an II/ECIUnit Processes Review
Pyrolysis of Coal and
Shale
b
World-wide interest is focused on pilot plant Carbonization of coal in fluidized bed systems
b
Commercial-scale coke oven technology is again a maior interest of Russian researchers
b
U.S. shale activity is still restricted to limited studies at pilot plant level
T H E
RELATION
OF
CARBONIZATION
products to the structure of coal continues to intrigue technologists. T h e carbonization reaction was investigated by means of vacuum, differential thermal analysis, and thermogravimetric techniques. Considerably less time was devoted to the study of carbonization behavior of maceral types. There appeared to be a greater interest in the pilot plant scale carbonization of coal. European workers continued to devote a substantial part of their effort to basic research. A significant trend in United States commercial coke oven technology appears evident from the number of nonrecovery type ovens under construction. New York Mining and Mfg. Co. is building a t Calvert City, Ky., a 200 Mitchelltype oven unit capable of producing 1000 tons per day of coke. A 70-footdiameter rotary furnace developed jointly by Salem-Brosium, Inc., and New York Mining and Mfg. Co. was recently constructed a t Dorchester, Va. Advantages claimed for these units include : lower investment cost, close control of product
.
size and quality, and urofitable oueration without income from by-products. An increase was noted in the number of reports published on fluidized-bed carbonization. Several articles reported on the problem of carbonizing agglomerating coal in fluidized-bed retorts. Reports of general interest include studies of factors relating bench-scale, pilot plant, and commercial coke oven product yields, pressure carbonization, the effect of coking rate, and the composition and carbonization of blends. Commercial scale coke oven technology again appeared to be a major interest of Russian researchers. Russian activity in oil shale continues to become more important on the world scene. The U.S.S.R. has announced that Soviet engineers will design a shale gasification and petrochemicals plant for Brazil’s Paraiba River area. As part of a crash synthetic oil development program, Red China will emphasize construction of small “backyard” shale oil retorting plants of around 300 tons per year capacity. U.S. shale research is still restricted to a few experimental
studies on both underground and abovev ground retorting. The Aspeco process of The Oil Shale Corp. is the only pilot plant presently in operation. No experimental oil shale mining red search has been reported during the review period, although a 15-foot-diamete~ drill bit under test by the Hughes Tool Co. appears to have application to the design of a rotary oil shale mining machine. The application of nuclear energy to in situ shale oil production is still indeterminate and untested. Lignin has been proposed as the chief progenitor of oil shale kerogen. T h e basic chemical unit of Estonian oil shale kerogen is concluded to be a n aromatic ring attached to a 13- to 17-carbon atom side chain, the units being interconnected through ether linkages. I n the pyrolysis of oil shale particles, secondary thermal reactions during diffusion of the volatile organic matter through the hot peripheral zone of the particle were found to control production of liquid degradation products. As this outer zone approached inner-zone particle temperatures more gas was produced.
Pyrolysis of Coal by Manuel Gomez, Bureau of Mines, Denver, Colo. This review on coal pyrolysis covers the year 1960 for most of the literature, although selected journals were reviewed through March 1961. Mechanism, Kinetics, Thermochemistry The relation of magnetic mass susceptibility, weight loss, and crystallite parameters to carbonization temperature was investigated by Cave11 and Berkowitz ( 8 A ) . The authors suggest that pyrolysis reactions below 400’ C. involve a progressive loss of functional groups coupled with aromatization and condensation.
674
This hypothesis is in disagreement with the contention that, a t low temperatures, the major carbonization reactions involve a depolymerization process. Holden and Robb ( 7 2 4 applied mass spectrometry techniques to the study of vacuum pyrolysis. Only the lowest rank sample investigated yielded alicyclic type spectra in appreciable quantities. The quantity and molecular weight of tarlike material released a t coal decomposition increased with increase in rank. Studies by Mazumdar and others (78A) indicate that aromatic carbon may not be lost on pyrolysis below GOO0 C. I t was postulated that tar is formed
INDUSTRIAL AND ENGINEERING CHEMISTRY
mainly from the alicyclic portion of the coal and hydrocarbon gases primarily from the aliphatic groups. Iyengar and Lahiri (74A) attempted to relate reactive groups in coal to coke formation. They suggested that, a t low temperatures, the mobility of coal units in noncoking coals is restricted by condensation reactions. With coking coals, there are no condensation reactions and the coal units are free to exhibit fusion and plastic flow,. High proportions of the para isomer were found by K a r r and others (75A) among cresols and ethylphenols of low temperature tar, although the thermody-
x a m i c equilibrium distributions and kinetic distributions a t 500' C. predict high proportions of the meta and ortho isomers. This divergence was interpreted as indicative of a relationship between coal structure and the composition of low temperature tar. The relation between diamagnetic susceptibility of carbons and carbonization temperature was studied by Honda (734. His data show that the ease of graphitization of coals depends on rank and structure. Coals with carbon content greater than 85% graphitize more readily. Bien and others ( 5 4 studied the thermal conductivity of bituminous coal briquettes. They concluded that the conductivity of briquetted coal is dependent on the nature of base coal and independent of the briquetting pressure. A fluidized-bed differential thermal analysis (DTA) technique was employed by Basden (4A) to observe the low-temperature reactions in fluidized-bed coal pyrolysis, A sudden drop in differential temperature a t about 