375
. 27, 375-390 Ind. Eng. Chem. Prod. RErg. D ~ v1982, Osterr, Studiengesellschaftfur Atomenergle, Austrlan Patent 300 527, 1969c. Osten. Studiengeselischaft f k Atomenergie, Austrian Patent 300 528, 1969d. Osterr. Studiengesellschaft fur Atomenergie. Austrian Patent 300529, 1969e. &ten. Studlengesellschaft fik Atomenergie, Austrlan Patent 338 499. 1973. Proksch, E. A&. Rakt. Ct”. 1988, 19, 267. Proksch, E. Hokfwsch. 1989a, 23, 93. Proksch, E. A&. R a k t . C h m . 1969b, 20, 281. Proksch, E. In “Large Redlation Sowces for Industrlal Processes”; International Atomic Energy Agency, Vienna, 1 9 6 9 ~ p ; 467. Proksch. E. Kunststoffe 1970, 60, 414. Proksch. E. AI@. R a k t . Chem. 1971, 22, 190. Schaudy, R. Instrumentenbau Musik Int. 1976, 30, 11. Schaudy, R. SQAE Ber. No. 2891 (Internal Report); bterr. Studiengesellschaft fiir Atomenergie: Vienna, 1978a. Schaudy, R. Insirumentenbau-musik Int. 1976b, 3 2 , 1.
-
Schaudy, R.; Proksch, E. Holzforsch. 1976, 30, 164. Schaudy, R.; Proksch, E. Holzforsch. Holzverwert. 196Oa, 32, 25. Schaudy, R.; Proksch, E. Holzforsch. 198Ob, 3 4 , 104. Schydy, R.; Proksch, E.; Slais, E. SGAE Ber. No. AOOlO (Internal Report); Osterr. Studlengesellschaft for Atomenergie: Vienna, 1978. Schaudy, R.; Skis, E. SGAE Ber. No. 2693 (Internal Report); Osterr. Studlengeselischaft fiir Atomenergle: Vienna, 1977. Schaudy, R.; Skis, E. SGAE Ber. No. A0192 (Internal Report); bterr. Studiengesellschaft fa Atomenergie: Vienna, 1981. Schaudy, R.; Wendrinsky, J.; Proksch, E. Holzforsch. 1982, in press. Win, E. A. Radiat. Phys. Chem. 1977, 9 , 271.
Received for review November 5, 1981 Accepted February 2, 1982
Cracking and Hydrogenation of Low-Temperature Coal Tars and Alkyl Phenols Mulpurl Janardanarao Coal Division, Regional Research Laboratoty, Hyderabad 500 009, India
Dr. M.Janardanarao, Scientist, has been working in the Regional Research Laboratory, Hyderabad, since 1958 after obtaining his B S c . from Andhra University and M S c . from Banaras Hindu University (B.H.U.). He was awarded the Ph.D. degree for his thesis on “Studies on Cracking of Low Temperature Tars” by B.H.U. in 1966. He has more than 20 years of R & D experience in various process development projects including upgrading of coal carbonization byproducts. Apart from his studies on cracking of low-temperature tars which is his field of specialization, he has been associated with projects on synthesis of unsymmetrical dimethylhydrazine (UDMH, alkylation of phenol, and modification of pine tar. He has developed catalysts for hydrocracking of tars and for the synthesis of organic intermediates such as anisole, o-cresol, 2,6-xylenol, isophorone, and 3,5-xylenol. I n 1971, he was deputed to the University of New South Wales, Australia, where he carried out investigations on kinetics and mechanism of oxidation of propane. At present he is associated with projects such as synthesis of 3,5-xylenol, liquid fuels, and chemicals from coal and biomass, etc. Dr. Janardanarao has 25 research and review papers in Indian and foreign journals and two patents (filed) to his credit.
This review covers the literature on thermal and catalytic cracking, hydrocracking, and hydrogenation of low-temperature coal tars and alkyl phenols for the production of valuable products such as ethytene, propylene, fuel gas, BTX, low-boiling phenols, gasoline, and middle distillates. Catalysts that have been trled for this purpose are those normally used in the petroleum industry. However, they have limited application because of the presence of high proportions of condensed polycyclic aromatics and heterocyclics which require severe process conditions. Coke formation in these thermal conversion processes poses a serious problem. The potentialities of coalderived products as raw materials for specific chemicals production have to be assessed carefully taking into conskleration their availabillty, price, and suitability.
Low-temperature carbonization (LTC) of coal is generally carried out in the temperature range 500-700 “C to produce mainly solid char or semicoke, together with liquid and gaseous products. The tar produced is a valuable byproduct. The yield and quality of the tar depend on the type of coal, carbonizing temperature, carbonizing equipment, mode of carbonization, residence time, etc. Increase in temperature of carbonization gives more aromatic tar. In the high-temperature carbonization (HTC) conducted at about lo00 “C, the difference in the composition of the tar is very small, irrespective of the type of coal carbonized. The high-temperature tar (HT tar) contains substantial amounts of individual compounds such as benzene, toluene, xylenes, phenol, naphthalene, anthracene, etc. On the other hand, low-temperature tar (LT tar) contains more saturated hydrocarbons (paraffins and naphthenes), olefins, less of simple and unsubstituted aromatic hydrocarbons, and large proportions (up to 40%) of high-boiling phenols compared to HT tar. This LT tar can be subjected to thermal conversion processes to yield valuable products. The production of LT tar dates back to 1846-1855 when brown coal was carbonized in Germany for producing illuminants, lubricants, and paraffin wax. Large amounts of LT tar have been processed into gasoline and diesel fuel by Coalite Corporation in England since 1906. Subsequently, LTC plants were installed in the USA, Canada, Japan, New Zealand, and Europe, primarily for the production of solid fuel for domestic and industrial uses. During 1942-1943, 20 million gallons of LT tar was cracked at the Rositz refinery (1). The Billingham plant 0196-4321/82/1221-0375$01.25/0
of Imperial Chemical Industries Ltd., was producing about 15OOOO tons of motor fuel in 1935, while the German motor fuel production from coal and coal tar hydrogenation reached about 1.5 million tons by 1938 (2). The situation in the USA was quite different from that in Germany in regard to petroleum supplies. LT tar,as a source of liquid fuels, could not stand competition against the large quantities of naturally occurring petroleum which became available cheaply during the period. Now there are doubts about the availability of crude oil in adequate quantities and there has been a steep price hike in petroleum products during the past decade. Serious efforts are therefore being made to produce synfuels and chemical feedstocks from coal. Improved processes for pyrolysis (or carbonization), solvent extraction, and direct and indirect liquefaction of coal are being developed to meet the challenge of the present energy crisis. The USA is leading in the development of technologies for the production of synthetic fuels and chemicals not only from 0
1982 American Chemical Society
376
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982
coal but also from other raw materials. Hydrocracking and hydrogenation play a very important role in these developmental programs on coal conversion technologies. The application of these processes to treat coal tars has long been known. Hydrocracking is the most versatile process and has great flexibility in operation, selection of feedstocks, and product distribution. Hydrogenation is essential to treat feedstocks containing highly condensed polyaromatics and heteroatoms, and where a high degree of saturation is required in the desired products. Advances made on hydrocracking and hydrogenation of petroleum feedstocks and pure hydrocarbons have been reviewed in the literature (3-15). In the earlier reviews, the work on cracking (16-23), hydrocracking (9, 17,19,20,22,24-26) and hydrogenation (2,9,16,17,20, 22,24,26-30) of LT tars and fractions and dealkylation of tar acids and alkyl phenols (19, 22, 23, 31) has been covered briefly. The present paper gives a comprehensive review on thermal and catalytic cracking, hydrocracking, and hydrogenation as applied to processing LT tars and some of the constituents of LT tar, particularly higher boiling phenols. Thermal Cracking As early as 1917, Jones (32) reported the thermal cracking of LT tars. Fischer (33,34)studied the effect of temperature on various constituents of primary tar. The decomposition of higher boiling phenols occurred resulting in an increase in the content of phenol and low-boiling homologues present in the tar. In the presence of hydrogen at high pressure, the fraction boiling up to 200 "C increased. Davis and Parry (35)compared the yields of gases from petroleum gas oil and LT neutral oil (b 175-275 "C) at various cracking temperatures. They found that the gases evolved in the cracking of gas oil had about the same thermal value as that obtained from neutral oil, but a somewhat larger quantity of gas was produced with gas oil. An additional quantity of 0.66 gal of motor spirit per ton of coal was obtained in the cracking operation. Dunstan (36)and Morrell and Egloff (37) made attempts to produce motor fuel by subjecting LT tars to cracking under pressure. LT tar from an Ohio-Indiana bituminous coal on cracking at 100 psig and 426 "C gave 33.9% gasoline containing 35% tar acids or an acid-free yield of 22% gasoline, whereas neutral oil from the same tar when cracked at 200 psig and 455 "C gave over 50% of highgrade, anti-knock motor fuel (38-40). Various coal tar fractions were subjected to thermal cracking in order to increase the product value or to convert them into useful products (41-58). Curtis and Beekhuis (59) studied the cracking of neutral oil from LT tar from West Virginia coal using pressures in the range 100-550 psig and found that the yield of oil boiling below 210 "C could be increased from 20% of the neutral oil initially present to about 34%. The application of cracking and hydrogenation to process LT tars has been recommended and the progress of the work has been reported by the Fuel Research Board (60-62). In 1940, Egloff et al. (63, 64) reported the processing of coal tars, creosote oil, and light tar fractions from LTC in a pilot plant cracking unit. The gasoline obtained had a greater heating value and the corrosion in the plant was much higher than in petroleum cracking. The gasoline obtained in 20.6% yield from creosote oil had an octane number of 78. Thermal cracking of tar fractions in a continuous pilot plant similar to the one used in petroleum industry has been carried out with a view to get solvent naphtha from paraffin containing oil and middle oil from which tar acids
were removed (65). LT tar boiling above 160 "C was cracked at 650-680 "C to give 10.1% benzene and 12.6% phenol (66). A cracking unit with a processing capacity of 90 OOO tons per year of lignite tar,along with 80 OOO tons of press oil, to yield 100000 tons per year of gasoline and diesel oil as well as tar products, gas, and coke was under construction in 1958 at the lignite carbonizing plant at Rositz, East Germany (67). Thermal cracking of neutral LT tar gave a gasoline containing 6-10% unsaturates which when purified by sulfuric acid gave stable petrol having a low octane rating of 50 (68). LT neutral oil (b 210-350 "C) was cracked in the temperature range 400-900 "C to give a gasoline (8.7 vol % on feed at 550 "C) containing 12.7% unsaturated and 87.3% aromatic hydrocarbons. More aromatized product was obtained at temperatures of 600-700 "C (69-71). The gasoline boiling up to 200 "C, obtained from Cheremkhovo primary tar,contained 0 and S compounds 13.3, aromatics 49.0, naphthenes 27.4, paraffins 9.1, and unsaturated hydrocarbons 1.2% (72). Addition of oxygen intensified the cracking of LT tars at 750-900 "C with the formation of carbonaceous residue, a gas, and secondary tar (73),and oxygen had a greater effect on the pyrolysis than did temperature or contact time (74). The thermal degradation of phenols, especially high-boiling polyalkyl phenols, was sharply increased. Phenol itself underwent less decomposition. Fuel Gas The advantages of converting LT brown coal tars into fuel gas have been described. The circulating solid heat carrier system was considered as the best method for tar cracking and the gaseous hydrocarbons obtained could be used for carburation of low calorific value gas (75). Lowtemperature fluid bed tar from flash-heating of a highvolatile coal at 500 "C was cracked at temperatures of 800 to 900 "C over high-temperature coke. The gas-obtained at 900 "C had a maximum heating value of about 4895 kcal/m3. High temperatures resulted in the decomposition of methane or in the reaction of methane with water formed in the pyrolysis reaction. Therefore, temperatures above 900 "C were considered not desirable for producing fuel gas (76). The calorific value of the gas varied between 9665 and 9256 kcal/m3 in the cracking of fluid bed tar at temperatures of 500 to 700 "C. It was suggested that LT tar is more suitable than vertical retort tar for the manufacture of fuel gas (77). Rapid pyrolysis of lignite tar fraction boiling up to 360 "C was carried out at 710-860 "C with residence times of 0.1 to 1.6 s with gas-suspended quartz sand (0.1 to 0.3 mm) as solid heat transfer agent (78). Joseph and Maguire (79) obtained 41.7% gas and 18.5% light oil in the rapid pyrolysis of lignite tar in the temperature range 600-1000 "C by heating the feedstock to the desired temperature in 0.1 s and maintaining a contact time of 1 s. Olefinic Gases The possibility of obtaining ethylene by pyrolysis of LT tars has been investigated by several workers. In an attempt to produce fuel gas with high olefinic content which could be used as a raw material for chemical synthesis, Wood (80) studied the thermal cracking of light oil and tar from LTC of cannel coals. Kishida and Chuto (81) obtained the best yields of gaseous olefins by thermal cracking of LT tars at 400-800 "C, the yields of ethylene and propylene being 10.3 and 8.6%, respectively, at 700 "C and 10 mmHg. Coal tar oil (b 180-320 "C) when cracked over a bed of coke at 680-750 "C gave a gas (370 L/kg) containing 22% ethylene, 17% propylene, and 5% butylenes by volume (82). Cracking of LT tar at 880 "C
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982
and a contact time of 0.1 s gave maximum yield of olefins (58.4 L/kg). The gas contained ethylene (61%) and propylene (32%) and had a calorific value of 7200 kcal/m3 (83). It was claimed in many investigations that higher yields of ethylene and propylene could be obtained with neutral oil fractions compared to those from tar fractions of the same boiling range. This was attributed to the low C/H ratio of the raw material required for the production of maximum quantities of olefins (84). The yield of ethylene from neutral oil boiling between 120 and 360 "C from bituminous coal was 22% at 700-900 "C, whereas ita yield was 17% from tar fraction (85). Janardanarao et al. (69, 71) studied the thermal cracking of LT tar fraction (b 210-350 "C) from LTC of noncaking coal in an internally heated LTC pilot plant and showed that higher yields of ethylene and propylene could be obtained with neutral oil. At 550 "C, the yields of ethylene and propylene were 10.3 and 11.5%, respectively, with neutral oil compared to 7.4 and 5.8% with the tar fraction of the same boiling range and containing 23% tar acids. Addition of tar acids to the fraction to raise the tar acids content to 50% reduced the yields and increased the coke formation in thermal cracking. Maximum yield of ethylene was 19.6% with neutral oil at 700 "C. A tar-acid free middle oil from LT tar when cracked at 780 "C in the presence of 14% steam gave 22% of Cz-C4 olefins or 30% of cracked gas containing 45% unsaturated hydrocarbons (86). The addition of steam to tar at 700-850 "C reduced the tar conversion and increased ethylene formation (87). The oil obtained in 57.6% yield from catalytic cracking of lignite tar fraction (b 180-360 "C) over bentonite at 430 "C was pyrolyzed at 700 "C in the presence of superheated steam to give a gas containing 35.9% olefins (88). The yield of C2-C4 olefins was about 15% at 800-850 "C in the cracking of LT tar fraction (b 81-324 "C) (89). Coke gave higher yields of gas compared to alumina from the fluidized bed carbonization of coal, and the yield of ethylene was maximum at 800-900 "C (90). It was concluded that a fluidized bed with the instantaneous heating of the feedstock does not provide an economical yield of olefins from a feedstock with high C/H ratio (91). The concentration of ethylene in the gas is another criterion of the suitability of the feedstocks. The amount of pyrolysis gas to be processed, based on ethylene yields, was about 50% greater with such feedstocks compared to crude oil feedstocks (91). When light tar was cracked at 720 "C with a contact time of 2 s the yield of lower boiling fraction was double of that present in the original tar,and ethylene and propylene constituted 50% of the total unsaturated hydrocarbons (92). The contribution of paraffins and the main steps involved in the formation of aromatic hydrocarbons in the decomposition of LT tar have been examined (93-95). Cracking of pristane and decane present in LT tar over coke or active carbon at 600 "C was found to be purely thermal resulting in C5-C9 a-olefins (94). The kinetics of thermal decomposition of hydrocarbons present in LT neutral oil have been reviewed (96). The vapor phase thermal cracking of a range of coal-derived materials and also model compounds (mesitylene, tetralin, decalin, and undecane) was carried out. Product yields could be predicted from the cracking patterns of the components. Undecane gave 37% ethylene compared to 20% from decalin, 3% from tetralin, and 0.2% from mesitylene (97). Thermal Cracking of Volatile Matter Low-temperature carbonization of coal has been con-
377
sidered as an alternative to crude oil cracking for the production of ethylene and aromatics. Thermal cracking of tars and volatile matter from carbonization has been carried out in order to produce olefinic gases for chemical synthesis or fuel gas and also electrode carbon for metallurgical industries. Two tars from vertical retort and fluidized bed Carbonization as well as volatile matter were cracked in a static bed reactor between 500 and 1000 "C and residence times of 1-440 s (98). Intensive cracking of primary volatile matter was achieved by passing the vapors and gas released from static bed carbonization at 500 "C through a static bed reactor at 500-1000 "C and at relatively short residence times 1.0-1.7 s. The main gaseous product was methane (43% based on dry tar at 900 "C), but olefins (23% at 800 "C) also were formed (99). When volatile matter released at 500 "C from a fluidized bed LTC was cracked in a fluidized bed of high-temperature coke at around 700 "C and residence times of 1.7-6.7 s using air or a mixture of nitrogen and recycle gas as a fluidized medium, a conversion of about 28% primary volatile matter into gas and coke was achieved (100). When nitrogen plus recycle gas was used as a fluidizing medium, product gases with calorific value more than 8900 kcal/m3 were obtained. In the pyrolysis of products from LTC, a gas yield of 390 L/kg of dry coal could be obtained. Conversion of coal potential heat into gas heat ranged from 20.9 to 27.5% and the coke yield was between 60 and 65% (101). The best yield of benzene was obtained at 970 "C in the cracking of vapors from LTC (102). Thermal decomposition of Agulaksk lignite with solid heat carrier system followed by secondary pyrolysis of the volatile products was carried out (103,104). At a pyrolysis temperature of -900 "C, the yield of gas was 301.5 L/kg and that of crude benzene was 0.3-0.4% by weight of coal. The effects of time and temperature of pyrolysis reaction on the yields and composition of various products in the rapid pyrolysis of lignites and their volatiles have been determined (105). LTC of North Dakota and Texas lignites at temperatures up to 550 "C followed by high-temperature cracking of tar vapors at 800 "C produced good yields of ethylene and benzene (106). When coal was carbonized in the presence of superheated steam and the vapors were cracked at steam to coal ratios of 1.0, 1.25, and 1.5 and residence times of 0.5, 0.7 and 0.9 s, maximum yields of ethylene and propylene obtained were 111.1kg and 18.6 kg per ton of coal, respectively (107). In spite of these very high yields of ethylene and propylene, the process appeared not to be competitive with a petroleum-based process. Bernhardt et al. (108) subjected the volatiles from carbonization of a low rank bituminous coal to cracking at temperatures up to 1100 "C to get BTX fractions. Cracking of Volatile Matter from LTC over Activated Carbons Investigations have been made on the cracking of tar vapors from LTC over activated carbon by several workers. Adams et al. (109) observed that certain pyrolysis products released in the carbonization process when left in contact with heated coal undergo reactions such as polymerization and condensation to give a solid product. Bond et al. (110) found that the tar yield considerably decreased, but that the yields of benzene and toluene considerably increased in the LTC of coal-carbon mixture, and the magnitude of the effect depended on the ratio of carbon to coal carbonized. Griffiths and Mainhood (111) used activated carbon, fused silica,and alumina for the cracking of volatile products from LTC at 350-900 "C. The optimum yields of benzene, toluene, xylenes, and ethylbenzenes were obtained at -500 "C with activated carbon and it was also
