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02702 First-stage direct liquefaction of a subbituminous coal with oil-soluble metal naphthenates as dispersed catalyst precursors
02
observed, the evidence did not demonstrate finely dispersed catalysts over conventional hydrocracking of coal liquefaction extracts.
clear advantages for the use of supported Ni-Mo catalysts in
Effects of hydrogen pressure and temperature on 97102699 free radicals produced in coal-tire coprocessing Ihrahim, M. M. and Seehra, M. S. Fuel Process. Technol., 1996, 49, (l-3), 197.205. In order to investigate the co-processing of Blind Canyon coal with Michelin tyre rubber, in-sirrr ESR spectroscopy of free radicals was employed. Comparing the free radical intensifies of the coal and the tyre alone with those obtained for the 1:l coal-tyre mixtures, the following observations are made: a strong synergism between the coal and the tyre polymer was indicated; increasing the Hz pressure from SO0 to 1000 psig reduces the free radical intensity; the tyre polymer gave a weak ESR-active signal whose characteristics changed dramatically between 140°C and 2OOC. indicating a phase change in the tyre material. The synergistic effect observed wa\ consistent with the reported improved yields in direct liquefaction experiments using coal-tyre mixtures.
Elucidation of coal liquefaction mechanism using a tritium tracer method. Effect of HZ!9 and Hz0 on hydrogen exchange reaction of Tetralin with tritiated molecular hydrogen
97lQ2700
Godo. M. et al. Gters~’ E‘lrrk, 1997, 11,(2) 470-476. Tetralin reactions with tritiated H2 in the presence of H2S or Hz0 were ohserved under practical coal liquefaction conditions. The experiment aimed to elucidate the effect of HzS and Hz0 on hydrogen-exchange reactions between Tetralin and H:(g). The amounts of hydrogen exchanged between Tetralin and tritiated HZ were estimated from hydrogen and tritium balance. The results indicated that the hydrogen exchange reaction between H,(g) and Hz0 was slower than that with HzS. 97102701
Ester-
and
ether
bond
cleavage
in
immature
kerogens Ambles, A. c/ al. Org. Grochemical, l9Y6, 24, (h/7, Proceedings of the 17th International Meeting on Organic Geochemistry, Pt. 2, 1995) 681-690. Hydrolvsis of Timahdit-M kerogen can he enhanced with quaternary ammoniun salt Aliquat 336 and 18-crown-h (1) when used as phase-transfer catalysts. The yteld of hydrolysis products was higher with Aliquat than with I. but identified products were observed in lower concentrations, the difference being the soluble heavy parts from kerogen which cannot be analysed direct!y. Both reactions afforded a series of aliphatic mono- and dicarboxylic actds, alkylsuccinic acids and alkanols, but produced differcnccs in distribution. Hydrocarbons and tertiary amines obtained from both reactions were obviously present in the kerogen as trapped molecules. Each reaction afforded the same number of n-alkanes, reflecting kerogen matrix modifications during the treatment. This results in tightly trapped molecules.
First-stage direct liquefaction of a subbituminous coal with oil-soluble metal naphthenates as dispersed catalyst precursors Yoon, W. L. et ul. Furl, 1997, 76, (5). 397-405.
97102702
An investigation into the activities of catalysts produced from MO, Co and Fe naphthenate oil-soluble precursors were investigated. The particle size and crystalline phase of each metal sulfide from each metal precursor were also determined by SEM-EDX, TEM and XRD. Also, the synergistic effect between Fe and Co or between Fe and Mo in the hydroliquefaction of Usihelli (Alaska) sub-bituminous coal was investigated. The addition of Co or MO as a promoter to Fe as a primary component was proved to give a synergistic effect on both coal liquefaction yields and the H/C ratio of the liquid product\.