400' C. was attributed to agglomeration of coal and subsequent loss of the bed of discrete particles. When air was used for fluidization, the exothermic heat of oxidation was noted. Gaines and Partington ( 7 7A) used the D T A technique to study the reaction between a low-rank coal and various inorganic compounds. The carbonization reaction was slightly endothermic u p to 400' C. but strongly exothermic between 400' and 500' C. Their results gave no indication of a chemical reaction between the low rank coal and SiOz, A1~08,MgO, CaO, Fe, or Fe804. A report by Boyer and Payen (6A) advanced the hypothesis that the steep rise of the D T A curve exhibited by a coking coal between 420' and 450' C. (generally interpreted as an exothermic effect) is due to the sudden rising of the thermal conductivity a t the moment when the coal particles melt. Thermogravimetric studies by Luther and others (77A) revealed that within established temperature ranges of tar separation, methane loss, and dehydrogenation the differential curves (weight loss us. temperature) show maxima. The temperatures a t which these maxima occur can be related to chemical groups with known dissociation energies. Piottukh (2OA) used the thermogravimetric technique to measure the consumption of heat and the evolution of volatile matter as a function of temperature. The effect of heat on the sulfur forms in lignite was observed by Fowkes and Hoeppner (70A). The significant thermal change noted was the reduction of pyritic and sulfate sulfur to the sulfide. Angelova (7A) investigated the thermal stability of the different groups of organic sulfur in coal. H e concluded that the sulfur associated with sulfide and mercaptan groups is easily methylated, while
heterocyclic sulfur is not. Subsequent coking of methylated and nonmethylated coals showed that the methylated sulfur is volatilized, while a large proportion of the nonmethylated sulfur remains in the coke. Brooks and Smith ( 7 A ) reported that oxygen is more readily driven from heated coals than nitrogen. The greater retention of nitrogen a t higher temperatures may indicate the presence of nitrogen in cyclic structures in the original coal. Reactivity, specific surface, and average pore radius of brown coal and residues produced from the carbonization of brown coal were studied by Kuczynski and Andrzejak (76A). At carbonizing temperatures of about 200' C. a significant increase in surface area and reactivity was observed; whereas a decrease in average pore radius occurred a t 300' C. Additional studies are listed in Table I.
Table I. Mechanism, Kinetics, and Thermochemistry in Pyrolysis of Coal Subject Possible compositions of organic bound S in coal Fluidized-bed differential thermal analysis Chemical structure and properties of coal Influence of volatile content of brown coals on desulfurization during dry distillation New method for investigating and describing transformation of coal Fractional thermogravimetric analysis
Ref. ($A) (8A) (9A) (19A)
(21A) ($%?A)
l o w and High Temperature Carbonization An experimental, gas-fired oven of 500-kg. capacity was described by Eisenberg and others (ZB). Expansion pressure is measured by means of two watercooled pistons that operate through the doors of the chamber. A 15-pound test oven was developed by the British Coke Research Association (6B) for evaluating the coking characteristics of coal blends. By careful control of the bulk density, cokes are produced whose apparent specific gravity is slightly lower than commercial oven coke. The development of a 2-inch-diameter, fluidized-bed, carbonization assay was reported by Shrikhande (70B). Depending upon the rate of heat input, carbonizing times varied between 15 and 40 minutes and 30 and 60 minutes for carbonization a t 500" and 600' C., respectively. A pilot scale fluidized-bed unit was described by Shrikhande and Sen (77B). Carbonization of Indian coal a t 480' to 510' C. indicated that this retort has a capacity of 240 to 300 pounds per square foot per hour. The fluidized carbonization of noncoking Japanese coals was reported by
Terui (72B). For these tests, a retort of 100 to 150 kg./hr. capacity employing preheated air as the fluidizing medium was used. Carbonization heat was supplied by partial combustion of the volatile matter. Riedel (8B) investigated the carbonization of brown coal in fluidized-bed retorts. His data indicate that throughputs of the order of 2020 kg. per square meter per hour were attained. Iida and others (5B) reported the feasibility of carbonizing caking coals in a fluidized-bed reactor. Agglomeration of the coal particles was prevented by decreasing the average diameter of the coal, addition of pulverized coke, and mixing sand, iron sand, coke breeze, or forsterite with the coal charged. A fluidized-bed process for carbonizing agglomerating coals has been patented by Consolidation Coal Co. (74B). The bed is held a t 725' to 825' C. for a t least 5 minutes and then raised to a temperature higher than 825' C. I t is claimed that the quantity of inert that must be added to prevent agglomeration is materially reduced. Pressure carbonization studies were reported by Gryaznov and Petrov (4B). Raising the coking pressure increased the strength of some cokes and reduced it with others. The increase in yield of coke was found to be a function of the gas pressure. With an increase in gas pressure, the plasticization of the coal increased concomitantly with the swelling of the coal and porosity of the coke. A pilot scale traveling-grate stokercarbonizer was described by Gopal Rao and others ( 3 B ) . Coal of 24 to 25% volatile matter was partially burned on the grate and the heat of combustion was used for carbonization. T h e air-to-coal ratio was found to have a significant effect on the properties of the coke. Strength indices and yields were satisfactory for cokes of 6 to 9% residual volatile matter. Samples from various parts of a 250-kg. experimental oven during carbonization were obtained by Echterhoff and Mackowsky (7B). I t was concluded that the plastic phase is decisive in coke formation. The rate of heating in the plastic range determines the strength and structural properties of the coke. Table I1 includes further studies in this area.