378
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982
concluded that activated carbon acts as a cracking catalyst for the low-boiling constituents of the tar, but promotes coking of the higher boiling ones. The optimum temperature for the production of BTX with activated carbon was much lower than that found when fused silica was used. Volatile products from the LTC of a high-volatile noncaking coal at 400-600 "C were decomposed in an empty tube and also over a bed of activated carbon. The thermal value of the gas produced was maximum at a bed temperature of 400 "C and a ratio of 5:l of coal carbonized to activated carbon used in the cracking zone in the decomposition of volatile matter obtained at a carbonization temperature of 600 "C. Addition of water vapor increased the formation of hydrocarbons (112). Shchegolev (113) carbonized coal at 510 "C and cracked the tar vapors on coke at 500 "C. The tar yield decreased by 20-40% and the gas yield increased by 30-70% as compared to the yields obtained when no coke was employed. Replacing coke with firebrick did not affect the yields. The vapors and the gaseous products from LTC were cracked on different catalysts at atmospheric pressure. Best results were obtained by using L T coke activated at 800 "C as catalyst and a cracking temperature of 400 "C. The yield of purified gasoline fraction increased by 142% and that of diesel fuel by 25% (114). When the pyrolysis of volatile products from coal carbonization was carried out at 950 "C in the presence of coke and steam as diluent, the yield of phenol, bases, and naphthalene increased by 20-30% (115). The volatile matter evolved during LTC of brown coal was cracked at >800 "C over the coke obtained from the same coal to obtain a gas rich in carbon monoxide and hydrogen. The yields and composition of products obtained in LTC of coal-coke mixture at 500-900 "C were also reported (116). The pyrolysis of the volatile coking products on the surface of coke has been investigated (117-119). It appears that the primary decomposition of the coal substance during carbonization in the coke-oven occurs in the space enclosed by plastic layers within the coal. The products of pyrolysis are further degraded outside the plastic layers yielding coke-oven gas, high-temperature tar, and coke (120). A mathematical model of high-temperature pyrolysis of LT tars was developed for predicting the yields of high-temperature coal tars, solid residue, gas, phenols, and hydrocarbons as functions of the pyrolysis temperature from 750 to 950 "C and residence time (0.5-6.5 s) and also rate of coal heating (121). The thermal decomposition of LT tar is intensified by the surface of coke. The data obtained on the pyrolysis of the tar constituents over coke beds at 750,800, and 850 "C can be used to predict the yields of products in the coking process (122). It is known that carbon (coke or charcoal) exhibits cracking activity in the reactions of hydrocarbons (123-127). Workers in the US.Bureau of Mines (128) investigated the changes that occur when the vapors from coal carbonized in a fluidized bed with steam were cracked prior to their condensation in a fluidized bed of high-temperature coke. The carbonizer was operated at 485 "C and the cracker at 600, 700, and 800 "C. I t was observed that most of the paraffins, naphthenes, and olefins decomposed, while the yield of the tar bases remained unchanged at a cracking temperature of 800 "C. Cracking of LT Tar and Pitch for the Production of Electrode Coke LT tars were pyrolysed to give electrode coke (129-131). Brown coal tar was cracked over a hot coke bed and the cracked product, rich in aromatics, was treated in conventional manner to give a coke of improved quality (132).
LT tar fraction (b < 300 "C) was treated under a pressure of 140-570 psig at 400-700 "C to give pitch which can be used for electrode carbon manufacture (45). Thermal cracking of LT lignite tar pitch has also been considered as an effective means of upgrading the pitch (133-135). It was observed that temperature had a much greater effect on product yields (coke, oil, and gas) than pitch feed rates. Highest yields of coke, oil, and gas were 30,28, and 30%, respectively (135). The gas contained 10-15% ethylene. The coke after calcination was used with the oil distillation residue pitch as binder to produce metallurgical electrodes (133).
Thermal Cracking of Tar Acids and Pure Alkyl Phenols In an attempt to convert high-boiling tar acids to lower boiling ones which have industrial importance, Senseman (136) subjected LT tar acids boiling above 207 "C to thermal cracking which yielded 25 % low-boiling phenols in a single pans and 36% by recycling. It was observed that pressures above atmospheric did not favor the production of low-boiling phenols. When a phenol fraction (b 200-268 "C) was cracked a t 675 "C in the presence of steam the yield of low-boiling phenols (b up to 200 "C) was 54% of the pyrolysis product and 23% of the original feed (137). An additional quantity of 5.38% of low-boilingphenols was obtained when the 200-270 "C fraction of the product was recycled. Without the addition of steam, the yield of low-boiling fraction by the cracking of the 230-300 "C phenols fraction at 625 "C was only 10% in the product and 3% of it boiled below 200 "C. Thermal cracking of LT tar at 700-800 "C resulted in the formation of considerable amounts of xylenols. High temperatures caused a decrease in the yield of xylenols, and maximum yield of cresols was obtained at 750 "C (138). Janardanarao et al. (71) reported 24% of low boiling fraction which contained 38.8% phenols in the cracking of tar acids feedstock (about 53% boiling between 220 and 350 "C). Thermal cracking of LT tar fractions containing 23.0, 33.3, and 50.0% tar acids was alos reported. Jones and Neuworth (139) reported a maximum yield of 17% of low-boiling phenols in the thermal cracking of tar acids (b 230-300 "C). Individual isomeric cresols have been subjected to thermal cracking (140-143). In order to determine the stability and to study the nature and sequence of formation of byproducts, the cracking of 2,4- and 3,5-xylenols was carried out at 650-850 "C. The main products were mcresol in the case of 3,5-xylenoland o- and p-cresols in the case of 2,4-xylenol. 3,5-Xylenol is more stable than 2,4xylenol (141). The mechanism of dealkylation of alkyl phenols has been suggested by Jones and Neuworth (143). Catalytic Cracking of LT Tars Of the different packing materials, Cu, Fe, Ni, coke, charcoal, bone charcoal, and Japanese acid clay, used in the reactors to enhance the thermal decomposition, coke was the best and the bone charcoal was the worst, but each packing had an optimum temperature for lower phenols formation (144). In the cracking of products from LTC, silica gel was found to be a better catalyst than active carbon, and high-cracking temperatures above 550 "C caused considerable loss of the product (145). Stephan (146)introduced a metal packed purifier in order to remove sulfur from the tar oil vapors before allowing them to enter the catalyst bed of nickel or cobalt. The yields of aviation spirit and light oil increased considerably. Low-boiling aromatic hydrocarbons were obtained from cracking of a neutral oil fraction (b 100-280 " C ) from LT tar over metallic catalysts. The product contained 16.8% benzene,
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 379
16.1% toluene, and 10% ethylbenzene (147). A number of synthetic as well as natural catalysts have been used in the cracking of coal tars and fractions therefrom. Cracking of oil fractions, b 180-280 "C and over 280 "C from LT brown coal tar was carried out in the presence of silica-alumina catalysts (148-150) and a lignite tar fraction (b 180-360 "C) over bentonite (88). The yield of light oil was about 25% from the cracking of brown coal tar fraction (b 180-280 "C) at 400 "C (148). Roy et al. (151) reported higher conversions with silica-alumina catalyst compared to active carbon in the cracking of neutral oil fractions (b 270-300 "C and 300-360 "C) from LT tar. The yield of lighter fraction was about 50% and the product had higher aromatic content. Investigations were carried out in the USSR on the catalytic cracking of neutral oil fractions (b 200-235 "C) from light tar at 450 "C using a moving bed silica-alumina catalyst. A liquid low in sulfur content and rich in aromatics was obtained (152). It was found that when a stream of hydrocarbon gas (mainly propane and butanes) was passed the production of coke and gas was reduced and the yields of gasoline boiling below 200 "C was increased (153). Catalysts containing rhenium on hydrogen fluoride-activated kieselguhr were found suitable for cracking brown coal middle oils at 735-4043 psig pressure to yield gasoline fractions (154). Catalytic cracking of LT tar at 450 "C gave low boiling fraction 30.5%, gas oil 38.290, and gas 10.5% (155). Janardanarao et al. (70,156,157) have carried out investigations on cracking of LT tar neutral oil (b 210-350 "C) using commercial silica-alumina, active carbon (Hykol-X), silica-alumina prepared in the laboratory, and clay as catalysts in the temperature range 350-500 "C. Commercial silica-alumina gave 20-21 % of low boiling fraction based on the feed at temperatures of 350-450 "C. Coke formation on this catalyst was also studied (156). Active carbon was effective for the production of low-boiling fractions but required higher temperatures compared to commercial silica-alumina in the cracking of neutral oil fraction (b 210-350 "C) and LT tar boiling above 220 "C (157). The use of various catalysts for the cracking of LT tar and its fractions to produce aromatic gasoline, olefinic gases, and low-boiling phenols, has been covered in patents (158-161) and in publications (57,162-164). Carbon deposition was substantially absent in the catalytic cracking of brown coal tar oil (b 240-260 "C) with a nickel catalyst in the presence of superheated steam. The catalyst was prepared by dipping dolomite chips in aqueous nickel nitrate or by spraying the same solution on dolomite (163, 164). The life of Moo3-alumina catalyst was prolonged by the addition of salts or oxides of Na, K, Li, Ca, and Mg in the cracking of a tar oil fraction (b 220-320 "C) and containing 32.8% tar acids (160). Refining and distillation with Japanese acid clay (165) and fluid bed catalytic cracking (166, 167) of LT tars were studied. Composition of Products from Catalytic Cracking The composition of liquid products from catalytic cracking of neutral LT tar has been determined (70,155, 157,168-170). The product from neutral oil of brown coal tar contained 16.9% normal paraffms (C12H26-C17H36), 9% isoparaffins, 4 % naphthenes, 9.7% monocyclics, 39.7% bicyclics, 19.9% polycyclic aromatics, and the remaining nonhydrocarbon part plus polymers formed during chromatographic separation (169). The saturated and aromatic hydrocarbons in the fraction boiling up to 210 "C of liquid products obtained with commercial SiO2-Al2O, and active carbon catalysts were separated on a silica gel column and these fractions, after fractionation in a spinning band column, were analyzed by gas chromatography. The
normal paraffins identified by gas chromatography accounted for 53.5% and 81.4% of the saturated fraction with silica-alumina and active carbon catalysts, respectively. The major constituents with active carbon were n-heptane (18.6%) and n-octane (20.0%). The aromatics identified and estimated constituted 58.1% and 49.8% of the fraction with silica-alumina and active carbon, respectively. Toluene was the major constituent with both the catalysts, the yield being 12.2% and 10.9%, respectively (157). The composition of gas obtained from catalytic as well as thermal cracking of LT tar fractions was also determined by a combination of conventional gas analysis and gas chromatography using silica gel column ( 1 71). Catalytic Cracking of Tar Acids Tar acids boiling above 230 "C from LTC of bituminous coal when cracked in the vapor phase at 7W850 "C in the presence of an inert diluent over silica-alumina catalyst resulted in at least 5% carbon deposited on the catalyst (172). Berber et al. (173-175) studied the catalytic dealkylation of tar acids from LT lignite tar. In the dealkylation of a tar acids fraction (b 230-266 "C), the yield of low-boiling phenols was 30% with silica-alumina catalyst at temperatures of 365-460 "C. A cobalt Girdler catalyst was highly selective but the conversion was very low. Vanadium pentoxide promoted dehydroxylation of high boiling phenols. In the catalytic cracking of LT light tar boiling above 220 "C and containing 33.3% tar acids over commercial silica-alumina and active carbon catalysts in the temperature range 350-500 "C, the conversion of tar acids to low-boiling phenols decreased with increase in temperature with silica-alumina, whereas the conversion increased with active carbon. The conversion to lowboiling phenols was 19.5% at 500 "C with active carbon. Dehydroxylation of tar acids was favored a t 500 "C with silica-alumina (70,157). Vanadium and tungsten sulfides with ammonia as diluent were used in the dealkylation of a phenolic fraction (b 230-270 "C) at 460-485 "C and 1470-3090 psig. A 55% yield of phenols boiling up to 225 "C containing 20% phenol and cresols was claimed (176). A catalyst containing FepO3 (5%) with tungsten and vanadium sulfides was found to be the best. Among the ~atalysts-Fe(OH)~,Al(OH),, Fe203,Al,03, natural bauxite, A1 shavings, and Cu dust-used for conversion of high-boiling phenols, the highest yield (17.2%) of lowboiling phenols was obtained with Fe(OH),. The best conditions for cracking were found to be 2 h run at 325-375 "C and a pressure of 1838-1911 psig (177). Bhaduri and Basu (31) critically reviewed the dealkylation of tar acids and alkyl phenols. Isomerization and disproportionation reactions took place when individual alkyl phenols were subjected to catalytic cracking (178-186). The reaction mechanism of pure alkyl phenols over cracking catalysts was studied (179, 180, 186). The kinetics of dealkylation of alkyl phenols over aluminum fluoborate on alumina were reported (187) and the influence of the structure of the alkyl phenols on the dealkylation reaction was also discussed (187-189). Hydrocracking and Hydrogenation of LT Tars Bergius first succeeded in converting heavy oils and LT tars into light oil by hydrogenation (190). The early work on hydrogenation of LT tars and tar fractions has been reviewed by Sander (191),Tupholme (192),and Storch (2). In Japan, Ando (193-222) and Ando and Usiba (223-227) have published a series of articles on hydrogenation of LT tars. The work on hydrogenation of tars and tar oils has been reported (228-232). During 1943, Germany hydro-
380
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982
genated 500 million gallons of brown and lignite LT tars (22). Liquid phase hydrogenation of both LT and HT tars has been reported (233-235). A catalyst containing 0.5% molybdic acid and 0.5 9% stannous chloride was tried at 450 "C and 2940 psig. The extensive investigations (236-242) made in the British Fuel Research Laboratory indicated that halogens were found to have high catalytic activity, iodine being more active than bromine or chlorine. Similarly, hydrogen halides and volatile organic halides were found to be good catalysts. Stannous chloride was much superior to stannic oxide. The presence of sulfur markedly enhanced the catalytic activity, particularly in the case of molybdic and tungstic oxides. Some improvement in catalytic activity of iron, cobalt, and chromium oxides was observed, whereas no improvement with cadmium, tin, and vanadium oxides was noticed. Molybdenum oxide on alumina was a satisfactory catalyst for vapor phase hydrogenation of LT tar at 480-500 "C and 2940-4410 psig of hydrogen pressure (204, 242). The activity of this catalyst declined slowly, but it could be regenerated by passage of air at 500 "C (242). The use of high pressures prolonged the life of the catalyst. Later molybdenum disulfide catalyst was developed. This catalyst was more active than those supported on alumina and could be used at lower temperatures of 400-430 "C compared to the earlier catalysts at 450-480 "C. Pier (243) discussed the development of vapor phase sulfide catalysts. Gosselin (244) reported a gasoline (b 55-186 "C) yield of 86% in the hydrogenation of LT lignite tar at 470 "C and 6000 psig using molybdenum disulfide catalyst and a mixture of hydrogen and nitrogen in the ratio of 3:l. The octane number of the gasoline was 75. Hydrogenation of LT tar over MoS2catalyst at 2940 psig and 500 "C gave a gasoline with octane number 81 (245). Hydrogenation of LT middle oil over A1203-supportedmolybdenum sulfide gave an oil of cetane number 21. Rehydrogenation over the same catalyst increased the cetane number to 46 (246). About one ton of gasoline with an octane number of 60 to 70 was obtained from 1.25 tons of brown coal tar (247). A few publications by the British Fuel Research Board (26,233,235-237) and by the Bureau of Mines (248)have covered liquid phase hydrogenation of high temperature horizontal and vertical oven tars. The effects of various process parameters and the reactions involved in hydrogenation-cracking (hydrocracking) of LT tars have been studied (238,240,249-255). The higher the temperature of carbonization of coal the less amenable is the tar to hydrogenation-cracking. A two-stage hydrogenation process involving liquid phase reaction followed by vapor phase treatment has been recommended for the production of gasoline from tar (254). Cawley and Hall (249) studied the behavior of LT tar under hydrogenation-cracking conditions of 440 to 500 "C and 2940 psig. A semitechnical scale plant with throughputs 1 to 2 tons/day was operated a t the Fuel Research Station in Greenwich (192,241,245,253,254,256).With LT tar,the formation of fraction boiling below 200 "C was about 50% at 480 "C and 2940 psig. The consumption of hydrogen was 5.5%. Molybdenum disulfide-alumina catalyst used lost its activity slowly and required regeneration after about 30 days. The quantity of tar that could be processed was 400 kg/kg of molybdenum disulfide. The hydrogenation-cracking of wax from LT tar was also reported (60, 257). The importance of application of hydrocracking and hydrogenation for processing LT tars has been stressed by Gordon (258), Clough (259), and Hill and Lyon (260).