97l62703
Fischer-Tropsch
synthesis
catalysts
and reactors
Skala, D. Hem. Inn., 1996, SO, (I I), 486-496. (In Serbian) The author claims that Fischer-Tropsch synthesis is a promising route for synthetic fuel production and is an indirect method of coal liquefaction. The initial phase of indirect coal liquefaction is coal gasification and synthetic gas (hydrogen and carbon monoxide) purification, which is followed by the Fischer-Tropsch synthesis and the utilization of different catalysts and reactor types. The catalyst used for FTS are described in addition to the Fe-catalyst preparation procedure and its characterization, More information is given on the analysis of reactor types for the FTS. as well as the problem of the mathematical modelling of fixed-bed and slurry type reactors. The suspension of catalyst particles and the model of a huhble column as a reactor for FTS were analysed with the goal of indicating the influence of the reaction rate constant and catalyst activity, as well as the influence of gas phase contraction on hydrogen consumption in a reactor (column) of defined height. Analysis of the influences of other hydrodynamic parameters was also completed and presented.
Hydrocarbon class analysis of coal-derived liquids using high-performance liquid chromatography Padlo, D. M. L’I lrl. Fncl Pwcess. Techno/., 1996, 49, (l-3), 247-258.
97102704
The development of a normal-phase HPLC analysis method to separate coal-derived liquids into six compound classes: aliphatics, l-ring aromatics, 2-ring aromatics. 3-ring aromatics, 4.ring aromatics, and polars. Three columns w’ere used for the separation A UV photodiode-array detector was used for compound class identification and an evaporative lightscattering
Liquid fuels (derived liquid fuels)
detector was used for quantitative analysis of compounds with boiling point >600”F. Quantification methods with the evaporative-light-scattering detector were discussed. A power-law model could mathematically describe the relationship between sample concentration and detector signal. Agreement between GC-simulated-distillation results and total mass detected in compound-class separations are excellent.
97lO2705 Hydrodeoxygenation of O-containing model compounds using a novel organometallic precursor Kirby, S. R. et al. Catal. Today, 1996, 31, (l-2), 121-135.
polycyclic catalyst
A study was carried out on a novel organometallic catalyst precursor, containing Co and MO, as a potential hydrogenation catalyst for coal liquefaction. It was developed to aid in in-situ hydrodeoxygenation of oxygen-containing compounds during liquefaction. The catalyst precursor was examined under liquefaction conditions using model compounds. The results are given.
Hydrogen transfer reactions in coal/tire liquefac97102706 tion: quantification of H-donor contents Harrison, G. R. and Andrew, B. Prepr. Pap. Am. Chcm. Sm., Div. Furl Chem., 1997, 42, (I), 142-145. The sulfur test approach uses various substituted aromatic compounds and relates the results to measurements of the hydrogen donor contents of tyre pyrolysis oil (TPO) and TPO-coal liquefaction process solvent mixtures. The sulfur test overestimates rather than underestimates the hydrogen donor content.
97102707 Hydrogenation of a mixture of coals from the Kansk-Achinsk and near-Moscow Brown Coal Basins under a pressure of 6 MPa Maloletnev, A. S. et al. Khim. Tverd. Topl., 19Yh. (S). 71-77. (In Russian) In order to obtain motor and boiler fuels from brown coals of the Moscow Basin containing up to 50% ash and 8% sulfur, hydrogenation in a mixture with other brown coals, e.g. from Kansk-Achinsk Basin, was necessary. One of brown coals did not require catalyst addition.
97102706 Hydrogenationldehydrogenation of polycyclic aromatic hydrocarbons using ammonium tetrathiomolybdate as catalyst precursor Dutta, R. P. and Schobert, H. H. C‘utal. Today, 1996, 31, (l-2) 6.5-77. Naphthalene, phenanthrene, and pyrcne were investigated for their hydrogenation and dehydrogenation behaviour, using ammonium tetrathiomolyhdate as a catalyst precursor. The factors used were product distribution and kinetic/thermodynamic parameters. Hydrogenation reactions were carried out in microautoclave reactors at 350, 400, and 4SO’C for various times up to equilibrium conditions. A lumped kinetic model was used to determine forward and reverse rate constants, which were then used to determine Arrhenius parameters. Enthalpy data were obtained and compared to calculated values in the literature. With increasing ring size, the favourahle temperature for dehydrogenation of hydroaromatics over hydrogenation reactions decreased, which was also shown by an increasing thermodynamic control over the reactions.
97102709 Hydroliquefaction of subbituminous A coal of Fushun, China Wang, S. and Li, S. Meitan Zhuanhuu, 1996, 19, (4). 7Y-84. (In Chinese) The process and its specific this paper.
