydrocarbon gilsonite to produce gasoline, railroad fuel, and electrolytic coke ( 4 0 ) . This plant is currently being expanded from 850 to 1100 tons per day capacity. Four companies have recently announced plans for a cooperative attempt to process the Athabaska tar sands to recover a “crude oil” bitumen and naphtha (5D).
General Reports on Oil Shale Pyrolysis Subject Ref. Index of oil shale and shale oil pat- (30) ents in United Kingdom and Europe Economic analysis of chemical re- ( 7 0 ) fining of Estonian shale
7
The Organization for European Economic Cooperation held a meeting in Paris in October 1959 to discuss possible sharing of knowledge regarding the processing of oil shale fines. The experts present concluded that the various shales throughout the world differed sufficiently to make any single common method of fines processing impractical. The Bureau of Mines has conducted a petrographic and chemical analysis of shales from Australia, Brazil, Canada, France, Manchuria, New Zealand, Scotland, Spain, Thailand, and the Union of South Africa (80). These represent most of the major oil shale areas outside of Germany, Estonia, and the U.S.S.R.
Basic Research The only basic research on U. S. shales reported during the year was performed by the U. S. Bureau of Mines.
In an extremely interesting study, Tisot and Murphy (5E) carefully removed the organic matter from Colorado shales of various richness and then examined the particle size of the primary inorganic particulate matter remaining. I t was found that 90% (weight) of these particles had equivalent spherical diameters less than 44 microns and were predominantly rhombic in form. Both lean and rich shales yielded similar particle size distributions, although the leaner shales had a higher percentage of conglomerated masses. This fineness of the basic “rock” of Colorado oil shale is significant in understanding the geologic origin of the shale and in studying the relationship between inorganic and organic constituents. From an examination of the extracts obtained from Colorado shale by thermal solution at 25” to 350” C., Robinson and Cummins (ZE) concluded that both a high nitrogen and a low nitrogen form of kerogen exist and that the latter is .t more difficult to solubilize. Similar conclusions were reached previously by Schnackenberg and Prien. From their study, Robinson suggests that Colorado kerogen may consist of 5 to 10% straightand branched-chain paraffins of 25 to 30 carbon atoms; 20 to 2501, of naphthenic structures together with 10 to 15y0 aromatic structures, both with 3 to 5 rings per molecule; and 45 to 60% of cyclic structures containing hetero atoms. A study of the stepwise oxidation of Yugoslavian (Aleksinac), U. S. (Green River), and English (Kimmeridge) oil shales was undertaken by Stefanovic (4E) with potassium permanganate in acetone solution instead of the usual stronger alkaline medium. Results on Yugoslavian shale indicate that it consists of comparatively long aliphatic chains with occasional isolated double bonds, together with partially unsaturated hydroaromatic rings, but no benzenoid structures. Results on U. S. and English shales will be reported later. Russian basic research on oil shale continues, as in the past few years, to be the dominant factor in this field. In examining the kinetics of decomposition of Baltic shales it was found ( 7 E ) that the activation energy of initial pyrolysis to thermobitumen was a first-order process with a n activation energy of 52,800 kcal. per mole. The molecular weight of the micromolecules formed by decomposition averaged 4300. A series of 22 Russian reports by Semenov and others (3E) describes a comprehensive attack on the fundamental properties of Baltic oil shales. Among the results of interest are the following: An analysis of the kerogen present indicates a predominantly cyclic structure with such saponifiable groups as esters, lactones, and anhydrides. By flotation I
concentration two major organic fractions differing in carbon, hydrogen, and oxygen content and in yield of acidic and neutral components were obtained. T h e heat of dissociation of the organic concentrate during semicoking was found to be about 90 to 100 cal. per gram. A considerable amount of work on “process properties”-e.g., reactivity with steam, particle segregation during coking, and the use of shale coke for cement manufacture-is also reported in this series, but it is too voluminous to review in detail.