Vaidyeswaran et al. (261) have presented a brief account of the need to process LT tars by hydrogenation. Lozovoi et al. (262,263)reported hydrocracking of LT tar in the liquid phase for the production of high octane gasolines. Hydrocracking of a fraction (b 300-400 "C) over tungsten catalyst and aromatization of the product boiling up to 300 "C over molybdena-alumina or chromia-alumina catalyst at 735-1470 psig produced the desired motor fuels. Reforming of gasoline and narrow boiling fractions obtained by high-pressure catalytic hydrogenation of LT tars from North Bohemian brown coals over Pt and Mo was carried out to produce BTX fractions (264). Several patents (232, 265-283) and publications (228,284-31 7) have described the production of low boiling aromatics, gasoline, and middle distillates from coal tar fractions by hydrocracking and hydrogenation. A two-stage hydrocracking process involved the treatment of LT tar at 500-650 "C in the presence of a catalyst containing 3-7% Mo on A1203 or metallurgical coke in the first stage and refining the 200-300 "C fraction of the product at 260-320 "C over a catalyst consisting of 6 1 2 % Mo oxide and 2-4% NiO or COOon active alumina (266). Southern Research Institute contemplated the disposal of tar from LTC by hydrocracking it to produce gasoline and simple aromatics (67). Hydrocracking of LT tar from low rank coals from Rocky Mountain at 735 psig over cobalt molybdate and metallic nickel catalysts gave a product resembling "synthetic petroleum" which on subjecting to conventional distillation yielded 36.4% high octane gasoline and 37.8% diesel fuel of cetane number 40 (22, 318). Lignite tar was hydrocracked at 4500 psig and 500 "C, using tungsten disulfide catalyst, to produce about 60 million gallons per year of gasoline and other liquid fuels (22,319). Hydrocracking of high boiling coal tar fractions a t 441 psig and 400-700 OC over active hydrogenating catalysts caused complete conversion of polycondensed aromatics to mono and dicyclic compounds. It was found that the use of a diluent increased the conversion and the life of the catalyst (300). Hydrocracking of LT tar over cobalt molybdate-alumina catalyst with dilution of the feedstock with benzene at 1:l and recycling the product boiling above 230 "C gave over 95% of the desired products (320). Hydrocracking of light tar, produced in LT Lurgi Spuelgas carbonization of lignite, at 3000 psig over cobalt molybdate catalyst gave gasolines with high aromatic and naphthenic contents. The yield of gasoline was 31-59% and contained higher percentages of aromatic and naphthenic hydrocarbons than typical petroleum reforming feedstocks (321). Hydrocracking of LT tar over Ni-W or Co-Mo on A1203at 450 "C produced a product boiling up to 220 "C rich in aromatic and saturated hydrocarbons (294). Catalysts containing 25% cobalt molybdate or 3% nickel sulfide on alumina were evaluated for hydrocracking and hydrogenation of light tar at 325 "C and 4410 psig (322). Qader et al. (323) observed that a static bed was more efficient in naphtha yield, desulfurization, denitrogenation, and deoxygenation than an ebullating bed in the hydrocracking of coal tar oil and petroleum oils over a catalyst containing sulfides of nickel and tungsten on silica-alumina and was more suitable for large scale operation. Gasoline yield of 75% was obtained in the hydrocracking of LT tar in a batch autoclave (324). A dual functional catalyst containing the sulfides of nickel and tungsten on silica-alumina gave better product distribution with respect to gasoline, and had higher cracking, isomerization, and hydrogenation activities than the catalyst containing sulfides of nickel and tungsten on alumina (324). Neutral oil from Lurgi LT tar was hydrocracked over molybdena catalyst
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 381
to yield high speed diesel and highly aromatic gasoline of 78 odane number (68). Extensive investigations conducted by Janardanarao et al. (70,325-330) on hydrocracking of LT tars obtained from carbonization of noncaking coal in a Lurgi Spuelgas pilot plant showed that in the hydrocracking of a neutral oil (b 210-350 "C) over three catalysts, viz., silica-alumina, cobalt molybdate on Si02-A1203, and nickel sulfide on Si02-A1203,the catalysts containing the hydrogenating component gave higher yields of better quality gasoline compared to Si02-A1203. Maximum yields of gasoline were obtained at 500 "C with all three catalysts. Desulfurization and denitrogenation were more with cobalt molybdate and nickel sulfide catalysts (325). In the hydrocracking of LT tar fraction (b 230-280 "C) over active carbon (Hykol-X) based catalysts at temperatures of 350-550 "C, the yield of low-boiling fraction was 50.7% at 475 "C with nickel sulfide-active carbon catalyst compared to 31% at 525 "C with active carbon alone at 711 psig (327). Various catalysts including a commercial hydrocracking catalyst containing 6% nickel and 19% tungsten both as sulfides have been evaluated for the hydrocracking of a neutral oil fraction (b 250-350 "C) in the temperature range 350-550 "C and at pressures of 425-1280 psig. A catalyst containing 10% nickel on active carbon gave higher yields of low-boiling fractions compared to active carbon alone. The yield of kerosene fraction (b 150-250 "Cl was 38.2% at 475 "C, 995 psig, and LHSV of 0.5 (330). Although commercial catalyst gave higher yields of low-boiling and kerosene fractions compared to tinnickel-silica-alumina and tin-nickel-active carbon, the cracking activity of the catalyst declined rapidly (329). LT tars were hydrogenated under 4410 psig at 460 "C and 475 "C with iron catalysts (331,332). LT tar distillates (b 2W350 "C) were hydrogenated at 375-400 "C and 1500 psig over molybdenum disulfide catalyst to give products with diesel index of more than 45 (333). In the hydrogenation of LT tars, iodine was found to be more active than cobalt molybdate or nickel tungsten catalyst (334). Middle oil (85% boiling between 186 and 363 "C) and tar (65% boiling up to 311 "C) from LTC were hydrogenated at 340-350 "C, 1280 psig over 15% MoS2 or WS2 catalyst with or without h e y nickel for desulfurization. Removal of tar acids and bases was necessary and hydrogenation of aromatic rings was not complete (335). The presence of Ha in the recycle gas in the hydrogenation of tar or raw materials containing aromatics increased the activity of the WS2-NiS-A1203 catalysts, probably due to the decomposition of Ni3S2to Ni. The degree of hydrogenation can be controlled by adjusting the partial pressure of H2S in the recycle gas (314). Arsenic from coal goes to tar in the LTC (336)and it has deleterious effects on the cracking and hydrogenation activities of WS2 and WS2-NiS-A1203 catalysts (337, 338). When arsenic was removed by hydrogenation over a deactivated catalyst the rate of hydrogenation using fresh catalyst was enhanced (339),but arsenic and vanadium have not produced any unfavorable effect when Fe-supported on brown coal semicoke was used as catalyst (340). Panfilov et al. (307) established the conditions for hydrocracking of coal tar fractions. Lower yield of coke was obtained at 550 "C, LHSV of 1.0 and hydrogen to feed ratio of 1.2 m3/kg. Preliminary refining on alumina-supported molybdenum sulfide catalyst in the first reactor protected the tungsten sulfide catalyst from the ash being deposited in the second reactor and operating life of the unit was prolonged by 3-4 times (341). Highpressure cracking of middle distillates from coal tars to give motor fuels was found to be rather expensive owing to the high consumption of hydrogen and catalyst, and low con-
versions (342). LT brown coal tar was hydrogenated and refined to produce low-boiling sulfur-free products (316). The Varga process (343) for hydrocracking of high asphaltic crudes was tried on a large scale and was found applicable to process coal tar and shale oil. The catalyst used was activated brown coal semicoke impregnated with ferrous sulfate and sodium hydroxide. The structure and surface properties of cobalt molybdate catalysts were evaluated in the hydrocracking of coal tar fractions (344,345). A 400 h duration of the run with 50 cycles of cracking and regeneration indicated Moo2 phase after 30 h which reached a maximum after 180 h but without loss in catalytic activity during the 400 h. The maximum regeneration time was 30 min and Moo2 phase was formed during regeneration with a mixture of 10% oxygen in nitrogen. The production of synthetic crude from LT tar was accomplished by treating it with hydrogen 3400-4250 m3/bbl over cobalt molybdate catalyst in two reactors at 350-370 "C and 450-490 "C, respectively, and an overall pressure of 700-2000 psig (346,347). Coke oven gas containing 58-68% hydrogen and also electrolytic hydrogen were used for the hydrogenation of certain coal tar resins over cobalt molybdate on alumina at 300;735 psig (298). Selective hydrogenation of a brown coal tar and a mixture of tar distillate and a crude oil fraction on Ni-W and Co-Mo catalysts gave a product free from nitrogen bases, phenols, or unsaturated compounds and having a high octane number. The Co-Mo catalyst had low cracking activity for the feedstocks, resulting in better product quality (315). Several investigators have established the optimum conditions for the hydrocracking and hydrogenation of LT tar fractions. Table I summarizes the results. The optimum conditions (400 "C, 735 psig, LHSV of 1.0, and hydrogen to feed ratio of 1OOO:l) were established in the hydrogenation of a mixture of 40% LT tar (b 90-230 "C) and 60% petroleum fraction (b < 240 "C) over a cobalt molybdate-alumina catalyst to give a product containing low percentages of sulfur (0.02%)and nitrogen (0.06%) (348). Morparia and Sarkar (306)established the optimum conditions-400 "C; 1422 psig, LHSV 0.5, and H2 to feed 400:l-for the hydrogenation of LT tar, resulting in a fraction (b 200-300 "C) with diesel index of 38.5. The low diesel index value may be improved by solvent extraction to remove part of the aromatics or by carrying out the reaction under hydrocracking conditions. Catalytic hydrorefining of LT tar oils over cobalt molybdate on alumina catalyst was carried out with a view to get gasoline and diesel fractions (349-352). A product with aniline point of 48 "C was obtained at 450 "C, 711 psig, and LHSV of 1.0 from neutral oil (b 200-300 "C) (349). Hydrogenation of various LT tar fractions boiling in the ranges 200-250 "C, 250-300 "C, and 300-350 "C in batch and continuous bench scale units showed that the 200-250 "C and 250-300 "C fractions can be converted to diesel fuels, while the 300-350 "C fraction was refractory to hydrogenolysis (353, 354). Mirza et al. (355-363)have evaluated commercial cobalt molybdate and nickel tungsten sulfide catalysts for the hydrogenation of various LT tar fractions in autoclaves and in continuous bench scale and small pilot plant units. With cobalt molybdate-alumina catalyst, a product containing maximum content of saturated hydrocarbons was obtained at 425-450 "C and 711-995 psig from neutral oil (b 225-290 "C). The diesel index of the fraction (b 200-340 "C) was low (-33) which makes the fraction unsuitable to be used as high speed diesel oil. The diesel index may be improved by solvent extraction of the hydrorefined
382 Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982
Q2
02
m
m
cg
0 9
CO
m
0
.m?
d
4
0 rl
0 0 0 000
3ooc-c-c-t-c-
omm
ri
2
m
0
0000000
0
0
N
N
NNNNNNN
c.1
N
0
0
0000000
0
0
mmmmmmmoooom
rl
rl
A A A A A A A A A A A A
m
m m
ri
rl
1
2
'?
0
m Q, Q,
m
N
mmmmmmm I
I
I
I
0 0
m
h
6
0 00
N I
0
m
N
U Li
I
c
I
I
u)
rlrlririrlriri
L"
0
L ? Y ~ L " L ? Y '?~
0000000
m
m
m
m m
,000000000000 rl r i d rl rl rl rl N N N N r i
d
0
m
Q, Q,
0 0
m
m
2m 2
d
drl
m 0 0 m m 0 0 t-omt-t-00 d m d d d m m
0
?
I
mmmmm m
rlrl
u
"
0
d m
3oorlririrlri 3oorirlrirlri
0
ri
rlrlrlrlrirlri
2
m
??????YY irirlrlrirloo
o o m m m ~ o0
Q, rl
(9
mmm
I
Q,
h
x
Q, Q,
m
t-
d
L?
0
m Q, Q,
In
c-
*
u
oooomoooomooooooooo oooot-wmocot-d***oocococo d*d*mdu)dmmmmmm+*mmm
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 383
a d
u
fraction or by high-pressure hydrogenation. With 200-305 " C neutral oil fraction, a temperature below 400 " C was optimum for getting a product, which has been hydrorefined to a maximum extent, without any decrease in the activity of cobalt molybdate alumina catalyst. A 2% concentration of H2Sis desirable in the recycle gas stream to keep the catalyst in the active form (357). A two-stage process using cobalt molybdate in the first stage and nickel tungsten in the second stage has been suggested (358).The activities of cobalt molybdate and nickel tungsten sulfide Catalysts for the hydrogenation of LT tar fraction (200-350 "C) and neutral oil were evaluated and compared. Both the catalysts were found to have almost the same hydrogenation activity for tar acids and sulfur compounds. Tungsten sulfide was more active than cobalt molybdate for the removal of nitrogen compounds (363). Nickel tungsten sulfide-alumina catalysts were prepared and evaluated for the hydrogenation of hydrorefined LT tar fraction at 360-400 "C and the results obtained at 380 "C, 1422 psig, and LHSV of 1.0 were compared with commerical nickel tungsten sulfide-alumina catalyst (362). Hydrotreating of LT tar produced a highly aromatic residue boiling above 315 "C which on processing gave good yields of carbon black. The lower boiling material was suitable for processing in conventional refinery to yield valuable products (364). Oil produced by the COED process was hydrogenated at 3000 psig over a fixed bed of nickel molybdate catalyst containing 3.0% NiO and 15% MooBon alumina. The product oils rich in cycloparaffins could be processed in a refinery (365). The diesel index of neutral oil from LT tar can be increased by hydrogenation with hydrorefining catalysts (280). Composition of Products The composition of aromatic and saturated hydrocarbons of the fraction boiling up to 210 " C obtained from hydrocracking of LT neutral oil (b 210-350 "C) with nickel sulfide catalyst at 550 "C was determined. The yield of low-boiling fraction was 40% of the liquid product. The saturated hydrocarbons constituted mainly methyl cyclohexane (51.2%) and the aromatic fraction contained about 40% of BTX fraction (326). The hydrocarbon content of fractions of crude oil prepared from hydrogenationcracking of LT tar was determined. The saturated fraction boiling between 95 and 105 "C which was 22% of the total spirit, contained entirely of methyl cyclohexane (366). Blonskaya and Lozovoi (367)determined the composition of 60-205 "C and 190-300 "C fractions of hydroaromatized product. The composition (368) and structural group analysis (369)of hydrogenated products of LT tar fractions were determined. Hydrocracking at Atmospheric Pressure High conversions of alkyl aromatic hydrocarbons were obtained at atmospheric pressure in a noncatalytic process when a mixture of hydrocarbons vapor and hydrogen was passed through a vessel containing electrically heated wires either in the form of extended filaments or as component gauze. Hydrocarbon oils boiling in the range 150-350 "C from vertical retort tars and Lurgi brown coal tars were converted by this process into benzene and naphthalene mixtures. Tar acid-free LT tar (80% boiling below 400 "C)gave a product (32%) containing 25% benzene and 12% naphthalene (370). Hydrocracking of a LT tar fraction (b 230-280 OC) over a fixed bed of catalyst at atmospheric pressure, using active carbon (Hykol-X) and nickel sulfide or cadmium chloride on active carbon as catalysts, was studied (371). Maximum yields of lowboiling fractions and low-boiling tar acids were obtained with active carbon at a cracking temperature of 550 "C,
384
Ind. Eng. Chem. Prod.