Table It. Low and High Temperature Carbonization of Coal Subject High temperature carbonization Production of domestic coke in continuous vertical retorts Thermal decomposition of Shargun coal under conditions of rapid heating Carbonization of weakly or noncoking coals Carbonizing properties of Boone County, W. Va., coals
VOL. 53, NO. 8
o
AUGUST 1961
Ref, (7B) (9B) (13B)
(16B)
(16Bj
675
Unit Processes Review
an
Oven Operation, Products, By-Products The feasibility of recirculating products of combustion in coke ovens was studied by Kuperman and Agapov (77C). Recirculation caused a redistribution of temperature over a large part of the height of the oven chamber but had little effect on heating the upper layers of the coal. Factors related to heat consumption during carbonization were investigated by Izraelit ( 7 4 ' ) . An increase in coking time of 1 hour increased heat consumption 6 to 7 kcal. per kg.; a 10" C. increase in coke oven gas temperature caused a 5 kcal. per kg. increase in heat consumption. Heat requirements for Russian and other coke plants were discussed by Virozub and others (24C). The relationship between the heat of carbonization and volatile matter \.vas studied by Terres and Schweitzer ( 2 3 C ) . They concluded that the heat of carbonization could be established if rhe volatilc matter and petrographic composition were known. Carbonization temperature-pressure relationships were investigated by Radmacher and LeMarie (78C). With increase in oven wall temperature, both expansion pressure and coke strength increased with coals containing less than 21y0 volatile matter and decreased with coals containing more than 24y0 volatile matter. Coke yields, heat of coke formation, and heat of carbonization were discussed by Barking and Eymann (2C). Studies by Das Gupta and others (6C) indicate that high volatile, high swelling coals may not form weaker cokes at high coking rates, as generally believed. These researchers contend that there is an optimum heating condition for all coals under which best results are obtained. Coking rate studies by Echterhoff (7C) indicate that coke strength is markedly influenced by the coking rate ; whereas the final coke temperature is controlling with respect to composition, porosity, and apparent density of the
Pyrolysis of Oil
coke. Stahl and others (22C) observed that charging of dry coal had no significant effect on coke physical properties. They listed the following advantages for charging dry coal: decrease in the amount of gas cooling required, decrease in the amount of N H B liquor handled, and improvement in the ease of handling of the coal. From an extensive study of gas evolution rates during carbonization, Gryaznov ( 7 IC) concluded that the development of coking pressure depends mainly on the permeability of the barrier on the hot side (that is, the semicoke), the transitional zone in the act of solidifying. and the part of the coal layer undergoing maximum softening. In a later study, Gryaznov ( 7 2 3 observed that swelling increases with decreasing viscosity of the plastic coal mass and with increasing volatile matter. The influence of gas evolution on the swelling capacity of the plastic coal mass appears to become significant as the viscosity of the softened coal decreases. Gorovoi and others (7OC) noted that the hydrogen content of coke oven gas is inversely proportional to the evolution of volatile matter. Correlation factors established for coke, tar, liquor, "8, and gas obtainable from the Gray-King assay- equipment, pilot plant retorts, and commercial coke ovens were reported by Das Gupta and others (92). Ghosal and others (SC) developed a formula for predicting the yield of coke from the proximate analysis of the coal carbonized. Regression equations were derived for predicting shatter, hlicum, and Haven indices of coke from the heat of wetting and volatile matter content of the coal carbonized. M'hen u p to 10% low temperature char is blended with a high volatile coal, the increase in the 1.!%inch shatter index is directly proportional to the decrease in volatile matter of the blend, according to a report by Waters and Hesp (25C). The change in the 0.25-inch tumbler index is due primarily to the change in the bulk density of the blend. Bandopad-
Table 111.
Oven Operation, Products, By-products of Coal
Subject Reactivity of cokes Heating coal in equipment with directional travel of suspended layer Carbonization of coals in fluidized bed S35 in study of the process of desulfurizing coal Dry quenching of high temperature brown-coal briquet coke Activated coke dust preparation and suitability for adsorption of hydrocarbons and purification of coal gas
Itcf.