Retorts and Retorting Processes The Bureau of Mines has released results of crushing experiments on Green River shales, as conducted several years ago in a jaw crusher, Jeffrey hammermill, gyratory crusher, and a number of other types (14F). Particle size distributions for the various crushers are given, but there are no adequate dxta on energy requirements. A more comprehensive study of the crushing of oil shale is still sorely needed. Three recent publications summarize the retorting research conducted at the Bureau of Mines on the gas flow retort (9F), entrained-solids, high temperature retort (79F), and the gas combustion retort (427). T h e last report is an interesting attempt to correlate statistically the complex interrelationship between the major process variables in gas-combustion retorting, the method believed by the Bureau to be commercially most promising. The authors d o not analyze the underlying causes of the results obtained in detail. Over 15 U. S. patents on oil shale retorting appeared during the review period. Six of these involve various aspects of the Union Oil Co. upflow shale retorting process. Basic retort design is described in three of these patents (7F, 2F, 20F). The remaining patents cover methods of solids feeding (72F) and segregation (73F) and sludge distribution ( 8 F ) . Esso Research and Engineering has improved the fluidizedsolids retorting method (76F)to minimize readsorption of oil on the finely divided spent shale and to increase heat transfer rates. T h e basic idea is to entrain the fines produced as a result of decrepitation in the fluidizing medium, thus making use of solid-to-solid heat transfer. I n a process described by Coulson (3F), shale is crushed to a fine powder with superheated steam, the fines are cooled, a wetting agent is added (and a diluent solvent, if necessary), and the mass is centrifuged to recover the oil. Features of the process are similar t o this inventor’s well known process for tar sands. The Dow Chemical Co. VOL. 52, NO. 8
AUGUST 1960
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Unit Processes Review
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Additional S t u d i e s of Retorting Subject
Ref.
Review of Russian research on (IOF) underground retorting of shale Separation of retorting, combus- ( 7 7 F ) tion, and preheating zones in individual vessels Fractional condensation of shale ( 6 F ) oil vapors on incoming raw shale Use of aerobic bacteria in the hy- ( 7 F ) draulic mining of oil sands
(5F) proposes that substantial benzene and ethylene yields can be obtained by retorting a t around 760" C. and thence immediately cracking the vapors before condensation in a separate cracking zone maintained at 700" to 900" C. The single-step entrained solids method of the Bureau of Mines (79F) has previously been employed for benzene and ethylene production. A comprehensive earlier internal publication ( 7 5 F ) of the Estonian oil shale ministry has recently been brought to this reviewer's attention. This is a book containing collected papers on the technology and economics of semicoking of Estonian oil shale. T h e five major sections of this work included studies on raw material properties, operation of tunnel ovens, the technology of the Kiviolli shaft-type kiln, beneficiation of raw shale feed to tunnel and shaft-kilns, and the processing of shale fines. The last section is particularly interesting in that a heated solid-thermosphere process is described with certain features related to the Aspeco thermosphere process now under development in the United States. A more concise summary of recent developments in Estonian oil shale technology than the above has been published by Sinel'nikov (78F). Estonian oil shale fines 0 to 25 mm. in diameter have been beneficiated by flotation in kerosine and a shale-tar fraction ( 7 7F). Organic concentration was increased from a n original 3670 to as much as 85%, with 4070 yield of concentrate. Throughput capacities, however, were low.
Shale Oil and By-products The result of single-pass hydrogenation of crude Colorado shale oil produced by the gas combustion process to gasoline was discussed by Carpenter and Cottingham (ZG); 17 different catalysts were used, of which molybdena-alumina produced the greatest gasoline yield. With zinc chromite catalysts the gasoline product was similar to that from thermal cracking, except that nitrogen and sulfur content was lower. I n a Russian study
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of catalytic hydrogenation of shale oil (73G) tungsten sulfide and molybdenum sulfide catalysts were found to be particularly effective a t 260 atm. pressure and 400' C. T h e treatment of Russian shale tars from Estonian tunnel kilns and gas generators by hydrogenation and the recovery of a gasoline fraction by catalytic polymerization was described by Zelenin (74G). The recovery of diesel oil and pitches is also mentioned. T h e use of zinc chloride treatment to reduce the bromine number of these Estonian shale tars prior to fractionation was outlined recently (5G). Another publication (6G) mentions the recovery of a lubricating oil fraction after preliminary zinc chloride treatment, or alternately, the use of the distillate fractions obtained for synthesis of surface active agents. The entire problem of utilization of the Estonian shales for chemical synthesis was reviewed in a conference at Tallin in May 1959 (70G). Among the reports presented were those on the use of the high-boiling phenol fractions of shale tar, refining methods for the shale tar hydrocarbon fractions, the manufacture of ammonia and light hydrocarbon gases, and the feasibility of producing varnishes, resins, detergents, and similar products. Feofilov (7G) has described the hydrogenation of neutral oxygen compounds of these shales to cyclic compounds, aromatic ketones, and phenyl esters using nickel oxide or molybdenum sulfide catalysts. The distribution of sulfur compounds in Baltic shale tar fractions was studied by Sillard ( I Z G ) , particularly in relation to the sulfur compounds appearing in gasolines produced therefrom. He found most of the sulfur to be concentrated in thiophene and sulfide structures. U. S. shale oils yield similar results. T h e manufacture of portland cement from oil shale and limestone has been patented by Texaco (77G). T h e process is unique in that the shale is suspended
O t h e r Publications o n S h a l e Oil a n d By-products Subject Ref. Hydrocracking of Maoming shale (3G) tar Use of molybdenum oxide contain- (8G) ing cracking catalysts for shale oil Utilization of shale phenols in plas- (75G) tics, antioxidants, and wetting agents Sulfonated detergents, wetting, and ( 9 G ) emulsifying agents from shale oils Use of oxidized shale concentrates (4G) as fertilizers Compression and heating of raw ( I G ) shale to molded articles
INDUSTRIAL AND ENGINEERING CHEMISTRY
in water and thence passed to two high velocity nozzles. T h e impingement of the two high velocity slurry streams so created produces the necessary disintegration of the shale to the fineparticle size required for subsequent burning to cement.