Res. Dev., Vol.
21, No. 3, 1982
LHSV of 0.5, and hydrogen to feed volume ratio of 1oOO:l. Coal tars were dealkylated by injection into a fluid bed of coke at 800 "C, the carrier gas containing at least 30% hydrogen, to give good yields of benzene and naphthalene (372). Molybdenum oxide supported on activated carbon was better than that supported on bauxite in the conversion of cresols but the spent activated carbon based catalysts could not be regenerated. The activity of the catalysts was maintained for a longer period if a large excess of hydrogen was used. Tar oils boiling up to 310 "C could be treated satisfactorily (373). Production of Jet Fuels Hydrocarbons with four or more aromatic rings found in the high-boiling fractions of coal tar may be used as raw material for the production of jet fuel by a combination of hydrogenation and cracking (374). Letort (375) discussed the development of jet fuels, general requirements, and their production from coal tar fractions over WS2MoSz catalyst. McGee (376) and Wainwright (29) have discussed the potentialities of LT tar for conversion to jet and missile fuels. It was pointed out that tetralins, naphthalenes, phenanthrenes, anthracenes, and fluoranthenes which constitute about 20% of LT tar could be basic raw materials (29). A two-stage process from highsulfur coke-oven tar fraction produced mainly naphthenic hydrocarbons free of sulfur. Cobalt molybdate was used in the first stage and a catalyst containing 65% nickel on kieselguhr was employed in the second stage. The product can be used as a motor, jet or diesel fuel, solvent, and plasticizer (377). Work carried out in France by CERCHAR (378) on HT tar and in America by U S . Bureau of Mines (379) on LT tar fractions showed that jet fuels can be produced. Feed boiling in the range 230-310 "C is suitable and hydrogenation can be carried out either by nickel or molybdenum sulfide as catalyst. The typical conditions were 3555 psig and 420 "C. The product from the pilot plant contained 89% saturated hydrocarbons and 11%hydroaromatics (380). In the Bureau of Mines work both desulfurization at 400 "C with commercial cobalt molybdate (Girdler G-35B) and saturation at 300 "C over a nickel kieselguhr catalyst (Harshaw Ni-0104T) were carried out in the vapor phase at 2500 psig with tar oil (b 230-300 "C) obtained in the carbonization of West Virginia coal in the pilot plant of the Consolidation Coal Co. The yield of final product was 20.4% of the starting material and contained bicyclics-41% noncondensed and 56% condensed (379). The final product, however, did not pass the stability test specified by the Air Force. The yield of jet fuel from LT tar was only 1% by weight of coal carbonized but that from coal hydrogenation oil was about 12% of the coal hydrogenated (381). The low yield obtained with LT tar fraction can be improved by using a wider boiling range fraction (382). Hydrocracking of Volatile Products of LTC Catalytic hydrogenation of LTC products before condensation has been recommended to stabilize them (383). Carbonization was carried out under a hydrogen pressure of 400 psig at 500-550 "C. The tar and vapors were passed over a hydrogenation catalyst containing 0.5% Ni, 1.0% Co, and 8.3% Mo on A1203in a separate zone at 425 "C and a pressure of 400 psig. A product rich in low-boiling phenols was obtained. Work was carried out by the US. Bureau of Mines (384,385) on the fixed bed carbonization of coal at around 500 "C in hydrogen atmosphere below 1000 psig followed by immediate fixed bed catalytic hydrogenation at 350-500 "C of tar vapor and liquid tar evolved from the coal bed. A maximum yield of 43.5 kg of oil in the gasoline boiling range per ton of moisture and
ash-free Pittsburgh seam coal was obtained at 600 psig with cobalt molybdate on alumina desulfurization catalyst at around 400 "C. This yield was about four times greater than that produced in ordinary LTC. The yields of benzene, toluene, and xylenes were 13.2, 13.2, and 5.9 kg per ton of coal carbonized, respectively, and the BTX fraction was 74% by weight of light oil. The product might be suitable for blending in the production of nonleaded gasoline. The reaction vessel, 14.9 cm i.d. and 50.8 cm depth, was designed to operate at 538 "C and 1000 psig. A two-stage hydropyrolysis process in which coal was carbonized in the first stage and the vapors were subsequently cracked at 500-950 "C under pressure gave a maximum benzene yield of 6% on daf coal (386). Kinetics and Reaction Mechanism of Hydrocracking of LT Tars Qader et al. (387,388) studied the hydrocracking of LT tar at constant hydrogen pressures of 1500 and 2000 psig and found that the reaction obeyed first-order kinetics. They observed that the rate constant for gasoline formation from tar varied with hydrogen concentration under low pressures but remained constant at higher pressures up to 2500 psig. They also found that the overall order was second order below 1500 psig and first order at and above 1500 psig for the hydrocracking of LT tar in an autoclave using a commercial catalyst containing 6% nickel and 19% tungsten both as sulfides supported on silicaalumina (389). An equation was given for the rate of gasoline formation. A mechanism involving simultaneous and consecutive cracking, hydrogenation, and isomerization was suggested. Cracking reaction involving the breakage of C-C, C-S, C-0, and C-N bonds on the surface of a dual-function catalyst was rate controlling (390). The mechanism of hydrocracking of polynuclear aromatics over ZnClz (391-393) and kaolin or zeolite cracking catalyst (394) has been suggested. In the hydrogenolysis of LT tar in the presence of a tungsten sulfide catalyst, it was indicated that the reactions of removal of sulfur, oxygen, and nitrogen compounds were all first order. Sulfur removal followed a true Arrhenius plot while oxygen and nitrogen removal showed a break at 400 "C in the Arrhenius plot (395). The hydrogenolysis of LT tar (396,397) over MOO, involves simultaneous consecutive cracking and hydrogenation reactions, and the formation of gasoline from tar was first order with an activation energy of 11.5 kcal/mol. Chemisorption of tar molecules on the catalyst was the rate-determining step (396). Hydrocracking of Tar Acids and Alkyl Phenols Low-boiling phenols were obtained by hydrocracking heavier fractions of LT tars using stannous chloride as catalyst (398). Tar acids (b 235-360 "C) were hydrocracked in a batch reactor at 420 "C in the presence of molybdate-alumina and 10% added water under hydrogen pressure of 2600 psig. The yield was 92% by volume and the product contained 8% tar acids and 23% boiling below 235 "C (399,400). Hydrogenolysis of tar acids has been investigated by several workers (189,195,265,401-409). High-boiling tar acids from LT tar were subjected to hydrogenolysis in an autoclave in the presence of cobalt molybdate, calcium oxide, and alumina catalysts (407). Maximum yield (37%) of low-boilingphenols was obtained at 400 "C with a contact time of 1 h and hydrogen pressure of 711 psig. During the hydrogenation of a phenolic fraction using 5% iron catalyst at 480-490 "C and 2350-5145 psig for 3 h, it was indicated that the amount of p-cresol decreased while that of m-cresol followed by o-cresol increased showing a weaker bond at the para position (405). The dihydric phenols are much less stable
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 385
than cresols a t 450 "C in the hydrogenation over ammonium molybdate catalyst, and the catalyst lost its activity rapidly (402). Dealkylation of high-boiling phenols was carried out in the presence of hydrogen using a catalyst which was either charcoal or material containing charcoal. A xylenol fraction (b 220-225 "C) was treated at 400 "C for 80 min to yield a product (91%) containing 42% of fraction boiling below 200 "C (410). Nickel sulfide on active carbon gave higher yields of low-boiling phenols from a 230-280 "C LT tar fraction under higher pressures compared to those obtained at atmospheric pressure. The conversion of tar acids to low boiling phenols was 29% at 475 "C under a hydrogen presesure of 711 psig compared to 10.6% at atmospheric pressure (327, 371). A catalyst containing 3-7% Cr203or Fe203on alumina or metallurgical coke or an A1-Mo was used in the conversion of higher boiling phenols to low boiling phenols (411). Hydrocracking over Fe203-A1203(1% Fe) at 475 OC and 1470 psig yielded 57% phenols. Addition of water or ammonium hydroxide failed to increase the degree of conversion (412). Hydrorefining LT tar in the presence of Co-Mo catalyst at 360 "C, 735 psig, and LHSV of 1.0 gave a product containing 25.9% phenols (413). The destructive hydrogenation of xylenols over an iron-molybdenum catalyst gave phenol and cresols, along with large amounts of aromatic hydrocarbons. Desulfurization took place, but organic bases present in the sample were unaffected (414). Hydrogenation of phenolic fraction was carried out using iron catalyst (415). Jelinek (416-419) studied the reactions of a cresols-xylenols mixture under hydrogen pressure. Fe203 catalyst containing 7.3% Cr203was more selective and gave higher yields of phenols compared to thermal hydrodealkylation (419). The best yields of low-boiling phenols were obtained with 1:2 molar ratio of tar acids and hydrogen at 600-700 "C. A higher concentration of hydrogen favored secondary cracking giving benzene (420). Catalytic hydrodealkylation of alkyl phenols was studied using charcoal-based catalyst containing alkali and fluorine (421-423). High-boiling tar acids (b 24e304 "C) were dealkylated over active charcoal at 475-550 "C and at around 750 psig. The use of metal impregnated charcoal gave more selective dealkylation than active charcoal alone, but these catalysts could not be regenerated by conventional methods. Aluminum borofluoride or zinc fluoride each on y-alumina caused extensive dealkylation and their activity could be fully restored by regeneration with air. Thermal dealkylation-hydrocracking of cresols and a mixture of xylenols at about 440 psig, 600-700 "C and in contact with coke bed in a flow reactor was carried out by Wells and Long (424). Demethylation (C6H4(OH)CH3 H2 C6H50H+ CHI), dehydroxylation (C6H4(OH)CH3 + H2 C6H5CH3+ H20),and demethylation/dehydroxylation (C6H4(0H)CH3+ 2H2 C6H6+ H20 + CHI) took place; the order of stability of cresols with regard to hydrocracking was m-cresol > p-cresol > o-cresol and the stability of xylenols was 3,5-xylenol > 2,5-xylenol > 3,4xylenol and 2,6-xylenol> 2,4-xylenol> 2,3-xylenol. Davies and Long (425,426) studied the thermal hydrocracking of o-, m- and p-cresols in the temperature range 580-700 "C at pressures up to 390 psig with hydrogen/cresols ratio ranging from 0.8 to 4.0 in a continuous flow reactor. In the presence of excess hydrogen, the results for overall rate of hydrocracking were found to fit a 1.5-order rate equation first order with respect to cresol and 0.5 with respect to hydrogen. As the hydrogenlfeed ratio was reduced below 1.0, the product became more complex and 1.5-order rate equation was no longer applicable. When nitrogen was
--
+
-
used instead of hydrogen, the results were found to fit in a first-order rate equation. The rate constants for the hydrocracking of the cresol isomers were found to be in the order ortho > para > meta. Cobalt molybdate supported on A1203favored dehydroxylation over demethylation in the hydrocracking of cresols. Disproportionation and isomerization reactions were more pronounced with cobalt molybdate than with the nickel catalysts (427). The thermal decomposition of the three cresols in a hydrogen stream at 670-730 "C and the residence time of 0.4 to 2.0 s proceeds through parallel as well as consecutive hydrogenolytic demethylation and dehydroxylation (428). Kubicka (429) studied the partial dealkylation of polyhydric phenols from LT tar fractions over sulfides and oxides of Mo, Ni, W, Co, and combinations of these on alumina or alumino-silicates at temperature around 360 "C. Catalytic activity was maintained for over 1500 h and could be regenerated by heating in air. The dealkylation of monohydric alkyl phenols to phenol over silica activated by HF was carried out at 880-1030 psig hydrogen pressure and temperatures up to 600 "C. The catalyst was found to be selective for phenol production. At 400-500 "C, mainly isomerization, disproportionation, and dehydroxylation occurred. The use of high pressures prolonged the life of the catalyst (416). Czechoslovakian workers have studied the dealkylation of alkyl phenols using various catalysts and in hydrogen atomsphere (430-436). Bakelite Ltd. (437) patented a process for the dealkylation of alkyl-substituted phenols over nickel sulfide or the silicate, oxide, or sulfide of Ba, Cd, Fe, Al, or Zn in an atmosphere of hydrogen. Methyl-substituted phenols were isomerized over ammonium fluoride or hydrogen fluoride treated alumina at 470 "C in the presence of hydrogen at about atmospheric pressure (438).
Carbon Formation in Hydrocracking Phenols were found to have no effect on the rate of carbon formation on the catalysts and initial separation of impurities of a basic character from the raw material increased the process life of a cobalt molybdate-alumina catalyst (439). Decrease in pressure increased the coke formation from 3.8 to 10% and decreased the gas yield from 18 to 10% in the hydrocracking of semicoking tar over cobalt molybdate on alumina and silica-alumina catalysts at 490 "C and 75 psig with dilution of 1:l with benzene (440). The coke deposition on a dual-functional catalyst (WS2-NiS-Si02-A1203)during hydrocracking of LT tar was about 1% , for processing a feed of 1L at 1500 psig and 475 "C, but was reduced to 0.9% when the hydrogen pressure was raised from 1500 to 3000 psig (324). Kinetics of coke formation on a cobalt molybdate-alumina catalyst were studied in the hydrocracking at 450-550 "C of a wide boiling coal tar distillate. The coke formation passed through a minimum at 510 "C (441). Among the diluents such as tetralin, cyclohexane, crude and pure benzene, and synthetic and low-temperature gasolines, decrease of coke yield was observed with tetralin and cyclohexane in the hydrocracking of LT tar (442). Literature Cited (1) Rhodes, E. 0. U S . Bur. Mines Inf. Circ. No. 7490 1949. (2) Storch, H. H. "Chemistry of Coal Utilization", Vol. 2: Lowry, H. H., Ed.; Wiley: New York, 1945: Chapter 38, pp 1750-96. (3) Bradley, W. E.; Hendrlcks, G. W.; Huffman, H. C.; Kelley, A. E. Proc. 5th WM. Pet. Congr. Sect 111, Paper 5. pp 55-70. (4) Choudhary, N.; Saraf, D. N. Ind. Eng. Chem. Prod. Res. D e v . 1975, 14, 74. (5) Corson, B. B. "The Chemlstry of Petroleum Hydrocarbons", Vol. 3.; Brooks, B. T.; Boord, C. E.; Kurtz, S. S.,Jr.: Schmerling, L., Ed.: Reinhold: New York. 1955; Chapter 51, pp 283-325. (6) Hesp. W. R. Mining Chem. Eng. Rev. 1961, 53(5),57. (7) Langlois, G. E.: Sulllvan, R. F. A&. Chem. Ser. 1970, No. 97, 38.