(4.C)
(8C) (I6C) (ISC)
(2W) (21C)
hyay and others (7C) observed that the conditions necessary to produce a stronp, hard coke from binary blends wrrc : maximum fluidity of the Gieseler plastometer not lower than 15 dial divisions per minute; plastic temperature range from the Gieseler test not lower than 25' C. ; rate of formation of semicoke as obtained from Gieseler tests at constant temperature of 420' C. not higher than 0.15 minute-'; and volatile matter, airdried basis, not higher than 32%;. Several Indian coals were alkylated by Iyengar and others (13C) in CS2 suspcnsion with benzyl chloride in the prrsence of AlC13. Alkylation increased tar yields to twice the original values. Coke yields decreased except with lignite. Gas yields decreased for all coals tested. The effect of carbonization gas, hydrogen, steam, and water gas as desulhrizing agents was studied by Roy and Basak (79C). Consolidation Coal Co. ( X ) patented a process in which noncaking coal is desulfurized by heating with an H2S acceptor at 1100' to 1600' F. 'Ihe coal and acceptor, consisting of M n O on an inert carrier, are then separated, and the acceptor containing the MnS is reoxidized by heating in air. Other rcports are summarized in Table 111.
Shale
by Charles H. P r i m , Denver Research Institute, Denver, Colo. For this 13th annual review on oil shale pyrolysis, over 80 technical articles have been examined and the most important selected for mention. The period of review is essentially from October 1959 through February 1961 for domestic journals and February 1959 through February 1961 for foreignjournals.
676
General
I n a survey of factors influencing the establishment of an American oil shale industry, Ertl (30) indicated his opinion that many oil industry leaders today are still misinformed as to the current status of oil shale technology and economics.
I N D U S T R I A LAND E N G I N E E R I N G CHEMISTRY
H e indicated that both capital and opcrating costs for shale oil production in America are now less than for new domestic petroleum. The use of nuclear energy to process U.S. shales in situ continues to be investigated. Project Plowshare ( I D ) conducted an underground chemical CY-
anb d -
Unit Processes Review
Basic Research
Oil Shale Corp. pilot plant, Denver Research Institute plosion 125 feet deep in Colorado oil shale, in the presence of krypton-85 as a chemical tracer. Migration of radioactive gases parallel to the shale bedding planes was detected. The test report concludes, however, that the results obtained cannot be quantitatively extrapolated to the case of a nuclear explosion in oil shale. Following any nuclear explosion, oil recovery must be accomplished by in situ The problems encountered are formidable. Murphy (5D)has surveyed the major factors involved, including permeability, air flux, pressure, rate of advance of pyrolysis zone, and consumption. Since oil shale is impermeable, mass permeability must be created by the nuclear
explosion. The finely divided burned “shale ash” may plug gas passage ways. Coke production would probably be sufficient to furnish fuel requirements. Additional work is listed in Table IV.
The degradation of various proteins, carbohydrates, plant and animal pigments, and lignins in diagenetic environments has been studied by Breger ( 2 3 ) . H e concluded that, of these biological materials. lignin, in the form of humic substances carried into marine basins, is probably the major progenitor of the organic matter in oil shale. The isolation of the organic matter from oil shale, unchanged, is a difficult and complex problem. Smith (73E)has examined available methods and concluded that mineral removal with HC1 and HF is most satisfactory. The ultimate analysis of Colorado oil shale kerogen, using this method, is described. The use of a modified Trent amalgamation procedure in concentrating the organic matter and determining its composition is detailed by the same author (74E). Chattanooga uraniferous black shale has been treated with moist ozone (6E)to decompose the organic matter and liberate the uranium present. As a by-product, over 60y6 of the organic carbon is converted to polyfunctional, water-soluble organic acids. Dicarboxylic acids from kerogen oxidation, using ” 0 3 have also been produced from Estonian shale organic matter (3E, 4 E ) . These acids contained 4 to 10 carbon atoms. In a report discussing the occurrence of uranium in oil shales (7E),it is concluded that the uranium is chemically combined with the porphyrins, asphaltenes, and humic acids of the organic matter. The mechanism of pyrolysis of an Estonian oil shale kukersite has been investigated by Raudsepp (SE), who concluded that the basic chemical unit is an aromatic ring attached to 13 to 17 carbon atoms bound together through ether linkages. The mode of formation of phenols, indanols, and naphthols during pyrolysis is postulated. Rikken (70E) stated that kukersite kerogen upon pyrolysis first undergoes a stabilization reaction resulting in a thermally more stable structure. No oil formation occurs during this stage. Other research is described in Table V.
Table V. Table IV.
General Studies on Oil Shale Pyrolysis Subject Ref.
Core analysis of Colorado oil shales,
(60)
1954-57 .._.
Chemical composition of Dicti- (40) onema shales Geology and resources of u.s* Utah ( B D ) naval oil shale reserve Oil yield and uranium content of ( 7 0 ) U. S. eocene shales
Basic Research in Oil Shale Ref.