literature Cited Coal Pyrolysis Mechanism, Kinetics, Thermochemistry
(IA) Berkowitz, N., Fuel 39, 47-58 (1960). (2A) Brown, J. K., Ladner, W. R., Sheppard, N., Zbid., 39,79-86 (1960)., (3A) Brown, J. K., Ladner, W. R., Ibid. 39, 87-96 (1960). (4A) Corrales, J. A., Krevelen, D. W. van, J . Znst. Fuel 33. 10-16 119601. (5A) Ergun, S., 'OO'Donnkll, H. J., Parks, B. C . , Fuel 38,205-10 (1959). (6A) Given, P. H., Zbid'., 39,147-53 (1960). (7A) Hertog, W. den, Berkowitz, N., Zbid., 39, 125-31 (1960). (8A) Holden, H. W., Robb, J. C., Zbid., . 39, 39-46 (1960). . (9A) Iyengar, M. S., Dutta, S. N., others, Zbid., 39, 189-92 (1960). (10A) Iyengar, M. S., Lahiri, A., Brennstof-Chem. 40, 8--13 (1959). (11A) Krevelen, D. W. van, Waterman, H. I., Wolfs, P. M. J., Brenstoff-Chem. 40, 155-9 (1959). (12A) Krevelen, D. W. van, Wolfs, P. M. J., Waterman, H. I., Zbid., 40, 371-7 (1939). (13A) Krevelen, D. W. van, Dormans, H. N. M., Huntjens, F. J., Fuel 38, 165-82 (1959). (14A) Krevelen, D. W. van, Goedkoop, M. L., Palmen, P. H. G., Zbid., 38, 256 (1959). (15A) Kroeger, C., Compt. rend. congr. intern. chim. ind. 31, Liege, 1958, published as Znd. chim. belge, Suppl. 1, 4.38-43 (1 959 ). (16A) Kuczynski, W., Andrzejak, A., others, Przemysl Chem., 38, 44-7 (1959). (17A) Maher, T. P., Harris, J. M., Yohe, G. R., Illinois State Geol. Survey Rept. Invest. No. 212 (1959). (18A) Mazumdar, B. K., Chakrabartty, S. K., Lahiri, A , , Fuel 38, 112-14 (1959). (19A) Mazumdar, B. K., Choudhury, S. S., Lahiri, A,, Zbid., 39, 179-82 (1960). (20A) Nadziakiewicz, J., Heilpern, S., Pampuch, R., Prace Inst. Hutniczych 2, 107-12 (1959). (21A) "Proc. Third Conf. on Carbon, Univ. Buffalo, 1957," Pergamon Press, New York, 1959. (22A) Rusinko, F., Jr., Weinstein, A., Walker, P. L., Jr., Division of Gas and Fuel Chemistry, 136th Meeting, ACS, Atlantic City, N. J., September 1959. (23A) Smidt, J., Krevelen, D. W. van, Fuel 38, 355-68 (1959). (24A) Urazovskii, S. S.,Voloshin, V. A., Vysotskaya, A. I., Doklady Akad. N a u k S. S. S. R. 120, No. 3, 595 (1959). (25A) Wolfs, P. M. J., Krevelen, D. W. van, Waterman, H. I., Fuel 39, 25-38 (1960). (26A) Wolfs, P. M. J., Krevelen, D. W. van, Waterman, H. I., Brenstoff-Chem. 40, 189-94 (1959). (27A) Ibid., pp. 215-19. (28A) Ibid.,pp. 314-26. (29A) Wolfs, P. M. J., Waterman, H. I., Krevelen. D. W. van, Zbid., 40, 241-51 ( 1959). (30.4) Ibid., 40, pp. 342-6.