97102710 behavior
The
qualities
influence
relating
to this coal are presented
of solvents
on
coal
in
liquefaction
Zheng, J. Meitarz Zhuunhua, 1996, 19, (4), 73-78. (In Chinese) Hydrogenated solvent, de-crystallized anthracene oil, and recycled solvent were investigated for their influence on the liquefaction hehaviour of coal. Hydrogenated solvents gave higher oil yield and required lower hydrogen consumption than the other solvents studied. The liquefaction ability of recycled solvents was between those of the hydrogenated solvents and the de-crystallized anthracene oil.
97lQ27ll bitumen
Kinetics
of
high-conversion
hydrocracking
of
Nagaishi, H. et al. Energy Fuels, 1997, I I, (2) 4022410. Bitumen and bitumen fractions were reacted in a I-L CSTR in a multipass operation in an attempt to determine the kinetics of residue conversion and yields of distillates at very high conversions. Products from the first pass was collected, then run through the reactor again and the process repeated. Experiments were conducted both with NiiMo on ?-alumina hydrocracking catalyst and without added catalyst. Products were analysed hy distillation, elemental analysis, microcarbon residue content, and “C NMR. Decreasing rate constants for residue conversion were witnessed, which correlated with the fraction of aromatic carbon in the residue fraction, both with and without added catalyst. Sulfur conversion kinetics in the presence of a catalyst were consistent with a simple model for converston of thiophenic species into sulfides.
Fuel and Energy Abstracts
July 1997
223
observed, the evidence did not demonstrate finely dispersed catalysts over conventional hydrocracking of coal liquefaction extracts.
clear advantages for the use of supported Ni-Mo catalysts in
Effects of hydrogen pressure and temperature on 97102699 free radicals produced in coal-tire coprocessing Ihrahim, M. M. and Seehra, M. S. Fuel Process. Technol., 1996, 49, (l-3), 197.205. In order to investigate the co-processing of Blind Canyon coal with Michelin tyre rubber, in-sirrr ESR spectroscopy of free radicals was employed. Comparing the free radical intensifies of the coal and the tyre alone with those obtained for the 1:l coal-tyre mixtures, the following observations are made: a strong synergism between the coal and the tyre polymer was indicated; increasing the Hz pressure from SO0 to 1000 psig reduces the free radical intensity; the tyre polymer gave a weak ESR-active signal whose characteristics changed dramatically between 140°C and 2OOC. indicating a phase change in the tyre material. The synergistic effect observed wa\ consistent with the reported improved yields in direct liquefaction experiments using coal-tyre mixtures.
Elucidation of coal liquefaction mechanism using a tritium tracer method. Effect of HZ!9 and Hz0 on hydrogen exchange reaction of Tetralin with tritiated molecular hydrogen
97lQ2700
Godo. M. et al. Gters~’ E‘lrrk, 1997, 11,(2) 470-476. Tetralin reactions with tritiated H2 in the presence of H2S or Hz0 were ohserved under practical coal liquefaction conditions. The experiment aimed to elucidate the effect of HzS and Hz0 on hydrogen-exchange reactions between Tetralin and H:(g). The amounts of hydrogen exchanged between Tetralin and tritiated HZ were estimated from hydrogen and tritium balance. The results indicated that the hydrogen exchange reaction between H,(g) and Hz0 was slower than that with HzS. 97102701
Ester-
and
ether
bond
cleavage
in
immature
kerogens Ambles, A. c/ al. Org. Grochemical, l9Y6, 24, (h/7, Proceedings of the 17th International Meeting on Organic Geochemistry, Pt. 2, 1995) 681-690. Hydrolvsis of Timahdit-M kerogen can he enhanced with quaternary ammoniun salt Aliquat 336 and 18-crown-h (1) when used as phase-transfer catalysts. The yteld of hydrolysis products was higher with Aliquat than with I. but identified products were observed in lower concentrations, the difference being the soluble heavy parts from kerogen which cannot be analysed direct!y. Both reactions afforded a series of aliphatic mono- and dicarboxylic actds, alkylsuccinic acids and alkanols, but produced differcnccs in distribution. Hydrocarbons and tertiary amines obtained from both reactions were obviously present in the kerogen as trapped molecules. Each reaction afforded the same number of n-alkanes, reflecting kerogen matrix modifications during the treatment. This results in tightly trapped molecules.