380
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 MacLaren, D. D.; Cunningham, A. R.; Hendricks, G. W.; Kelley, A. E. Can. J . Chem. Eng. 1964, 42(2), 68. Retallick, W. E.; Doelp. L. C. “Klrk-Othmer’s Encyclopedla of Chemical Technology”, 2nd ed.; Voi. 11, 1966; p 418. Scott, J. W.; Bridge, A. G. Adv. Chem. Ser. 1971, No. 703, 113. Scott, J. W.; Paterson, N. J. R o c . 7th WM. Pet. Congr. 1967, 4 , 97. Slttig, M. “Handbook of Catalyst Manufacture”; Noyes Data Corporation: 1978; pp 260-348. Voorhles, A., Jr.; Smith, W. M. “Advances in Petroleum Chemistry and Refining”, Vol. 8; McKetta, J. J., Jr., Ed.; Interscience: New York, 1964; p 169. Weller, S. W. “Catalysis”, Vol. 4.; Emmett, P. H., Ed.; Reinhold: New York, 1956; Chapter 7, pp 513-28. Winsor, J. Chem. Eng. (London) 1972, N o . 267, 194. Cox, J. L. “Clean Fuels from Coal“; Symp. ll., White, J. R.; Sprague, R.; McGrew, W., Ed.; Instltute of Gas Technology: Chicago, 1975; pp 271-97. Coal Research in C.S.I.R.0 (Australia) Report No. 18, 1962, pp 4-9. Gentry, F. M. “The Technology of Low Temperature carbonization“, The WilHams & Wlikins Co.: Baltimore, 1928 Chapter 3, pp 73-128. Janardanarao, M. Erdol Kohle, Erdgas, Petrochem. Brennst. Chem. 1979, 32(3), 127. Janardanarao, M. J . Sci. Ind. Res. (Indie) 1980, 39(8), 429. Jastrzebski, J.; Wiszniowski, K. Koks, Smoki, Gar 1977, 22(3), 78. Karr, C., Jr. “Chemistry of Coal Utilization”, Suppi. Vol.; Lowry, H. H., Ed.; Wiley: New York, 1963 Chapter 13, pp 539-79. Ladner. W. R.; Newman, J. 0. H.; Sage, P. W. J . Inst. Energy 1980, No. 6, 76. “Hydrogenation of Coal and Coal Tars”; United Nations Pubiicatlon, New York, 1972. Janardanarao, M.; Vaidyeswaran, R. “Proceedings. International Symposium on Coal Science and Technology for the Eighties, Central Fuel Research Institute, Cbnbad, Feb 1-3, 1979”, 1980; Paper 45, pp 498-502. King, J. G. ”The Science of Petroleum”, Vo1.3; Oxford University Press: London, 1938; pp 2156-63. Donath, E. E. “Chemistry of Coal Utllization”, Suppl. Vol.; Lowry, H. H., Ed., Wlley: New York, 1963 Chapter 22, pp 1041-80. Sarkar, S. Chem. f n g . WorM(Ind&) 1979, 74(11), 49. Walnwright, H. W. U S .Bur. Mlnes Inf. Clrc. No. 8054 1961. Wu, W. R. K.; Storch, H. H. U S .Bur. Mines Bull. No. 633 1968. Bhaduri, T. J.; Basu, A. N. Chem. Age Indie 1964, 75(7), 818. Jones, D. T. J . Chem. SOC. Ind. 1917, 36, 3. Fischer, F. Brennst.-Chem. 1920, 7 , 31, 47. Fischer, F. Brennst.-Chem. 1921, 2, 327, 347. Davis, J. D.; Parry, V. F. “Low Temperature Carbonization of Pennsylvania Coals, the Pittsburgh and Upper K h n i n g Beds”; Carnegie Inst. Technol. Bulletin No. 8, 1923. Dunstan, A. E. “Proceedings, Second International Conference on Bituminous Coal”; Carnegie Institute of Technology, Pittsburgh, Vol. 1. 1928; pp 210-38. Morrell, J. C.; Egloff, G. Ind. Eng. Chem. 1925, 77, 473. Egloff, 0.; Morrell, J. C. Proceedings, International Conference on Bituminous Coal, Plttsburgh, 1926; p 788. Egloff, G.; Morrell, J. C. 0 1 Gas J . 1927, 25(30), 156. 158. Morrell, J. C. U.S. Patent 1954091, Apr 10, 1934; Chem. Abstr. 1934; 28, 3876. Birthler, R. Acta. Chlm. Acad. Scl. Hung. 1957, 72, 161. Bunkina, N. A.; Bentsiinov, Yu. V.; Bronshtein, A. P.; Makarov, G. N.; Platonov, V. V.; Shul’ga, V. A. Sint. Anal. StruM. Org. Soedin. 1974 (6), 66; Chem. Abstr. 1976, 84, 76653. Cypres, R. Ann. Mines Be@. 1971, (9, 575. Cypres, R. Rech. Charbonniere: Appl. Tech. Miniere Base Nouv. Prod., Journees Inf. 1970 (Pub. 1971); Manly R. S., Ed.; Cent. Inform. Doc: Luxemburgh, pp 53-86.; Chem. Abstr. 1971, 75, 131531. Cypres, R.; Bredael, P. Ann. Mlnes Be@. 1989, (9). 983. Dvoskin, G. I.; Khmelevskaya. E. D.; Kablikov, V. A.; Chukhanov, 2 . F.; Turenko, F. P. Energ. Tekhnol. Ispol’s Topl. 1977, (59), 117. Godman, J. E.; Detrick, R. S. U S . Bur. Mines Rep. Invest. No. 5534, 1959. Hagemann, A. Z . Angew, Chem. 1929, 42, 503. Kosaka, Y. J . Soc. Chem. Ind. Jpn. Suppl. Binding 1931, 34, 10; Chem. Abstr. 1931, 25, 1971, 1972. Kosaka, Y. J . Soc.Chem. Ind. Jpn. Suppl. Blndhg 1931, 34, 241; Chem. Abstr. 1991, 25, 5542. Kosaka, Y. J . Soc. Chem. Ind. Jpn. Suppi. Binding 1931 34, 243; Chem. Abstr. 1931, 25, 5542. Krichko, A. A.; Sovetova, L. S. Khim. Tekhnoi. Smol. Term. Perera b . Tverd. Topliv, Akad. Nauk SSSR Inst. Goryuch. Iskop . 1965, 206-14; Chem. Abstr. 1965, 63, 5410. Morrell, J. C. U.S. Patent 1993520, Mar 5 , 1935; Chem. Absh. 1935, 29, 2698. Morrell, J. C.; Egloff, G. “Proceedings, Second International Conference on Bituminous Coal”, Voi. 2; Carnegie Institute of Technology: Pittsburgh. 1928; p 580. Morrell, J. C.; Faragher, W. F. Ind. Eng. Chem. 1929, 21. 1084. Nakai, R. Bull. Chem. Soc.Jpn. 1930, 5, 136. Topchlev, A. V.; Mamedaiiev, G. M.; Aliev, S. M. I z v . Akad. Nauk SSSR, Otd. Khlm. Nauk 1959, 861. Waddington. W.; Betts, W. D. Coal Tar Research Association (CTRA) Report No. 0317, 1983. Curtis. H. A.; Beekhuis, H. A. Chem. Met. Eng. 1926, 33, 666. Hartley, H.; Sinnatt, F. S., et ai. Dept. Sci. Ind. Research (Brit), Fuel Research Board, Report for the year ended March 1936.
-
(61) King, J. 0.; Cawiey, C. M. J . Inst. Petrol. Tech. 1936, 22, 595; Pet. Times 1936. 35, 583. (62) King, J. G.; Cawley, C. M. J. Inst. Fuel 1937, 70, 48. (63) Egloff, G.; Morrell. J. C.; Zimmerman, G. E.; Lemen, W. E. Ind. Eng. Chem. 32111. 39. -. .-. . . . 1940. .. (64) Egloff, 0.; Zimmerman. G. E.; Morrell, J. C.; Lemen, W. E. Oil Gas J . 1940. 38 1351. 36. 39. 52. 53. (65) Suzuki, A.; Kitahara, A.; M. J . Chem. Soc. Jpn., Ind. Chem. Sect. 1951, 54, 789; Chem. Abstr. 1953, 47, 7780. (66) Stramkovskaya, K. K. Izv. Tomsk. PoMekhn. Inst. 1959, 702, 119; Chem. Abstr. 1963, 58, 4342. (87) Chiton, C. H. Chem. Eng. 1958, 65(2), 53, 56. (68) Kuwata T.; Ueda, H. J . SOC. Chem. Ind. Jpn. 1944, 4 7 , 627; Chem. Abstr. 1948, 42, 6088. (89) Janardanarao. M. “Low Temperature Carbonization of Non-caking Coals & Lignites and Briquettlng of Coal Fines”, Symp. Vol. 2., CSIR, New Delhi, 1964; pp 148-53. (70) Janardanarao, M. Ph.D. Thesis, Banaras Hindu University, Varanasi, Indla, 1965. (71) Janardanarao. M.; Ramacharyulu, M.; Krishna, M. G. Brennst .Chem. 1968, 49(1), 10. (72) Rapoport, I.E. J . Appl. Chem. (USSR) 1940. 73, 1455. (73) Bunkina, N. A.,; Makarov, G. N.; Bronshtein, A. P.; Platonov, V. V. Koks Khlm. 1975, (E), 26. (74) Bunkina, N. A.; Bronshtein, A. P.; Makarov, G. N.; Platonov, V. V. Koks Khlm. 1976. (6), 28. (75) Nadenik, 0.;Ludvik, V.; Novak, J. Pram Ustavu Vyzkum Paliv 1965, 70, 143 Chem. Ab&. 1986, 64, 4820. (76) Coal Research in C.S.I.R.O. (Australla) Report No. 42, 1970, pp 2-5. (77) Hesp, W. R.; Philipp, D. H.; Waters, P. L. C.S.I.R.0 (Australia), Div. Mlner. Chem., Invest. Report No. 78, 1969. (78) Smirnova, T. S.; Pui’kina, M. K.; Davtyan, N. A.; Kashurichev, A. P.; Kazakov, E. I.; Zhuravleva, M. A.; Naumov, A. N.; Dvoskin, G. I. “Khim. Rod. VysokoskorostmgoPiroliza Burykh Uglei”, 1969; pp 34-48. Kazakov, E. I.; Ed.; Izd. “Nauka”: Moscow; Chem. Abstr. 1970, 72, 23267. (79) Joseph, R. T.; Maguire, J. E. US. Patent 2977299 Mar 28, 1961; Chem. Abstr. 1961, 55, 18079. (80) Wood, W. L. Oil Shale Cannel Coal Conf. 1951, 2, 690. (61) Klshida. M.; Chuto, M. Cas/ Tar(J.Japan Tar Ind. Assoc.) 1952, 4 , 398. Chem. Abstr. 1953, 47, 8120. (82) Ando, S.; Uchida. M.; Matsunami. T.; Saoti, S.; Takamitsu, N. Japanese Patent 6431, July 31, 1956; Chem. Abstr. 1958, 52, 5795. (83) Apter, D. M.; Kalinichenko, F. I. I z v . Sibrisk. otd. Akad. Nauk SSSR 1962, (2). 120; Chem. Abstr. 1962. 57, 6230. (84) Schbgut, S.; Sykwa, M. Chem. Prumysll957, 7, 581. (85) Imai, K.; Suzuki, M.; Nomwa, S . Nenryo-Kyokaishi 1957, 36, 526; Chem. Abstr. 1958, 52, 1591. (66) Marczewska, K.; Muslerowicz, J. Przem. Chem. 1960, 39, 97. (87) Hesp, W. R.; Phiiipp, D. H.; Waters, P. L. C.S.I.R.0 (Australia), Div. Miner. Chem. Invest. Report No. 79 1969. (88) Kuczynski, W.; Gilewicz, J. R z e m . Chem. 1960. 39, 785. (89) Kubicka, R.; Kvapii, 2.; Sykora, M. Chem. Prumysl 1962, 72, 598. (90) Ito, S.; Iida, T. Koru Taru 1962, 14, 158; Chem. Abstr. 1962, 57, 15433. (91) Schongut, S.; Prochazka, J. Sb. Pr. Vyzk. Chem. VyuzltiUhli, Dehtu Ropy 1965, 5, 27; Chem. Abstr. 1968, 64, 12429. (92) Toiubinskil, V. I.; Shkuratov, I. Ya.; Klimenko, Yu. G.; Govorova, R. P. Khlm. Prom., Nauk.-Tekhn. Zb. 1982, (2), 28; Chem. Abstr. 1963, 59, 7271. (93) Bredaei, P. Ann. Mines &/g. 1975. ( l l ) , 1045. (94) Erlcteux, J. Ann. Mines Be@. 1966, (9), 1095. (95) Cypres, R. Compend. Dtsch. Ges . Mlneraloelwks Kohlechem . 1976, 76-77(1), 435; Chem. Abstr. 1978, 88, 107728. (98) Buchtele, J.; Romovacek. J.; Weisser, 0. S b . Vys. Sk. Chem. Technol. Praze, Technol. Paliv 1971, 27, 69; Chem. Abstr. 1972, 76, 74578. (97) Bernhardt, R. S.; Ladner, W. R.; Newman, J. 0. H.; Sage, P. W. Fuel 1981, 60, 139. (98) Hesp, W. R.; Waters, P. L. Ind. Eng. Chem. prod. Res. Dev. 1970, 9, 194. (99) Hesp, W. R.; Hamor, R.; Waters, P. L. C.S.I.R.0 (Australia), Div. Miner. Chem. Invest. Report No. 77, 1969. (100) Hesp, W. R.; Neronowicz, R. J.; Waters, P. L. C.S.I.R.0 (Australia), Div. Miner. Chem. Invest. Report No. 76, 1969. (101) Ter-Akopyants, L. D. Tr. Lenlngr. 1nzhener.-Ekon. Inst.. Khim. i Khim. Robvodstva 1959, (25), 141; C h . Absh. 1960, 5 4 , 9254. (102) Tomkow, K. Prace Badawcze Glow. Inst. Gorn. Komun No. 68, 1950; Chem. Abstr. 1953, 47, 5094. (103) Kazakov. E. I.; Bekbulatova, Kh. I. Vop. Energ. Ispol’z. Energ. Resur. Kkg. 1970, 260-64; Chem. Abstr. 1972, 77, 91084. (104) Kazakov. E. I.; Bekbulatova, Kh. I.; Dzhamanbaev, A. S. Vop. Energ. I s p d ’ z . Energ. Resur. Kirg. 1970, 285-71; Chem. Abstr. 1972, 77, 91048. (105) Kazakov, E. I.; Smirnova, T. S.;Davtyan, N. A.; Dizengof, L. L.; Zhuravleva. M. A.; Naumov, A. N. “Khim. Prod. Vysokoskorostnogo Pirollza Burykh Uglei”; 1969; pp 9-24; Kazakov, E. I., Ed.; Izd. “Nauka”: Moscow; Chem. Abstr. 1970, 72, 23277. (106) Montgomery, R. S.;Decker, D. L.; Mackey, J. C. Ind. Eng. Chem. 1959, 51(10), 1293. (107) Montgomery, R. S.;Decker, D. L. Hydrocarbon Process. Pet. Refiner 1964, 43(12). 101. (108) Bernhardt, R. S.; Ladner, W. R.; Newman, J. 0. H.; Sage, P. W. Prepr. Am. Chem. Soc., Div. Fuel Chem. 1980, 25(1), 188. (109) Adams, W. N.; Gaines, A. F.; Gregory, D. H.; PM. G. J. Nature (London) 1959, 183, 33.
--.
~
..
~~
--I,.
.--,. - ~ . ~~1
~~
KG,
.
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 387 (110) Bond, R. L.; GodrMge, A. M.; Murnaghan, A. R.; Napier, D. H.; WIIliams, D. J. Nature (London) 1959, 184, 425. (111)Ollftiths, D. M. L.; Mainhood, J. S. R. Fuel 1967, 46(3), 167. (112) Rajasekhara Rao, K.; Seshagkl Rao, K.; VaMyeswaran, R. Erdiil Kohle Erdgas Petrochem. Brennst.-Chem. 1972, 25, 191. (113) Shchegolev, G. M. Akad. Nauk Ukr. S .S.R. Inst. Teploenerget Zb. RatsNo. 17, 1959, 71;Chem. Abstr. 1961. 55, 7801. (114) Zhukov, V. A.; Tagusheva. L. D.; Solodovnikova, K. S.; Lebedeva, P. I. Tr. Lenlngr. Inzhener.-Ekon. Inst. 1955, (g),97;Chem. Absb. 1959, 53, 8589. (115) Bezdvernyl, 0. N.; Gryaznov, N. S.; Kotelenets, M. S.; Orekhova, T. P. Coke Chem. (USSR) 1966 (3),29. 123. (116) Mashenkov, 0.N.; Syskov, K. I.Khim. Tverd. Topl. 1967, (9, (117) Ades, V. I.; DzhaparMze, P. N. Koks Khim. 1975, (12),25. (118) Naumov, L. S.;Akulov, P. V.; Kostenko, A. R.; Makarov, G. N.; Bronshtein, A. P.; Platonov, V. V. Koks Khim. 1976, (4).32. (119) Riedel, R. Sb. Vys. Sk. Chem. Technol. Raze, Technol. fallv 1986, 12, 5; Chem. Abstr. 1987, 67, 55997. (120) Romovacek, J.; Buchtele, J.; Welser. 0. Fuel 1972, 51(3). 228. (121) Bentsianov, Yu. V.; Bronshteln, A. P.; Bunklna, N. A,; Makarov, G. N. Khlm. Tverd. Topl. 1977. (5),132. (122) Bronshteln, A. P.; Makarov, G. N.; Naumov, L. S.; Platonov, V. V. Koks Khlm. 1977, (12),19. (123) Berl, E.; Hofmann, K. W. 2.Angew. Chem. 1931, 44, 259. (124) Bunte, K.; Lang, A. Gas Wasserfsch 1935, 78, 73. (125) Oleensfelder, B. S.;Voge, H. H.; Good, G. M. Ind. Eng. Chem. 1949, 41(11),2573. (126) Klnney, C. R.; Del Bel, E. Ind. Eng. Chem. 1954, 46, 548. (127)Tesner, P. A.; Rafalkes. I. S. m i . Akad. Nauk SSSR 1952, 87, 821. (128) Naugle, B. W.; Ortuglio, C.; Mafrlca, L.; Wolfson, D. E. U.S.Bur.