a n v d Unit Processes Review Low- a n d High-Temperature Carbonization (1B) Allied Chemical Corp., Brit. Patent 814,791 (June 10, 1959). (2B) Batchelor, J. D., Gorin, E., Zielke, C. W., IND.ENC.CHEM.52,161-8 (1960). (3B) Berg, L., Atkinson, D. E., Chem. Eng. Progr. 5 6 , 73-7 (1960). (4B) Coal Age 65, No. 2, 26-7 (1960). (5B) Dainton, A. D., Kaye, W. G., J. Znst. Fuel 32, 571-8 (1959). (6B) Gerlach, G., Bergbautechnik 9, NO. 1, 7-16 (1959). (7B) Glenn, R. A., Jacoby, J. W., BituminousCoal Research 19,No.3,13-15 (1959). (8B) Nandi, S. P., Kini, K. A., Lahiri, A., Brennstoff Chem. 40, 85-7 (1959). (9B) Odell, W. W., U. S. Patent 2,898,272 (Aug. 4, 1959). (10B) Parks, B. C., O’Donnell, H. J., others, U. S. Bur. Mines, Rept. Invest. 5453 (1959). (11B) Poindexter, F. E., Lowe, F. W., U. S. Patent 2,903,400(Sept. 8, 1959). (12B) Pound, G. S., Coke and Gas 21, 395401 (1959). (13B) Zbid., pp. 446-53. (14B) Zbid., pp. 521-3. (15B) Schulz, E., U. S. Patent 2,907,698 (Oct. 6, 1959). (16B) Solyakov, V. K., Nauch. Doklady Vysshei Shkoly, Energet. No. 1, 207-14 (1959). (17B) Steinbrecher, H., Novotny, R., Brennstof-Chem. 40, 50-2 (1959). (18B) Taits, E. M., Andreeva, I. A., Nauch. Dokladv Vvsshei Shkolv. Khim. i Khim. Tekhnh., N o . 1, 169-f2 (1959). (19B) U. S. Bur. Mines, Inform. Circ. 7905 (1959). (20B) Wilson, J. E., Naugle, B. W., Wolfson, D. E., U. S. Bur. Mines, Rept. Invest. 5537 (1959). (21B) Yavorsky, P. M., Friedrich, R. J., Gorin. E.. IND.ENC. CHEM.51. 833-8 (1959). ’
Oven Operation, Products, By-products (1C) Angelova, G. K., Syskov, K. I., Nauch. Doklady Vysshei Shkoly, Khim. i Khim. Tekhnol., No. 1, 166-8 (1959). (2C) Brisse, A. H., Brice, J. G., Blast Furnace Steel Plant 47, 1285-90 (1959). (3C) Cameron, A., Stacy, W. O., Australian J . Appl. Sci. 10, NO. 4, 449-57 (1959). (4C) Dahme, A., Gluckauf 95,680-7 (1959). (5C) Dell, M. B., IND.ENG. CHEM.51, 1297-8 (1959). (6C) Dmitriev, G. N., Enik, G. I., Zzuest. Akad. N a u k S.S. S.R., Otdel. Tekh. N a u k , Met. i Topliuo No. 1, 114 (1959). (7C) Durand, G., Lahouste, J., Assoc. Tech. de 1’Industrie du Gaz, Congres, Aix-les-Bains (Savoie), 1959. (8C) Erkin, L. I., Petrov, V. K., Bernatskaya, M. A., Koks i Khim. No. 2, 13-16 (1959). (9C) Gayle, J. B., Eddy, W. H., Zbid., 5592 (1960). (1OC) Gayle, J. B., Eddy, W. H., Sutton, P., U. S. Bur. Mines Rept. Invest. 5479 (1959). (11C) Grosskinsky, Otto, “Handbuch des Kokereiwesens 11,” Karl Knapp Verlag, Dusseldorf, West Germany, 1959. (12C) Harrison, J. A., Illinois State Geol. Survey Circ. 289 (1960). (13C) Jackman, H. W., Eissler, R. I., Helfinstine, R. J., Ibid., 278 (1959). (14C) Kalinowski, B., Fedyk, K., Kmiotek, J., Koks-Smola-Gaz 4,No. 1, 43-6 (1959). (15C) Krevelen, D. W. van, Huntjens, F. J., Wilms, A. H., J . Znst. Fuel 33,3-9 (1 960). --,\ - -
(16C) Kroger, C., Dobmaier, N., Brennstof-Chem. 40, 1-8 (1959).