Subject
Use of diazomethane to determine (f%E) active hydrogen in kerogen Heats of adsorption between kuker- (7E) site and various organic solvents Thermal and physical properties of (8E) Baltic oil shales Characteristicsof bituminous shales, (6E) humous clays, and similar materials Bibliography on constitution of oil (11E) shale kerogen, through 1957
VOL. 53,
NO. 8
AUGUST 1961
677
a
n
r
d Unit Processes Review
Retorts and Retorting Processes A number of patents by the Swedish Shale Oil Co. are of interest. I n the first two of these (3F, 4 F ) a vertical, gravity-fed retort is described, which is surrounded by an external circular furnace. T h e furnace fuel is spent shale with its associated carbonaceous residue. Water cooling coils in the furnace may be used to control combustion temperature. The retort gas is also water-cooled to avoid cracking and tar formation. The third patent ( 9 F ) covers the in situ recovery of oil from tar sands by moving a heating device progressively through a verticle hole drilled in the sands. The slower pyrolysis leads, it is claimed, to higher yields of gasoline. A U. S. patent ( 8 F )suggests that, in in situ pyrolysis of oil shale, inverse air injection from surrounding bore holes can be used to control heating and also plugging of the formation. T o reduce sulfur in the gases obtained from burning oil shale, it has been proposed ( 7 F ) that burning be conducted in a fluidized bed at 700' to 900' C., in the presence of finely divided limestone and a halogen salt. Shale normally producing gases containing 1% sulfur yielded less than O.l?yo sulfur by this method. An examination of the effect of particle size in oil shale pyrolysis has been made by Milk ( 7 F ) , using a kukersite shale graded into various fraction ranges between l and 25 mm. in diameter. Secondary pyrolysis of the volatile pyrolysis products diffusing through the peripheral hot zone in the lump was found to be the most important phenomenon. Maximum production of liquid products occurred while the peripheral zone temperature was relatively low. This is a significant article on the mechanism of retorting. Medium to high temperature (480' to 720' C.) pyrolysis of shale chips less than 1 inch in diameter was studied by Kyll (6F) using recycled shale ash at 750' to 800' C. as a heat carrier. Greater hydrocarbon production, including olefins, ethylene, and light gases was obtained. The Bureau of Mines entrained-solids retort, tested a number of years ago, yielded similar results. Table V I contains further studies on retorting.
Table VI. Retorts and Retorting Processes in Oil Shale Pyrolysis Subject
Ref.
Technical and economic survey of ( 2 F ) oxygen use in oil shale processing Process details on gasification of (10F) shale Process variables of the Bureau of ( 6 F ) Mines gas-combustion retort
be reduced before plasticizers comparable to those from Baltic shale were obtained. A detailed chromatographic study of the phenols present in Baltic shale oil has been reported by Lanin (IOG). Among the compounds specifically identified were phenol, rn- and p-cresol, and both 1,2,3- and 1,2,4-xylenols. Table VI1 lists other articles on this subject. Literature Cited Pyrolysis of Coal
be a first-order reaction influenced by nitrogen poisoning of the active catalyst centers. Nitromethane was found (2G) to be superior to liquid SO2 and 80% alcohol in the countercurrent extraction of nitrogen compounds from a Fushun crude shale oil. A light diesel oil was obtained by subsequent refining. I n analyzing the chemical composition of the nonaromatic portion of a Russian shale gasoline, Klesment (8G) noted that the pentanes and hexanes present were straight chain and that the olefins contained terminal double bonds. The Bureau of Mines has reported (6G) the detailed composition of a shale oil naphtha obtained by destructive recycle hydrogenation of a gas-combustion retort shale oil. Some 70% of the hydrocarbons present were paraffins and cycloparaffins, with the latter uniformly distributed throughout the naphtha. Mapstone (77G) has shown that the gums in shale gasoline are probably condensed pyridine homologs, quinones, and carboxylic acids or ketones. I n subjecting various narrow fractions of a U.S.S.R. shale oil to chemical treatment, it was found (5G) that polymerization and alkylation in the presence of metal halides could produce distillates containing u p to 90% mono-olefins. Alkylation of similar fractions yielded alkyl aromatics susceptible to complete sulfonation. Baltic and Volga shale oil heavy fractions have been compared as raw materials for plasticizers (4G). The high phenol content of the Baltic shale had to