-
Mines Report Invest. No. 6625 1965.
(129) Dell, M. B. Ind. f n g . Chem. 1959, 51, 1297. (130) Dell, M. 6.; Stowe, V. M. U S . Patent 2967815,Jan 10, 1961; Chem. Abstr. 1961, 55, 14883. (131) Dell, M. B.; Stroup, P. T. US. Patent 2983665,May 9,1961;Chem. Abstr. 1961, 55, 19207. (132) Scholz. W.; Richter, H.; Anders, W.; Schiller, H. German (East) Patent 51 318,Nov 5, 1966;Chem. Abstr. 1987, 66.87424. (133) Berber, J. S.;Rice, R. L.; Fortney, D. R. Ind. Eng. Chem. Prod. Res. Dev. 1987, 6(3),197. (134) Jones, D. C.; Kelley, T. E.; Neuworth, M. B. Ind. f n g . Chem. 1954, 46, 12. (135) Rice, R. L.; Fortney, D. R.; Berber, J. S. Ind. Eng. Chem. Prod. Res. Dev. 1970, 9(1), 30. (136) Senseman, C. E. Ind. Eng. Chem. 1930, 22(1), 81. (137) Katkovskli, A. P.; Frldman, G. E.; Dorskaya, F. L. Akad. Nauk Belorusskoi S . S . R . Sbornlk Nauch Trudov 1939, 135-55;Khim. Reterat Zh. 1940, (2),27;Chem. Abstr. 1942, 36, 2390. (138) Braekman-Danheux, C.; Cypres, R. Ann. Mlnes Be@. 1969, (7,8), 813. (139) Jones, B. W.; Neuworth, M. B. Ind. Eng. Chem. 1953, 45, 2704. (140) Bronshtein, A. P.; Bunklna, N. A.; Makarov, G. N.; Platonov, V. V. Khim. Tverd. Topi. 1977, (l),96. Chem. Abstr. 1977, 87, 41592. (141) Cypres, R.; Braekman-Danheux, C.; Bredael, P.; Elnhorn, L. Ann. Mlnes Be@. 1970, (9),1105. (142) Cypres, R.; Lejeune, C. Ann. Mines Be@. 1985 (74,1091. (143) Jones, B. W.; Neuworth, M. B. Ind. Eng. Chem. 1952, 44, 2872. (144) Kosaka, Y. J . SOC. Chem. Ind. Jpn. (Suppi. Blnding) 1931, 34, 345,348; Chem. Abstr. 1932, 2 6 , 829. (145) Deshaltt, G. I. Khim. Tverd. ToDl. 1935, 6 , 918 Chem. Abstr. 1937, 31, 1982. (146) Stephan, M. J. Colliery Guardian 1929, 139, 2169. Chem. Abstr. 1930, 24, 945. (147)Welzmann, C. U.S.Patent 2430416,Nov 4, 1947; Chem. Abstr. 1948, 42, 1042. (148) Kuczynskl, W.; Baczyk, St. Rocz. Chem. 1953, 27, 170. (149) Kuczynskl, W.; Gliewlcz, J. Rzem. Chem. 1956, 35, 400. (150) Kuczynskl, W.; Gllewlcz, J. frzem. Chem.; Chem. Ind. (Warsaw) 1957. .--., 1217). - ~ . , ,400. Roy, P. R.; Gulati, I.B.; Basu, A. N.; Lahlrl, A. "Low Temperature Carbonization of Non-caklng Coals & Llgnttes and Brlquettlng of Coal Fines"; Symp. V01.2, C.S.I.R.: New Delhl, 1964 pp 138-47. Dal, V. I.; Ruban, I.N. Ukr. Khim. Zh. 1957, 23, 411. Dal, V. I.; Ruban, I.N. Ukr. Khim. Zh. 1958, 24, 107. i154j Liider, H.; Drescher, K. Chem. Tech. (Berlin) 1960, 12, 16. (155) Dal, V. I.; Zakupra, V. A. Kompleksne Vlkorlstannya falivnoenerg. Resursiv Ukrainl (Kiev: Akad. Nauk Ukr R .S.R .) Sbornik 1959, 13, 209. Chem. Absh. 1962, 56, 6275. (156) Janardanarao, M.; Ramacharyulu, M.; Krlshna, M. G. Brennst Chem. 1986, 49(3), 65. (157) M.; Krishna, M. G. Brennst. . . Janardanarao. M.; Ramacharyulu, . Chem. 1966, 49(4), 1 1 1. (158) Free, 0.; Funer, W.V. German Patent 767817,Oct 13, 1953;Chem. Abstr. 1955, 49, 2060. (159) I. 0. Farbenlnd Akt. Ges. French Patent 863502, Apr 3, 1941; Chem. Abstr. 1948, 42, 9154. (160) Kublcka, R.; Kvapll. 2.; Kostkova, H. Czech. Patent 118990,Dec 15, 1965;Chem. Abstr. 1986, 65, 13611. (161) Welzmann, C. British Patent 574963,Jan 29, 1946;Chem. Abstr. 1949, 4 3 , 1951. (162) Barlot, J. Mat. Grasses 1939, 31, 14; Chem. Abstr. 1939, 31,
.
.
2690. (163) Wencke, K. Monatsber. Deut. Akad. Wiss. Berlin 1959, 1 , 499; Chem. Abstr. 1981, 55, 19203. (164) Wencke, K. Freiberg. Forsch. 1960, A151, 30.
(165) Kobayashl, K.; Ishikawa, H. J . SOC. Chem. Ind. Jpn. 1942, 45, 1171;Chem. Abstr. 1949, 43, 7667. (166) Gallagher, J. P.; Humes, W. H.; Slemssen, J. 0. Chem. f n g . frog. 1979, 75(6),56. (167) Jones, J. F., Jr. Diss. Abstr. 1981, 2 1 , 3031;Chem. Abstr. 1981, 55, 15889. (168) Dal, V. I.; Zakupra, V. A. Nauch. Dokl. Vysshei Shkoly, Khlm. i Khlm. Tekhnol 1959, (l),173. (169) Dal, V. I.; Zakupra, V. A. Ukr. Khim. Zh. 1959, 25, 268. (170) Zakupra, V. A.; Dal, V. I. Ukr. Khim. Zh. 1959, 25, 532. (171)Janardanarao, M.; Ramacharyulu, M.; Vaidyeswaran, R. Indian J . Technol. 1967, 5(12),399. (172) Neuworth, M. B. British Patent 743707,Jan 25, 1958;Chem. Abstr. 1956, 50, 12450. (173) Berber, J. S.; Little, L. R., Jr. frepr. Am. Chem. SOC., Dlv. Fuei Chem. 1962, 86-94. (174) Berber, J. S.;Little, L. R., Jr. U . S . Bur. Mines RepoH Invest. No. 6585 1985.
s.; Rice, R. L.; Spencer, J. D. U . S . Bur. Mines Bull. No, 663 1973. (176) Perna, F.; Pelcik, J. faliva 1953, 33, 126;Chem. Abstr. 1955, 49, (175) Berber, J.
7514. (177) Kuznetsov, M. I.; Belov, K. A. Ukr. Khim. Zh. 1937, 12, 412. (178) Given, P. H. British Patent 695464,Aug 12, 1953; Chem. Abstr. 1954, 48, 11490. (179) Given, P. H. Chem. Ind. 1958, 525. (180) Given, P. H. J . Appl. Chem. 1957, 7 , 172. (181) Given, P. H. J . Appl. Chem. 1957, 7 , 182. (182) Kochloefl, K.; Kraus, M.; Bazant, V. Collect. Czech. Chem. Commun. 1959, 24, 958. (183) Kraus, M.; Kochloefl, K.; Komers, R.; Bazant, V. Collect. Czech. Chem. Commun. 1959, 24, 1188. (184) Nickels, J. E. U.S. Patent 2551 628,Nov, 8, 1951; Chem. Abstr. 1951, 45, 10259. (185) Melssner, H. P.; French, F. E. J . Am. Chem. SOC.1952, 74, 1000. (186) Plgman, I.; Del Bel, E.; Neuworth, M. B. J . Am. Chem. SOC.1954, 76, 6169. (187) Schneider, P.; Kraus, M.; Bazant, V. Coiiect. Czech. Chem. Commun. 1982, 27, 9. (188) Kraus, M.; Bazant, V. Collect. Czech. Chem. Commun. 1983, 28, 1877..
(189) Kraus, M.; Kochloefl, K.; Beranek, L.; Bazant, V. f r o c . I n t . Congr. Catal., 3rd, Amsterdam 1984, 1 , 577. (190) Roberts, J.; Jenkner, A. "International Coal Carbonization"; Sir Isaac Pitman & Sons, Ltd.: London, 1934 pp 431-44. (191) Sander, A. Teer Bitumen 1934, 32, 149, 163;Chem. Abstr. 1934, 28, 7481. (192) Tupholme, C. H. S. Ind. fng. Chem. News Ed. 1938, 16, 221. (193) Ando, S. J . SOC. Chem. Ind. Jpn. Suppi. Binding 1933, 36, 86; Chem. Abstr. 1933, 27, 3061. (194) Ando, S.J . SOC. Chem. Ind. Jpn. Suppi. Binding 1933, 36, 243; Chem. Abstr. 1933, 2 7 , 3585. (195) Ando, S.J . Fuel. SOC.Jpn. 1933, 12, 62;Chem. Abstr. 1933, 27, 3702. (196) Ando, S.J . SOC.Chem. Ind. Jpn., Suppi. Binding 1934, 37, 357; Chem. Abstr. 1934, 28, 6983. (197) Ando, S. Pet. Times 1934, 32, 1976; Chem. Abstr. 1934, 28, 7481. (198) Ando, S. J . SOC.Chem. Ind. Jpn. Suppi. Binding 1934, 37, 570; Chem. Abstr. 1935, 29, 912. (199) Ando, S. J . SOC.Chem. Ind. Jpn. Suppi. Bindlng 1935, 38, 145; Chem. Abstr. 1935, 29, 4922. (200) Ando, S. J . SOC.Chem. Ind. Jpn. Suppi. Bindlng 1935, 38, 196; Chem. Abstr. 1935, 29, 5251. (201) Ando, S. J . SOC.Chem. Ind. Jpn. Suppi. Binding 1935, 38, 267; Chem. Abstr. 1935, 29, 6402. (202) Ando, S. J . SOC.Chem. Ind. Jpn. Suppi. Binding 1935, 38, 567; Chem. Abstr. 1938, 30, 1211. (203) Ando, S. J . SOC.Chem. Ind. Jpn. Suppl. Binding 1938, 39, 133; Chem. Abstr. 1938, 30, 5394. (204) Ando, S.J . SOC.Chem. Ind. Jpn. Suppl. Binding 1938, 39, 278; Chem. Abstr. 1938, 30, 8577. (205)Ando, S.J . SOC.Chem. Ind. Jpn. Suppi. Binding 1938, 39, 447; Chem. Abstr. 1937, 31, 4475. (206)Ando, S. J . SOC. Chem. Ind. Jpn. Suppl. Binding 1937, 4 0 , 12; Chem. Abstr. 1937, 31, 4796. (207) Ando, S.J . FuelSoc. Jpn. 1937, 16, 21;Chem. Abstr. 1937, 31, 5540. (208)Ando, S.J . SOC. Chem. Ind. Jpn. Suppl. Binding 1937. 40, 83; Chem. Abstr. 1937, 31, 6851. (209) Ando, S.J . SOC.Chem. Ind. Jpn. Suppl. Binding 1937, 4 0 , 124; Chem. Abstr. 1937. 31, 6851. (210) Ando, S.J . FuelSoc. Jpn. 1938, 17, 33: Chem. Abstr. 1938, 32, 6440. (211) Ando, S. J . SOC. Chem. Ind. Jpn. Suppi. Binding 1938, 41, 126; Chem. Abstr. 1936, 32, 6839. (212) Ando, S.J . SOC.Chem. Ind. Jpn. Suppl. Binding 1938, 4 1 , 191; Chem . Abstr. 1938, 32, 8745. (213) Ando, S. J . SOC.Chem. Ind. Jpn. Suppl. Binding 1936, 41, 215, 247; Chem. Abstr. 1938, 32, 9448. (214) Ando, S. J . SOC. Chem. Ind. Jpn. Suppl. Binding 1936, 41, 292; Chem. Abstr. 1939, 33, 1473. (215) Ando, S. J . SOC. Chem. Ind. Jpn. Suppi. Binding 1938, 41, 411; Chem. Abstr. 1939, 33, 4405. (216) Ando, S.J . SOC. Chem. Ind. Jpn. Suppl. Binding 1939, 42, 89; Chem. Abstr. 1939, 33, 6030.