(17C) McNamara, J. H. (to Aluminum Co. of America), U.S. Patent 2,916,432 (Dec. 8, 1959). (18C) Medvedev, K. P., Zzuest. Akad. N a u k S. S. S. R., Otdel. Tekh. Nauk, M e t . i TogLivo No. 1, 100-5 (1959). (19C) Medvedev, K. P., Petropolskaya, V. P., Nikitina, K. A., Koks i Khim. NO.8,15-18 (1959). (20C) Moutach, M . , Guerin, H., Bull. SOC. chim. France 1959, pp. 102-15. (21C) Partington, R. G., Sidebottom, R., J.Inst. Fuel 32, 417-21 (1959). (22C) Sapozhnikov, L. M., Koks i Khim. NO. 3, 22-7 (1959). (23C) Terres, E., Raven, W., Gas-u. Wasserfach 100, 993-1001 (1959). (24C) Walters, J. G., Birge, G. W., U. S. Bur. Mines, Rept. Invest. 5467 (1959). Oil Shale Pyrolysis
General (1D) Andrianov, V. M., Lageda, P. R., others, Khim. i Topliua i Masel 4, No. 10, 57-61 (1959). (2D) Cornell, P. A., “An Appraisal of Current Prospects for a U. S. Shale Oil Industry,” M.S. thesis, Univ. of Southern California Press, Los Angeles, 1959. (3D) Klosky, S.,U. S. Bur. Mines Bull. 574, Pt. 11, United Kingdom Patents (1959); Zbzd., Pt. 111, European Patents (1359). (4D) Morris, L. P., Chem. Eng. Progr. 5 6 , NO. 4, 49-53 (1960). (5D) Pasternack, D. S., Zbzd., 56, No. 4, 72-5 (1960).
5504 (1959). Basic Research (1E) Mitzurev, A. K., Trudy Vsesoyuz Nauch-Zssledouatel. Znst. Po Pererabotke Slantsev 1958. No. 6. 245-65. (2E) Robinso;, W. E., Cummins, J. J., J . Chem. €3 Eng. Data 5 , 74-81 (1960). (3E) Semenov, S. S., Kornilova, Yu. I., others, Trudy Vsesoyuz Nauch-Zssledouatel; Znst. Po Pererabotke Slantsev 1955, No. 3, 5-228. (4E) Stefanovic, G., Vitorovic, D., J. Chem. 6 3 Eng. Qata 4, 162-7 (1959). (5E) Tisot, P. R., Murphy, W. I. R., Division of Gas and Fuel Chemistry, 136th Meeting, ACS, Atlantic City, N. J., September 1959. Retorts and Retorting Processes (1F) Berg, C., Hines, J. E., others (to Union Oil Co. of Calif.), U. S. Patent 2,881,117 (April 7, 1959). (2F) Bewley, W. L., Hotz, J. L., Switzer, R. L. (to Union Oil Co. of Calif.), Zbid., 2,895,885 (July 21, 1959). (3F) Coulson, G. R. (to Can-Amera Oil Sands Development, Ltd.), Zbid., 2,911,349 (Nov. 3, 1959). (4F) Dannenberg, R., Matzick, A., U. S. Bur. Mines Rept. Invest. 5545 (1960). (5F) Dow Chemical Co., Brit. Patent 816,537 (July 15, 1959). (6F) Evans, L. P. (to Socony Mobil Oil Co.), U. S. Patent 2,885,338 (May 5, 1959). (7F) Hitzman, D. 0. (to Phillips Petroleum Co.), Zbzd., 2,907,389 (Oct. 6, 1959).