Shale Oil and By-products
Mechanism, Kinetics, Thermochemistry
(1A) Angelova, G. K., Freiberger Forschungsh. A141,97 (1960). (2A) Angelova, G. K., Syskov, K. I., Izvest. Khim. Inst. Bulgar. Akad. Nauk 7 , 67 (1960). 3A) Basden, K. S., Fuel 39,270 (1960). 4A) Zbid., p. 359. 5A) Bien, A. S., Phillips, O., Wolkstein, M., Division of Gas and Fuel Chemistry, 138th Meeting, ACS, New York, September 1960. (6A) Boyer, A. F., Payen, P., BrennstqChem. 41,104 (1960 (7A) Brooks, J. D., k i t h , J. W., Division of Gas and Fuel Chemistry, 138th Meeting, ACS, New York, September 1960. (8.4) Cavell. P. A., Berkowitz, N., Fuel ' 39,401 (1960). (9A) Dormans, H. N. M., Krevelen, D. W. van, Ibid.,39, 273 (1960). (10A) Fowkes, W. W., Hoeppner, J. J., U. S. Bur. Mines Rept. Invest. 5626, 1960. (11A) Gaines, A. F., Partington, R. G., Fuel 39,193 (1960). (12.4) Holden. H. W., Robb, J. C., Zbid., 39, 485 (1960). ' (13A) Honda, H., J . Mines, Metals 6 Fuels (Spec. Issue) 7,25 (1959). (14A) Iyengar, M. S., Lahiri, A., Ibid., 7,16 (1959). (15A) Karr, C., Comberiati, J. R., Estep, P. A4., Fuel 39,475 (1960). (I6A) Kuczynski, W., Andrzejak, A., Zbid., 39, 361 (1960). (17A) Luther, H., Abel, O., others, Brennstof-Chem. 41, 257 (1960). (18A) Mazumdar, B. K., Chakrabartty, S. K., Lahiri, A., in "Proc. Symposium on Nature of Coal, 1959," p. 253, Central Fuel Research Inst., Jealgora, India, 1960. (19A) Mirev, D., Zlateva, Iv., Izvest. Khim. Inst. Bulgar. Akad. Nauk 7 , 3 (1960). (2OA) Piottukh, Yu. N., Irvest. Sibir. Otdel. Akad. ;Ihuk S. S. S. R. 1960, No. 3, p. 11. (21A) Ritter, H., Juranek, G., BrennstoffChen. 41,171 (1960). . -. ^^ (2ZA4)Waters, P. L., Anal. Chem. YZ, 852 (1960). '
Low and H i g h T e m p e r a t u r e Carbonization
Conversion of a 20° API Colorado shale oil to 78% gasoline by hydrocracking at 1000' F. and 700 p.s.i. over a platinum (0.67,) on ?-alumina catalyst was described by Kirshenbaum (7G). Details of catalyst preparation are given. I n hydrogenating a Maominsk shale tar crude a t 400' C. and 260 atm. over an MoS catalyst, both cracking and nitrogen removal were shown (7G) to
678
Table VII.
Shale Oil and By-products Subject
Chemical compounds present in a Russian oil shale tar Complete chemical analyses of constituents of a Baltic shale oil gasoline Products obtained by short-time thermal cracking of a Fushun shale oil residue
INDUSTRIAL AND ENGINEERING CHEMISTRY
Ref.
(Sc) (913)
(lac)
(IB) Echterhoff, H., Mackowsky, M. T., Gluckauf 96,618 (1960). (2B) Eisenberg, A., Juranek, G., others, Brennstof-Chem. 41,110 (1960). (3B) Gopal Rao, S., Mookherjee, M.K., others, J . Sci. Ind. Research (India) 19A,No. 1, 26 (1960). (4B) Gryaznov, N. S., Petrov. V. K., Coke and Chem. U.S.S.R. 1960, NO. 1, P. 27. (5B) Iida, T., Okuyama, T., others, J. Fuel Soc. Japan 39, 333 (1960).
a n b ! w Unit Processes Review (6B) Mott, R. A., J . Mines, Metals &? Fuels (Spec. Issue) 7, 290 (1959). 7B) Nakahara, M., Zbid., 7, 96 (1959). 8B) Riedel, H. G., Freiberger Forschungsh. A158,61 (1960). (9B) Shrikhande, K. Y., Chakrabarti, H. C., J . Mines, Metals ti3 Fuels 8, No. K. Y., Das Gupta, Zbid., 7, 264 (1959). f11B) Shrikhande. K. Y., Sen,. M.,. Zbid 7,!75 (1959). ’ 12B Terui, A., Ibid., 7, 260 (1959). 13B Vishnevskii, N. F., Zzvest. Akad. Nauk Uzbek S. S. R., Ser. Tekh. Nauk 1960, No. 3, p. 12. (14B) Welinsky, I. H. (to Consolidation Coal Co.), U. S. Patent 2,955,077 (Oct. 4, 1960). (15B) Williams, F. A. (to Minister of Power, London), Brit, Patent 829,498 (March 2, 1960)’: (16B) Wolfson, D. E., Birge, G. W., Lvnch. J. H., U. S. Bur. Mines Rept. &vest.’ 5628, ‘1960.