388
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 Ando, S. J. SOC.Chem. Ind. Jpn. Suppl. Bhding 1939,42, 147; Chem. Abstr. 1939,33, 7077. Ando, S. J. SOC.Chem. Ind. Jpn. Suppl. Binding 1939,42, 171; Chem. Abstr. 1939,33, 8961. Ando, S . J. SOC.Chem. Ind. Jpn. Suppl. Binding 1939,42, 232; Chem. Abstr. 1939,3 3 , 9596. Ando, S . J. SOC.Chem. Ind. Jpn. Suppl. Binding 1939,42, 268; Chem. Abstr. 1940,3 4 , 872. Ando, S.J. SOC.Chem. Ind. Jpn. Suppl. Binding 1939,42, 358; Chem. Abstr. 1940,34, 3052. Ando, S. J. SOC. Chem. Ind. Jpn. Suppl. Binding 1940, 43, 35; Chem. Abstr. 1940.34, 4255. Ando, S.; Usiba, T. J. SOC.Chem. Ind. Jpn. Suppl. Binding 1936, 41, 315;Chem. Abstr. 1939,33, 1474. Ando, S.;Usiba, T. J. Soc.Chem. Ind. Jpn. Suppl. Bindlng 1936, 41, 317; Chem. Abstr. 1939,33, 1474. Ando, S.;Usiba, T. J. SOC.Chem. Ind. Jpn. Suppl. Binding 1936, 41, 390;Chem. Abstr. 1939,33, 3564. Ando, S.;Usiba, T. J. SOC.Chem. Ind. Jpn. Suppl. Binding 1939, 42, 27;Chem. Abstr. 1939,33, 4406. Ando, S.;Usiba, T. J. SOC.Chem. Ind. Jpn. Suppl. Binding 1940, 43, 221; Chem. Abstr. 1941,35, 1603. Alekseeva, K. A,; Mddavskli, 8. L. Khlm. Tekhnol. Topliv. Masel 1956,3(10), 7; Chem. Abstr. 1959,53, 1684. Birthler, R.; Szkibik, C. freiberg. forsch. 1955,A36, 42. Giinther, G. Freiberg. forsch. 1954,A23, 5. Holroyd, R. U.S.Bur. Mines I n f . Circ. No. 7370 1946. Schnabel, B.; Kubicka, R. Czech. Patent 85992, Oct 15, 1956; Chem. Abstr. 1959,53, 697. Cawley, C. M. Gas J. 1935,212, 571;Gas World 1935, 103. 531. Cawley, C. M. Gas World, Coking Sect. 1936,54, 13. Cawley, C. M. Gas Workj, Coking Sect. 1936, 103 (2692),31. Cawley, C. M. Dept. Sci. Ind. Research (Brlt.), Fuel Research Board, Report for the year ended March 1938,pp 150-58. Cawley, C. M. Dept. Sci. Ind. Research (Brit.), Fuel Research Board Report for the year ended March 1939. pp 134-37. Cawley, C. M.;King, J. G. Dept. Sci. Ind. Research (Brit.), Fuel Research Board Tech. Paper No. 45, 1937. Cawley, C. M.; Klngman, F. E. T. fuel 1943,22, 156. Hartley, H. et ai. Dept. Sci. Ind. Research (Brit.), Fuel Research Board Tech. Paper No. 40, 1935. King, J. G. Gas Eng. 1935,52, 15. King, J. G.; Cawley, C. M. Dept. Sci. Ind. Research (Brit.), Fuel Research Board Tech. Paper No. 41, 1935. Pier, M. Roc. WM. Pet. Congr. 1933,2 , 336. Gosselin, A. Rev. Inst. franc. Petrol. 1946, 1, 145;Chem. Abstr. 1948, 42, 4333. King, J. G.; Shaw, J. F. Trans. Chem. Eng. Congr.; WM. Power Conf. 1936,3 , 463. Cawley, C. M. Fuel 1944,23, 19. Heinze, R. Gas Wasserfach 1942, 85, 413.;Chem. Abstr. 1943, 37, 5847. Storch, H. H.; Hirst, L. L.; Fischer, C. H.;Work, H. K.; Wagner, F. W. Ind. Eng. Chem. 1941,33(2),264. Cawley, C. M.; Hall, C. C. J. SOC. Chem. Ind. 1934,53, 806. Cawley, C. M.; Hall, C. C. J. SOC. Chem. Ind. 1944,63, 33. Cawley. C. M.; Hall, C. C.; King, J. G. J. SOC.Chem. Ind. 1935,5 4 , 58T. Cawley, C. M.; King, J. G. Dept. Sci. Ind. Research (Brit,), Fuel Research Board Tech. Paper No. 48, 1938. Hartley, H.; Slnnatt, F. S. et ai. Dept. Sci. Ind. Research Board, Report for the year ended March 1935, 188 pp. King, J. G.; Cawley, C. M. Congr. Mondial fetrole 2, Sect 2 , Phys ., Chim., Raffinage 1937,249;Chem. Abstr. 1939,33, 345. Sinnatt. F. S.;King, J. G. Gas WorM, Coking Sect. 1935, 102(2652),
61 Cawley. C. M.; King, J. G. Dept. Sci. Ind. Research (Brit,), Fuel Research Board Tech. Paper No. 51, 1939. Cawley, C. M.; Hall, C. C. J. SOC. Chem. Ind. 1937, 5 6 , 445T. Gordon, K. J. Inst. fuel 1947,21, 53. Clough, H. Ind. Eng. Chem. 1957,49(4),673. Hill, G. R.; Lyon, L. B. Ind. Eng. Chem. 1962, 54(6),36. Vaidyeswaran, R.; Krishna, M. G.; Zaheer, S. H. "Low Temperature Carbonization of Noncaking Coals 8 Lignites and Briquetting of Coal Fines", Symp. Vol. 2,C.S.I.R.: New Delhi, 1964;pp 232-41. Lozovoi, A. V.; Krichko, A. A.; Pchelina. D. P. U.S.S.R.Patent 111825,June 25, 1958;Chem. Abstr. 1956,5 2 , 19091. Lorovoi, A. V.; Muselevich, D. L. Blonskaya, A. I.; Ravlkovich, T. M.; Titova. T. A. U.S.S.R. Patent 1 1 1769,June 25, 1958;Chem. Abstr. 1956,52, 19091. Vybihal, J.; Schiingut, S. Chem. frumysl 1956, 6 , 133. Basak, N. G.; Bose, S. K.; Ganguly, A. K.; Lahirl. A. Indian Patent 66095,Mar 15, 1981;Chem. Abstr. 1961,55, 14882. El'bert, E. I.; Katsobashvili, Ya. R. U.S.S.R. Patent 189405,Nov 30, 1966;Chem. Abstr. 1967,67, 66465. Flinn, R. A.; Tarhan, M. 0. U.S. Patent 3503872,Mar 31, 1970; Chem. Abstr. 1970, 72, 123745. French Patent (to charbonnages de France) 1 270 703,Jan 8, 1962; Chem. Abstr. 1962,57, 15436. Friedman, L. D.; Eddinger. R. T. U S Patent 3 453 202,July 1, 1969: Chem. Abstr. 1969, 71, 41106. Gorin. E.; Struck, R. T.; Zielke, C. W. Belgian Patent 663 191,Oct 29, 1965;Chem. Abstr. 1966,65, 2022. Herbert, W.; Gross, H. W. German Patent 1012718,July 25, 1957; Chem. Abstr. 1960,54, 9273.
(272) Ibing, 0. German Patent 867387, Feb 16, 1953; Chem. Abstr. 1956,52, 15882. (273)Katsobashvill, Ya. R.; El'bert, E. I.U.S.S.R. Patent 212241,Feb 29, 1968;Chem. Abstr. 1966,69, 21005. (274) Katsobashvill, Ya. R.; El'bert, E. I.; Belenko, 2. G. U.S.S.R. Patent 203652,Oct 9, 1987;Chem. Absh. 1968,68, 97380. (275) Katsobashvili, Ya. R.; Garber, Yu. N.; El'bert, E. I.; Belenko, 2. G.; Borts, A. 0. U.S.S.R. Patent 143786,Jan 27, 1962;Chem. Abstr. 1962,57, 6239. Belenko, 2. G. (276)Katsobashvili, Ya. R.; Garber, Yu. N.; El'bert, E. I.; U.S.S.R. Patent 145581. Mar 21, 1982; Chem. Abstr. 1962, 57, 10122. (277) Katsobashvlll, Ye. R.; Garber, Yu. N.; Ei'bert, E. 1.; Lukanin, A. A. U.S.S.R. Patent 148038,June 21, 1962;Chem. Abstr. 1963,58, 3244. (278) Krichko, A. A.; Borts, A. G.; Konyashina, R. A,; Lozovoi, A. V.; L vova, L. N.; Sovetova, L. S.; Tsitron, I. L. U.S.S.R. Patent 140434, Oct 9, 1961;Chem. Abstr. 1962,56,11933. (279) McNeil, D.; Waddington, W.; Popper, F. B. British Patent 761 755, Nov 21, 1956;Chem. Abstr. 1957,51, 10582. (280) Rao, B. S.N.; Murad, K. M.; Vaidyeswaran, R.; Ramaswamy, A. V.; Krishna, M. G.; Zaheer, S. H. Indian Patent 80742,May 9, 1964; Chem. Abstr. 1965,63, 4063. (281)Stowe, V. M. U.S. Patent 2983668,May 9, 1961; Chem. Abstr. 1961,55,19207. (282) Tarhan. M. 0.US. Patent 3623973,Nov 30, 1971;Chem. Abstr. 1972, 76, 48106. (283) Waddlngton, W.; Betts, W. D.; Freeman, J. W. Briiish Patent 1008756, Nov 3, 1965; Chem. Abstr. 1966,64, 1860. (284) Birthler, R. Chem. Tech. (Berlin) 1956,8,266. (285) Blonskaya, A. I.; Lozovoi, A. V.; Muselevich, D. L.; Ravikovich, T. M.; Titova, T. A. Tr. Inst. Goryuch. Iskop., Akad. Nauk SSSR 1959,9. 5. (286) Borts, A. G.; Kirchko, A. A,; Konyashina, R. A,; Lozovoi, A. V.; L'vova, L. N. Koks Khim. 1961,(lo),53. (287)Borts, A. G.; Krichko, A. A.; Konyashina, R. A.; Lozovoi, A. V.; L'vova, L. N. T r . Inst. Goryuch. Iskop ., Akad. Nauk SSSR 1962, 17, 250. (288) Bovkun, R. A.; El'bert, E. I.; Panfilov, I.A.; Smirnov, V. K.; Gur'ya-
nova, S. N.; Usenko, L. L. Tekh. f r o g . Dostizh Naukl Khlm. from. 1973, 14-17;Chem. Abstr. 1974,81, 80040. (289) El'bert, E. I.; Katsobashvill, Ya. R.; Smirnov, V. K.; Rewa, M. K. Kompleks Isspol'z Khim . Prod. Podzemn Gazif. Kuznetsk lJg/ei 1966,(3),10;Chem. Abstr. 1971, 74, 144343. (290) El'bert, E. I.; Kostyuk, L. B.; Blryukova, M. E.; Katsobashvili, Ya. R. Koks Khim. 1966,(12),43. (291) Eqbal, J.; Sarkar, S. I n d . J. Techno/. 1971,9(8),313. (292)Graves, R. D.; Kawa, W.; Hiteshue, R. W U . S . Bur. Mines Report Invest. No. 6124 1962. (293)Huang, C. Y.; Wei, Y. H. Jan Liao Hsueh Pa0 1960, 5, 21;Chem. Abstr. 1960,54, 17849. (294) Ihnatowicz, M.: Sobolewski, L. Koks, Smda, Gar 1977,22(2),29. (295) Ipat'ev, V. N.; Petrov, A. D.; Ivanov, I.2. Zh. Prlk/. Khlm. 1929,2 ,
.
.
429. (296) Katsobashvili, Ya. R.; El'bert, E. I.Koks Khim. 1966,(I), 43. (297) Katsobashvili, Ya. R.; Ei'bert, E. I.Coke Chem. (USSR) 1966,( I ) , 41. (298) Katsobashvili, Ya. R.; El'bert, E. I.Khim. Tekhnol. Topliv Masel 1966, 11(11), 16. (299) Katsobashvili, Ya. R.; El'bert, E. I., Smirnov, V. K. Khim. Tekhnol. Topliv. Masel 1964,9(2),5; Chem. Abstr. 1964,60, 13071. (300)Katsobashvili, Ya. R.; Garber. Yu. N.; El'bert, E. I.;Belenko, 2. G. Coke Chem. (USSR) 1961,(IO), 41. (301)Klimke, R.; Gondzik, J. freiberg. Forsch. 1962,A 2 2 1 , 29. (302)Krichko, A. A.; Lozovoi, A. V.; Pchelina, D. P. T r . Inst. Goryuch. Iskop., Akad. Nauk SSSR 1959,9,37. (303)Kubicka, R.; Kvapii, 2. Sb. f r . Vyzk. Chem. Vyuzlti Uhll, Dehtu Ropy 1970,(lo),3. (304)Lozovoi, A. V.: Muselevich, D. L.; Ravikovich, T. M.; Titova, T. A.; Cherkasova, V. F. Tr. Inst. Goryuch. Iskop., Akad. Nauk SSSR 1962, 17, 174. (305) Matsuda, S . ; Kikkawa, Sh.; Uchida, A. Kogyo Kagaku Zasshi 1962, 65, 568. (306)Morparia, N. P.; Sarkar, S. "Proceedings, Symposium on Chemicals and Oil form Coal", Dec 6-8, 1969 (Pub. 1972),Central Fuel Research Institute: Dhanbad, India, Paper 13,pp 156-60. (307) Panfilov, I.A.; El'bert, E. I.; Titushkin, V. A. Kostyuk, L. 8.; Smirnov, V. K. Tekh. f r o g . Dostizh. NaukiKhlm. from. 1973,58-61. (308) Paviovich. L. 8.; Gavrilov, N. N. Koks Khim. 1979,(12),30. (309) Pavlovich, L. B.; Gavrilov, N. N.; Titushkin, V. A,; Katsobashvili, Ya. R. Koks Khlm. 1977,(3),26. (310) Sakabe, T.; Horie. M.; Ogo, Y.; Sassa, R.; Takahashi, Sh.; Konbayashi, Y. Resources Res. Inst. Report No. 66, 1966. (311)Sakabe, T.; Sassa. R.; Horie, M. Kogyo Kagaku Zasshi 1966, 69,
1085. (312) Schnabel, B. Chem. frumysl 1959,9(l),10. (313)Shono, Sh.; Yamada, M. Koru Taru 1963, 15(9),405;Chem. Abstr. 1964,61, 6823. (314) Svajgl. 0.; Smrr, 2. Chem. Frumysl 1966, 76(6),294. (315) Smrz. 2. Sb. f r Vvzk. Chem. Vvuziti Uhli, Dehfu RODY . . Svaial, 0.: .. 1977,(Il),43. (316)Varga, J. Trans. 5th WM. Power. Conf. Vienna, 1956,Div. 2,Sect D, Paper 220. D17, 6 pp. (317)Wang. Pang-Nien. Hua Hsueh Shlh Chleh 1959, 14, 7;Chem. Abstr. 1960.54, 21712.
Ind. Eng. Chem. Prod. Res. Dev., Vol. 21, No. 3, 1982 389 (318) Law, R. D. Western Petroleum Refiners Associatlon, Rocky Mountain Reglonal Meeting, Casper, WY, 1957; Tech. 57-29. (319) Most Hydrogenation Works in Czechoslovakia, Spl. Report Sept 1957. (320) Bovkun, R. A.; El’bert, E. I.; Panfibv, I.A.; Mwozova, S. N.; Usenko, L. L. Pererab. Tverd. Topl. 1070, (2), 225. W. W. (321) Carpenter, H. C.; Cottlngham, P. L.; Frost, C. M.; Fowkes, ’ U S . Bur. Mlnes Report Invest. No. 6237 1063. (322) . . Wille. H. C. French Patent 1401 376, June 4, 1965; Chem. Abstr. 1086, 64, 17303. (323) Qader, S. A.; Wiser, W. H.; Hill, G. R. E r a Kohle Erdgas Petrochem. Brennst. Chem. 1070, 23(12), 801. (324) Qader, S. A.; Hill, 0. R. Ind. Eng. Chem. Proc. Des. Dev. 1060, 8, 450.
(325) Janardanarao, M.; Krishna, M. G. Chem. Age India 1066. 77(3), 233. (326) Janardanarao, M.; Krishna, M. G. Ind. J . Technol. 1060, 7(5). 160. (327) Janardanarao, M.; Sahrapatl, G. S.;Srlkanthareddy, P.; Valdyeswaran, R. Er&l Kohle Erdgas Petrochem. Brennst. Chem. 1070, 23(1), 20. (328) Janardanarao, M.; Salvapati, G. S.; Srlkanthareddy. P.; Vaidyeswaran, R. Pet. Hydrocarbons 1070, 5(2), 19. (329) Janardanarao, M.; Sahrapati, 0. S.; Vaidyeswaran, R. Erd6l Kohle Erdgas Petrochem. Brennst. Chem. 1074, 27(6), 309. (330) Janardanarao, M.; Srikanthareddy, P.; Salvapatl, G. S.; Vaidyeswaran, R. Pet. Hydrocarbons 1070, 5(2), 11. (331) D a r k A. D.; Levin, S. 2. Tr. Vost. Slb. Tekhnol. Inst. 1070, 3(3), 3. (332) Knyazeva. M. S.,; Lanin, V. A.; Murzaeva, A. I.; Pronina, M. V. Izv. Akad. Nauk SSSR, Otd. Tekh. Nauk 1055, (4), 112; Chem. Abstr. 1056, 5 0 , 2955. (333) Brahmachari. B. B.; Saha, M. R.; Choudhury, P. B.; Ganguil, A. K. “Proceedings. Symposium on Chemicals and Oil from Coal”; Dec 6-8, 1969 (Pub. 1972); Central Fuel Research Institute; Dhanbad, India, Paper 15, pp 170-74. (334) Eddlnger, R. T.; Friedman. L. D. Fuel 1988, 47, 320. (335) Landa, S.; Mandlk.; L.; Kuras. M. Sb. Vys. S k . Chem., Technol R a z e , Technol. Pallv 1073, 029, 145. Chem. Abstr. 1076, 84, 138167. (336) Svajgl, 0. Chem. Prumysl 1050, 9(5), 230. (337) Svajgl, 0. Collect. Czech. Chem. Commun. 1050, 2 4 , 3829. (338) Svajgl, 0. Sb. Vys. S k . Chem., Technol Praze, Techno/. Paliv 1067, 73, 163; Chem. Abstr. 1068, 68, 88900. (339) Svajgl, 0.Collect. Czech. Chem. Commun. 1080, 25, 1883. (340) Svajgl, 0. Chem. Prumysl 1058, 8(1), 13. (341) Allendorf, M.; Joachim. R., Meyer, G.; Mlchel, W.; Sommer, P. German (East) Patent 84438, Sept 12. 1971; Chem. Abstr. 1073, 78, 86923. (342) Svajgl, 0. S b . Pr. Vyzk. Chem. Vyuziti Uhli, Dehtu Ropy 1088, 6 , 129; Chem. Abstr. 1067, 67, 55899. (343) Varga, J.; Karolyi, J.; Stelngaszner. P.; Zaiai, A.; Blrthler, R.; Rabo, Gy. Pet. Reflner 1060, 39(4), 182. (344) El’bert, E. I.; Tryasunov. B. G. Klnet. Katal. 1073, 74, 1073. (345) El’bert, E. I.; Tryasunov, B. G.; Sukhoveev, S. G. Koks Khlm. 1074, (12), 25. (346) Bennett, H. L. US. Patent 3576734, Apr 27, 1971; Chem. Abstr. 1071, 74, 144387. (347) Strom, A. H.; Eddinger, R. T. Chem. Eng. Prog. 1071, 67, 75. (348) Krichko, A. A.; Yulin. M. K.; Museievich, D. L.; Ravikovich, T. M.; Skvortsov, D. V. Khim. Tverd. Topl. 1072, (6), 70. (349) Plchier, H.; Vaidyeswaran, R. Brennst. Chem. 1061, 42. 47. (350) Vaidyeswaran, R. Dr.Ing. Thesis, Technische Hochschule, Karisruhe, West Germany, 1959. (351) Vaidyeswaran, R.; Krishna, M. G., Zaheer, S. H. J . Sci. Ind. Res. (India) 1061, 200(10), 369. (352) Vaidyeswaran, R.; Mlrza, A.; Krishna, M. G.; Zaheer, S. H. “Low Temperature Carbonlzatlon of Non-caklng Coals 8 Lignites and Briquetting of Coal Fines”; Symp. Voi. 2. C.S.I.R.: New Deihi, 1964; pp 254-64. (353) Banerjee, P. K.; Basu, A. N.; Basak, N. G.; Lahiri, A. “Low Temperature Carbonizatlon of Non-caking h i s 8 Lignites and Briquetting of Coal Fines”; Symp. Vol. 2. C.S.I.R.: New Delhi, 1964; pp 265-78. (354) Bose, S. K.; Ganguii, A. K.; Basak, N. G.; Lahiri, A. J. Inst. Pet. 1050, 45(428), 252. (355) Mirza, A.; Masood, M. A.; Mallikarjunan, M. M.; Valdyeswaran, R. Chem. Age India 1066, 77(3),240. (356) Mirza. A.; Masood, M. A,; Mallikarjunan, M. M.; Vaidyeswaran, R. Brennst. Chem. 1067. 48, 310. (357) Mirza. A.; Masood, M. A.; Mallikarjunan, M. M.; Vaidyeswaran. R. Pet. Hydrocarbons 1068, 3(1), 13. (358) Mlrza, A.; Masood, M. A.; Malllkarjunan, M. M.; Vaidyeswaran, R. Pet. Hydrocarbons 1068, 3(2), 81. (359) Mlrza, A.; Masood, M. A.; Malllkarjunan, M. M.; Vaidyeswaran, R. ”Proceedings, Symposium on Chemicals and Oil from Coal”; Dec 6-8, 1969 (Pub. 1972) Central Fuel Research Institute, Dhanbad, India, Paper 14, pp 161-69. (360) Mirza, A.; Masood, M. A.; Malllkarjunan, M. M.; Vaidyeswaran, R. “Proceedings, International Symposlum on Coal Science and Technology for the Eighties. Central Fuel Research Institute, Dhanbad, Indla, Feb 1-3, 1979”, 1980 Paper 46, pp 503-510. (361) Mirza, A.; Masood, M. A.; Ramaswamy, A. V.; Vaidyeswaran, R. Brennst. Chem. 1065, 46(11), 355. (362) Mlrza, A.; Masood, M. A.; Valdyeswaran, R. Chem. Ind. Dev. I n corp. CP&E 1974, 8 , 12. (363) Mlrza, A.; Ramaswamy, A. V.; Masood, M. A.; Qader, S. A,; Valdyeswaran, R . Ind. J. Technol. 1065, 3(2), 57.