(8F) Hotz, J. L., Switzer, R. L. (to Union Oil Co. of Calif.), Ibid., 2,892,758 (June 30, 1959). (9F) Kalcevic, V., Lankford, J. D., U. S. Bur. Mines Rept. Invest. 5507 (1959). (10F) Krukovskii. V. K.. Pitin. R. N.. ‘ Farberov, I. L.; Prodzemnaya GaszJikatsiya Uglei 1959,No. 3, 8-10. 1F) Lakota, B. M., Vseyoyuz NauchIssledouatel. i Proekt. Inst. M k h . Obrabotki Polezn. Zzkopaemykh 1957,No. 102,303-14. 2F) Lieffers, W. C. (to Union Oil Co. of Calif.), U. S.Patent 2,875,137 (Feb. 24, 1959). 3F) Lieffers, W. C., Riddick, F. C., Switzer, R. L. (to Union Oil Co. of Calif.), Zbid., 2,891,669 (June 23, 1959). 4F) Matzick, A., Dannenberg, R. O., Guthrie, B., U. S. Bur. Mines Rept. Invest. 5565 (1960). 5F) Ministry of Regional and Oil ShaleChemical Industry, Estonian S.S.R., Oil Shale-Chemical Combine “Kiviyli,’’ “Problems of Technology and Economics of Industrial Semicoking of Oil Shale,” State Scientific and Technical Publishing House of Petroleum and Mineral Fuel Literature, Leningrad, 1957. 6F) Murphree, E. V. (to Esso Research and Engineering Co.), U. S. Patent 2,908,617(Oct. 13, 1959). 7F) Scott, J. W., Jr. (to California Research Corp.), Zbzd., 2,899,365(Aug. 11, 1959). (18F) Sinel’nikov, A. S., Trudy Vsesoyut Nauch-Issledouatel. Znst. Po Pererabotke Slantseu 1958, No. 6, 5-23. (19F) Sohns, H. W., Jukkola, E. E., Murphy, W. I. R., U. S. Bur. Mines Rept. Invest. 5522 (1959). (20F) Switzer, R. L. (to Union Oil Co. of Calif.), U. S. Patent 2,895,884 (July 21, 1959). Shale Oil a n d By-products (1G) Bauman, W. C., Graham, E. L. (to Dow Chemical Co.), U. S. Patent 2,900,269 (Aug. 18, 1959). (2G) Carpenter, H. C., Cottingham, P. L., U. S. Bur. Mines Rept. Invest. 5533 (1959). (3G) Chaing, Ping-nan, Kalechits, I. V., Wei, S.-P., Khtm. i Tekhnol. Topliu z Masel 4,NO. 19, 16-21 (1959). (4G) Degtereva, Z. A., Fomina, A. S., others, Russ. Patent 115,343 (Nov. 29, 1958). (5G) Faingol’d, S. I., others, Zzuest. Akad. Nauk Eston. S.S.R. Ser. Tekh. i Fiz.-Mat. N a u k 7. No. 3. 208-18 (1958). (6G) FaiAgol’d,’S. I., Kh&. i Tekhnol. Topliu i Masel 4, No. 10, 21-7 (1959). (7G) Feofilov, E. E., Garnovskaya, G. N., Trudy Vsesoyuz. Nauch-Zssledouatel. Znst. po Pererabotke Slantseu 1958,No. 6, 183-96. (8G) Kirshenbaum, I., Kearby, K. K., Ogorzaly, H. J. (to Esso Research and Engineering Co.), U. S. Patent 2,884,371 (April 28, 1959). (9G) Lapin, V. A., Trudy Vsesoyuz. NauchZssledouatel. Znst. Po Pererabotke Slantseu 1959, NO. 2, 118-23. (1OG) Pinyagin, N. B., Khim. i Tekhnol. Topliu. i Masel 4, No. 10, 65-7 (1959). (11G) Sellers, F. B., Chapin, H. M. (to Texaco Develo ment Corp.), U. S. Patent 2,904,445 &ept. 15, 1959). (12G) Sillard, Kh. A., Trudy Tallin Politekh. Znst. Ser. A 1958, No. 97, 119-28. (13G) Tsang, Pin-Nan, Wei, S.-P., others, Izuest. Sabir. Otdel. Akad. Nauk S.S.S.R. 1959,NO. 2, 81-96. (14G) Zelenin, N. I., Trudy Vsesoyuz. NauchZssledouatel. Znst. po Pererabotke Slantseu 1958. NO. 6. 24-38. (15G) Zelenin, N. I., Feofilov, E. E., Ibid., 1958, NO. 6, 131-43. VOL. 52, NO. 8
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