i
Oven Operation, Products, By-products (1C) Bandopadhyay, J., Tarafder, T. G., others, J . Inst. Fuel 33, 592 (1960). (2C) Barking, H., Eymann, C., Gas-u. Wasserfach 101, 49 (1960 (3C) Batchelor, J. D., Jurran, G. P., Gorin, E. (to Consolidation Coal Co.), U. S. Patent 2,927,063 (March 1, 1960). (4C) Boyer, A. F., Durand, G., Chim. @ ind. (Paris) 83, 223 (1960). (5C) Das Gupta, N. N., Ghosh, S . R., others, J . Mines, Metals t 3 Fuels (Spec. Issue) 7, 340 (1959). (6C) Das Gupta, N. N., Mukherjee, D., others, Zbid., 7,108 (1959). (7C) Echterhoff, H., Gluckauf 96, 929 (1960). (R??. Fidelman, E. Y., Novitskii, P. L., . Semenenko, D. P., Coke and Chem. U.S.S.R. 1960, No. 4, p. 12. (9C) Ghosal, A., Sinha, B. K., others, J . Mines, Metals @ Fuels (Spec. Issue) 7, 318 (1959). (1OC) Gorovoi, G. P., Belgorodskii, M. L., Bolshakov, G. I., Coke and Chem.
.
I--,
~ . c c ino m
N~ i *.-. -,=. i n
(11C2) Gryaznov, N. S., Zbid., 1960, NO. 6, p. 16. (12C) Zbid.. PJo. 8, p. 6. (13cj Iyen’gsir., M. S.. Baneriee. D. D.. Banerjee, D. K., Nature 186,*38? (1960): (14C) Izraelit, E. M., Coke and Chem. U.S.S.R. 1960, No. 2, p. 21. (15C) Kulikowski, G., Nadziakiewicz, J., Warmuzinski, J., Koks Smola Gaz 5, 138 (1960). (16C) Kulishenko, A. Z., Medvedev, K. P., Coke and Chem. U.S.S.R. 1960, No. 7,p. 5. (17C) Kuperman, P. I., Agapov, B. G., Zbid., 1960, No. 7, p. 24. (18C) Radmacher, W., LeMarie, H., Brennstoff-Chem. 41,166 (1960). (19C) Roy, K. K., Basak, N. G., J. Mines, Metals €3 Fuels (Spec. Issue) 7, 365,370 (1959). (20C) Schadlich, H., Freiberger Forschungsh. A159, 102 pp. (1960). (21C) Spichal, W. H., Brennstg-Chern. 41,113 (1960). (22C) Stahl, C . W., Symser, J. M., Aikman, R. P., in “Proc. Blast Furnace,
Coke Oven, and Raw Materials Committee,” 19, p. 131, Am. Inst. Mining Met. Petrol. Engrs., New York, 1960. (23C) Terres, E., Schweitzer, A., Gas-u. Wasserfach 101, 414 (1960). (24C) Virozub, I. V., Voloshin, A. I., Lgalov, K. I., Coke and Chem. U.S.S.R. 1960, No. 5, p. 23. (25C) Waters, P. L., Hesp., W. R., Australia Commonwealth Sci. Ind. Research Organization, Div. Coal Research, Ref. T. C. 41, March 1960. Pyrolysis of Oil Shale
General (1D) Adelman, F. L., Bacigalupi, C. M., Momyer, F. F., Univ. Calif. Radiation Lab. ReDt. No. UCRL 6274. 1960 (2D) Cashion, W. B., U.S. Geol. Survey Bull. NO. 1072-0, p. 753, 1959. (3D) Ertl, T., Natl. Western Mining and ’ Energy Conf., Denver, Colo., -April 1960. (4D) Kirret, O., Koch, R., Rundal, L. Izvest. Akad. Nauk Eston. S.S.R., Ser. Tekh. i Fiz.-Mat. Nauk 8, No. 4, 243 (1959). (5D) Murphy, W. I. R., Univ. Calif. Radiation Lab. Rept. No. UCRL 5678, p. 80,1960. (6D) Stanfield, K. E., Smith, J. W., U.S. Bur. Mines Rept. Invest. 5614.1960. (7D) Swanson, V. E., U.S. Geol. Survey, Profess. Paper No. 356-A, p. 1, 1960. Basic Research (1E) Alekperov, R. A., Efendiev, G. Kh., Doklady Akad. Nauk Azerbaidzhan. S.S.R.15,821 (1959). (2E) Breger, I. A., Geochim. Cosmochim. Acta 19, No. 4, 297 (1960). (3E) Degtereva, Z . A,, Fomina, A. S., Goryuchie Slantsy, Khim. i. Tekhnol., Akad. Nauk Eston. S. S. R., Inst. Khim. 1959, No. 3, p. 5. (4E) Degtereva, Z. A., Fomina, A. S., Nutre, E. O., Russ. Patent 127,653 (April 12, 1960). (5E) Jacobs, H., Erdtl u. Koftle 14, 2 ‘ (1961). (6E) Kinney, C. R., Leonard, J. T., Pennsylvania State University, University Park, Pa., private communication, 1960. (7E) Kniga, M. V., Mishchenko, K . P., Goryuchie Slantsy, Khim. i Tekhnol., Akad. Nauk Eston. S. S. R., Inst. Khim. 1959, No. 3, p. 21. (8E) Kollerov, D. K., Trudy Vsesoyuz NauchIssledovatel. Inst. po Pererabotke Slantsev 1959, No. 7 , p. 64. (9E) Raudsepp, Kh. T., Trudy Tallin. Politekh. Inst. Ser. A 1956, No. 73, p. 120. (10E) Rikken, J., Goryuchie Slantsy, Khim. i Teckhnol., Akad. Nauk Eston. S. S. R., Inst. Khim. 1959, No. 3, p. 31. (11E) Robinson, W. E., Stanfield, K. E., U.S. Bur. Mines. Inform. Circ. No. 7968,1960. (12E) Semenov, S. S., Kornilova, Yu. I., Dokshina, N. D., Trudy Vsesoyuz. Nauch-Issledouatel. Inst. Pererabotkz i Zspo1’zovan Topliva 1959, No. 8 , p. 28. (13E) Smith, J. W., U.S. Bur. Mines Rept. Invest. 5725,1960.