BerkebUe, D. C.; Hicks, H. N.; Green, W. S. Ind. Eng. Chem. Prod. Res. Dev. 1070, 9, 376. Jacobs, H. E.; Jones, J. F.; Eddinger, R. T. Ind. Eng. Chem. Process Des. Dev. 1071, 70(4), 558. Hail. C. C.; Cawiey, C. M. J. Soc. Chem. Ind. 1037, 56, 303T. Lozovoi, A. V. T r. Inst. Goryuch. Iskop. Akaa. Blonskaya, A. I.; Nacrk SSSR 1082, 77, 187. Vaidyeswaran, R.; Zaheer, S. H.; Pichler. H. Chem. Age In& 1061, 72(2), 105. Valdyeswaran, R.; Rao, G. S.; Krishna, M. G.; Zaheer, S. H. J. Sci. Ind. Res. (India) 1061, 208, 361. Coal Research In C.S.I.R.0 (Australia) Report No. 18, 1962, pp 10-12. Srlkanthareddy, P.; Sahrapati, G. S.; Janardanarao, M.; Vaidyeswaran, R. Ind. J. Technol. 1088, 6(11), 325. Sawyer, E. W. British Patent 759 159, Oct 17, 1956; Chem. Abstr. 1057, 57, 6129. Newall, H. E. Dept. Sci. Ind. Research (Brit.) Fuel Research Board Tech. Paper No. 48, 1938. Malkova, S. S. Tr. Inst. Goryuch. Iskop., Moscow 1068, 24(2), 106; Chem. Abstr. 1060, 70, 89466. Letort, M. Hydrocarbon Process. Pet. Reflner 1962, 47(7), 83. McGee, J. P. Coal Utilization 1058, 72(9), 31. McNell. D.; Waddington, W.; Popper, F. B. drltish Patent 769293. Mar 6, 1957; Chem. Abstr. 1057, 57, 11698. Chem. Eng. News 1061, 39(43), 56. Schlesinger, M. D.; Hiteshue, R. W. U . S . Bur. Mines Report Invest. N o . 5902 1061. Letort, M. Chlm. Industr. (Paris) 1062, 87, 371. Hawk, C. 0.; Schiesinger. M. D.; Dobransky, P.; Hiteshue, R. W. U . S . Bur. Mines Report Invest. No. 6655 1065. Perry, H.; Elliot, M. A.; Linden, H. R. Pet. Press Service 1062. 29, 461. Perry, R. C.; Albrlght, C. W. US. Patent 3231 486, Jan 25, 1966; Chem. Abstr. 1066. 6 4 , 12426. Karr, C., Jr.; Mapstone, J. O., Jr.; Little, L. R., Jr.; Lynch, R. E.; Comberiati, J. R. Ind. Eng. Chem. Prod. Res. Dev. 1071, 70, 204. 011 Gas J . 1070, 68(46), 190. Finn, M. J.; Fynes, G.; Ladner, W. R.; Newman, J. 0. H. Fuel 1080, 59,397. Qader, S. A.; HIII, G. R. Ind. Eng. Chem. Process Des. Dev. 1080, 8, 462. Qader, S.A.; Wiser, W. H.; Hill. G. R. Prepr., Am. Chem. SOC.,Div. Fuel Chem. 1068, 72(2), 28. Qader, S. A.; Wiser, W. H.; Hili, G. R. Fuel 1072, 57(1), 54. Qader, S. A.; Hili, G. R. Ind. Eng. Chem. Process Des. Dev. 1080, 8, 456. Konieczynski, J. S. Pr. Nauk. Inst. Chem. Technol., NatYy Wegla Politech. Wroclaw 1073, (17), 3; Chem. Abstr. 1074, 8 l S 123946. Morita, M.; Hirosawa, K. Nippon Kagaku Kaishi 1075, (9), 1555; Chem. Abstr. 1076, 84, 20042. Zleike, C. W.; Struck, R. T.; Evans, J. M.; Costanza, C. P.; Gorln. E. Ind. Eng. Chem. Process Des. Dev. 1066, 5, 151. Wiser, W. H.; Singh, S.; Qader, S. A.; Hill, G. R. Ind. Eng. Chem. Prod. Res. Dev. 1070, 9, 350. Qader, S. A.; Wiser, W. H.; Hili, G. R. Ind. Eng. Chem. Process Des. Dev. 1068, 7, 390. Anderson, L. L.; Badawy. M. L.; Qader, S. A.; Hili, G. R. Prepr. Am. Chem. Soc.,Div. FuelChem. 1068, 72(3), 181. Badawy, M. L. Univ. Utah Mlmfilms 1080, 117 pp; Diss. Abstr. Int. 81080, 30(3), 1095; Chem. Abstr. 1070, 72, 113566. Salimgareeva, F. G.; Davldovich. B. V.; Ivanova, M. F. Tr. Vostoch. SibirFlIiah, Akad. Nauk SSSR, Ser. Khim. 1059, (18), 95; Chem. Abstr. 1060, 54, 14635. Lang, E. W.; Lacey, J. C., Jr. American Chemical Society, 135th Natlonal Meeting, Boston, Abstr. Papers, 1959; P-2J. Lang, E. W.; Lacey, J. C., Jr. Ind. Eng. Chem. 1060, 52, 137. Aiekseeva, K. A.; Moldavskii, B. L. Khlm. Tekhnol. Topllv. Mesel 1050, 4(1), 43. Cawiey, C. M. Fuel 1033, 72, 29. Cawley, C. M. Research (London) 1048, 7 , 553. Kalechits, I.V.; Saiimgareeva, F. G.; Tr. Vostoch. Sibir Flliaia, Akad. Nauk SSSR, Ser. Khim. 1055, (3), 79. Kalechlts, I.V.; Saiimgareeva, F. G. T r . Vostoch. Sibir Flliaia, Akad. Nauk SSSR, Ser. Khim. 1056; (4), 5 ; Chem. Abstr. 1057, 57, 13361. Orchln, M.; Storch, H. H. J . SOC. Chem. Ind. 1050, 69, 121. Saha, N. C.; Basak, N. G.; Lahiri, A. J. Sci. Ind. Res. (India) 1960, 79B. 67. Saha, N. C.; Basak, N. G.; Lahiri, A. Indian Patent 65890, Jan 25, 1961; Chem. Abstr. 1061, 55, 14883. Sih, Tsu-Wei; Kalechits, I. V. Jan Lbo Hsueh Pa0 1057, 2. 152, 333; Chem. Abstr. 1958, 52, 6763, 20006. Grosskinsky, 0.; Thurauf, E. German Patent 1001 998, Feb 7, 1957; Chem. Abstr. 1060, 5 4 , 1425. Katsobashvili, Ya. R.; El’bert, E. I.U.S.S.R. Patent 189407, Nov 30, 1966; Chem. Abstr. 1987, 6 7 , 66467. D’yakova, M. K.; VoCEpshtein, A. B.; Zharova, M. N.; Zasukhina, E. A. Z h . Prlkl. Khim. 1050. 32, 2120. Krichko, A. A.; Yulin, M. K.; Voi-Epshtein, A. B.; Dembovska. E. A. Khim. Tverd. Topl. 1077, (4), 83. Shapiro, M. D.; Kiimenko, V. I.; Artem’eva, L. N.; Nabivach, V. M.; Kipkalov, B. N.; Tertychko, L. E. Khim. Tekhnol. Resp. Mezhved. Nauch.-Tekh. Sb. 1960, (15), 119; Chem. Abstr. 1971, 7 4 , 141153.
390
Ind. Eng. Chem. Prod. Res. Dev. 1982, 21, 390-397
(415) Sallmgareeva, F. G.; Davidovlch, B. V.; Ivanova, M. F.; Kalechlts, I. V. Tr. Vostoch. a i r . Fib&, Akad. Neuk SSSR, Ser. Khhn. 1959, (18). 87; Chem. A b s f . 1060. 54. 14636. (416) Jelinek, J. F. Chem. Rumysl1956, 8 , 397. (417) Jellnek, J. F. Chem. PTUmysl 1961, 72, 4. (418) Jellnek, J. F. Sb. R . Vyzk. Chem. Vyuzffi Uhli, Dehfu R q y 1962, 2, 70; Chem. Abstr. 1965, 62, 5117. (419) Jellnek, J. F. qollect. Czech. Chem. Commun. 1963, 28, 504. (420) Wells, 0. L.; Long, R. British Patent 999 472, July 28, 1965; Chem. Abstr. 1965, 63,9711. (421) Mllnes, M. H. Coal Tar Research Association (CTRA) Report No. 0283, 1961. (422) Milnes, M. H.; Dean, R. E. J . Appl. Chem. Blofechnoi. 1971, 27, 287. (423) Mllnes, M. H.; Dean, R. E. J . Appl. Chem. Biofechnol. 1972, 22(10), 1095. (424) Wells. G. L.; Long, R. Ind. Eng. Chem. Prod. Res. Dev. 1962, I , 73. (425) Davies, G. A. Report on Gas Council Research Scholarships 1963; Res. Commun. QC 95. (426) Davles, G. A.; Long, J . Appl. Chem. 1965. 75, 117. (427) Moghul, Y. A.; Yamazakl, Y.; Kawai, T. Bull. Jpn. Pet. Inst. 1973, 15(1), 23. (428) Kawase,'T.; Arai, H.; Tominaga, H.; Kunigl. T. Kogyo Kageku Zasshi 1970, 73(5)959; Chem. Abstr. 1971, 7 4 , 12437. (429) Kubicka, R. Czech. Patent 103744, May 15, 1962; Chem. Absfr. 1964, 60, 2832. (430) Beranek, L.; Kraus, M.; Bazant, V. Collect. Czech. Chem. Commun. 1964, 29, 239.
(431) Jost, F.; Bazant, V. Collect. Czech. Chem. Commun. 1961, 26, 3020. (432) Jost, F.;Kadlec, J.; Bazant, V. Czech. Patent 99012, Mar 15, 1961; Chem. A b s f . 1982, 57, 13680. (433) Jost, F.; Klyachko Gwvlch, A. L.; Rubinshtein, A. M. I z v . Akad. Nauk SSSR, Ser. Khlm. 1963. (12), 2105. (434) Jost, F.; Tomanova, D.; Banner-Volgt, A.; Collect. Czech. Chem, Commun. 1964, 29(7), 1626. (435) Kadlec, J.; Bazant, V. Coltect. Czech. Chem. Commun. W61, 26, 1201. (436) Kadlec, J.; Jost, F.; Bazent, V. Collecf. Czech. Chem. Commun. 1961, 26, 818. (437) Bakelite Ltd. British Patent 519721, Apr 4, 1940; Chem. Absfr. 1942, 36,97. (438) Good, G. M.; Holzman, G. U.S. Patent 2678337, May 11, 1954; Chem. Abstr. 1955, 49, 9038. (439) El'bert, E. I.; Kostyuk, L. B.; Panfiiov, I . A,; Biryukova, M. E. Pererab. Tverd. Top/. 1970, (2), 146. (440) Bovkun, R. A.; El'bert, E. I.; Morozova, S. N.; Usenko, L. L. Pererab. Tverd. Topl. 1970, (2), 130. (441) El'bert, E. I.; Katsobashvili, Ya. R.; Smirnov, V. K., Barino, G. I . , Splglazova, E. V. Pererab. Tverd. Topl. 1970, (2), 99. (442) Rutkowskl, M. Zesqfy Nauk. Mitech. Wroc&w., Chem. 1965, (12), 3; Chem. Abstr. 1966, 64, 17301.
Received for review December 10, 1981 Accepted March 22, 1982
CATALYST SECTION Deactivation by Carbon of Nickel, Nickel-Ruthenium, and Nickel-Molybdenum Methanation Catalysts A. Douglas Moeller and Calvin H. Bartholomew' &pami"
of Chemlcal Engineeringr Brigham Young University, Rovo, Utah 84602
The deactivation of Ai,03-support6d Ni, Ni-Ru, Ni-Mo, and Ni-Mo-Cu catalysts during high-temperature, combined shift/methanatlon was investigated. Activii-time measurements were conducted for each catalyst over a period of 24 h at 723 K, 138 and 2600 kPa in a fixed bed reactor and at 138 kPa in a fluidized bed reactor. Effects of carbon deposits and regeneration treatments in air or oxygen on metal surface area and specific intrinsic activii were measured for each catalyst. The results establish that Ni and Ni-Ru are significantly more resistant to deactivation by carbon deposits than Mo-containing catalysts. Ni-Mo-Cu deactivates more rapidly than Ni-Mo in a fluidized bed at 138 kPa and in a fixed bed at 2600 kPa. Regeneration of these catalysts in air at 573 K restores specific intrinsic activity but causes signiflcant loss of metal surface area. A model for deactivation is proposed which c a n be used to estimate catalyst life under carbondepositing conditions. Mechanisms of deactivation are discussed.
Introduction
A serious problem in the catalytic methanation of coal synthesis gas is fouling of the catalyst by carbon deposits (Bartholomew, 1982). This problem can be avoided by increasing the hydrogen content of the feed stream so that kinetics or thermodynamic equilibria are unfavorable toward carbon deposition (Gardner and Bartholomew, 1981a; Whalen, 1976); however, process economics favor minimizing hydrogen usage. Since most gasifiers produce a hydrogen-deficient gas, the application of a methanation catalyst which deposits carbon at negligible rates would be highly desirable since it would eliminate the need for the shift reactor prior to methanation. Except for a few recent studies in this laboratory (Weatherbee et al., 1980; 0196-4321/82/ 1221-0390$01.25/0
Bartholomew, 1977, 1980; Gardner, 1979; Gardner and Bartholomew, 1981a), there has been very little research to determine the effects of carbon deposits on adsorption and activity/selectivity properties of methanation catalysts or to understand the kinetics and mechanisms of catalyst deactivation by carbon during methanation. Such information is needed to establish catalyst types which resist deactivation by carbon and to determine optimum operating conditions for methanation of hydrogen-poor synthesis gas mixtures in combined shift/methanation processes. A previous study in this laboratory (Fowler and Bartholomew, 1979) showed that Ni-Mo catalysts are promising for use in the BI-GAS since they are as active as Ni 0 1982 American Chemlcal Society