(14E) Smith, J. W., Higby, Anal. Chem. 32, 1718 (1960).
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Retorts a n d Retorting Processes (1F) Berglund, B. E. A,, Hormander, H. O., Senke, J. E. K. (to Aktiebolaget Atomenergie), U.S. Patent 2,928,718 (March 15, 1960). (2F) Bezmozgin, E. S., Barshchevskii, M. M., Vasil’eva, M. M., Trudy Vsesoyur. Nauch-Issledovatel. Inst. Pererabotki i Ispol’zouan Topliva 1959, No. 8 , p. 66. (3F) .Brandberg, A. R. L. (to Svenska Skifferolje Aktiebolaget), Swedish Patent 166,313 (Feb. 24, 1959). (4F) Dalen, D., Gejrot, C. J., Hedback, T. J. (to Svenska Skifferolje Aktiebolaget), Ibid., 167,120 (May 12, 1959). (5F) Dannenberg, R. O., Matzick, A., U.S. Bur. Mines Rept. Invest. 5545, 1960. (6F) Kyll, A. T., Stepanov, I. I., Goryuchie Slantsy, Khim i Tekhnol. Akad. Nauk Eston. S. S. R., Inst. Khim. 1959, No. P2.76. ilk, A., Ibid., 1959, No 3, p. 39. 8F) Prentiqs, S. S. (to Phillips Petroleum Co.), U.S. Patent 2,917,296 (Dec. 15, 1959). (9F) .Salomonsson, G. J. W. (to Svenska Skifferolje Aktiebolaget and Husky Oil Co.), U.S. Patent 2,914,309 (Nov. 24, 1959). (10F) VaYnshteYn, Ya. I., Bezmozgin, E. S., Sinel’nikov, A. S., Trudy Vsesoyuz. Nauch-Zssledouatel. Inst. $0 Pererabotke Slantsev 1959, No. 7, p. 147.
I‘”
Shale Oil and By-products (1G) Chiang, Ping-Nan, Lin, Li-Y, Trudy Vostochno-Sibir. Filiala, Akad. Nauk S.S.S.R., Ser. Khim. 1959, No. 18, p. 107. (2G) Chu, Hung, Fang, Ch’ing-Chi, Ch’i, Cheng-Chung, J a n Liao Hsueh Pao 4, 357 (1959). (3G) EYzen, 0.G., Kiviryakhk, S.V., Khim. z Tekhnol. Topliu i Masel 5, No. 9, 37 (1960). (4G) Eustratova, Z . F., Lapin, V. N., Trudy Vsesoyuz. Nauch-Issledovatel. Inst. $0 Pererabotke Slantsev 1960, No. 7, p. 226. (5G) Faingol’d, S. G., Vallas, K. R., Izvest. Akad. Nauk Eston. S. S. R., Ser. Tekh. i Fir.-Mat. Nauk 8, No. 4, 225 (1959). (6G) Heady, H. H., Adams, L. G., Dinneen, G. U., U.S. Bur. Mines Rept. Invest. 5662,1960. (7G) Kirshenbaum, I., Hinlicky, J. A., (to Esso Research and Engineering Co.), U.S. Patent 2,958,652 (Nov. 1, 1960). (8G) Klesment, I., Arumeel, E., Zzvest. Akad. Nauk Eston. S.S.R., Ser. Tekh. i Fiz.-Mat. Nauk 8, No. 3, 180 (1959). (9G) Kobyl’skaya, M. V., Semenov, S. S., Trudy Vsesoyuz. Nauch-Issledovatel. Inst. Po PererabotkSlantseu 1959, No. 7, p. 209. (10G) Lanin, V. A., Siderov, R . I., Izvest. Sibir. Otdel. Akad. Nauk S.S.S.R. 1959, No. 12, p. 65. (11G) Mapstone, G. E., J . Inst. Petrol. 47,35 (1961). (12G) Su, Wei-Han, Brodskil, A. M., Lavrovskii, K. P., J a n Liao Hsueh Pa0 4,352 (19591.
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