First-stage direct liquefaction of a subbituminous coal with oil-soluble metal naphthenates as dispersed catalyst precursors Yoon, W. L. et ul. Furl, 1997, 76, (5). 397-405.
97102702
An investigation into the activities of catalysts produced from MO, Co and Fe naphthenate oil-soluble precursors were investigated. The particle size and crystalline phase of each metal sulfide from each metal precursor were also determined by SEM-EDX, TEM and XRD. Also, the synergistic effect between Fe and Co or between Fe and Mo in the hydroliquefaction of Usihelli (Alaska) sub-bituminous coal was investigated. The addition of Co or MO as a promoter to Fe as a primary component was proved to give a synergistic effect on both coal liquefaction yields and the H/C ratio of the liquid product\.
97l62703
Fischer-Tropsch
synthesis
catalysts
and reactors
Skala, D. Hem. Inn., 1996, SO, (I I), 486-496. (In Serbian) The author claims that Fischer-Tropsch synthesis is a promising route for synthetic fuel production and is an indirect method of coal liquefaction. The initial phase of indirect coal liquefaction is coal gasification and synthetic gas (hydrogen and carbon monoxide) purification, which is followed by the Fischer-Tropsch synthesis and the utilization of different catalysts and reactor types. The catalyst used for FTS are described in addition to the Fe-catalyst preparation procedure and its characterization, More information is given on the analysis of reactor types for the FTS. as well as the problem of the mathematical modelling of fixed-bed and slurry type reactors. The suspension of catalyst particles and the model of a huhble column as a reactor for FTS were analysed with the goal of indicating the influence of the reaction rate constant and catalyst activity, as well as the influence of gas phase contraction on hydrogen consumption in a reactor (column) of defined height. Analysis of the influences of other hydrodynamic parameters was also completed and presented.
Hydrocarbon class analysis of coal-derived liquids using high-performance liquid chromatography Padlo, D. M. L’I lrl. Fncl Pwcess. Techno/., 1996, 49, (l-3), 247-258.
97102704
The development of a normal-phase HPLC analysis method to separate coal-derived liquids into six compound classes: aliphatics, l-ring aromatics, 2-ring aromatics. 3-ring aromatics, 4.ring aromatics, and polars. Three columns w’ere used for the separation A UV photodiode-array detector was used for compound class identification and an evaporative lightscattering
Liquid fuels (derived liquid fuels)
detector was used for quantitative analysis of compounds with boiling point >600”F. Quantification methods with the evaporative-light-scattering detector were discussed. A power-law model could mathematically describe the relationship between sample concentration and detector signal. Agreement between GC-simulated-distillation results and total mass detected in compound-class separations are excellent.
97lO2705 Hydrodeoxygenation of O-containing model compounds using a novel organometallic precursor Kirby, S. R. et al. Catal. Today, 1996, 31, (l-2), 121-135.
polycyclic catalyst
A study was carried out on a novel organometallic catalyst precursor, containing Co and MO, as a potential hydrogenation catalyst for coal liquefaction. It was developed to aid in in-situ hydrodeoxygenation of oxygen-containing compounds during liquefaction. The catalyst precursor was examined under liquefaction conditions using model compounds. The results are given.
Hydrogen transfer reactions in coal/tire liquefac97102706 tion: quantification of H-donor contents Harrison, G. R. and Andrew, B. Prepr. Pap. Am. Chcm. Sm., Div. Furl Chem., 1997, 42, (I), 142-145. The sulfur test approach uses various substituted aromatic compounds and relates the results to measurements of the hydrogen donor contents of tyre pyrolysis oil (TPO) and TPO-coal liquefaction process solvent mixtures. The sulfur test overestimates rather than underestimates the hydrogen donor content.
97102707 Hydrogenation of a mixture of coals from the Kansk-Achinsk and near-Moscow Brown Coal Basins under a pressure of 6 MPa Maloletnev, A. S. et al. Khim. Tverd. Topl., 19Yh. (S). 71-77. (In Russian) In order to obtain motor and boiler fuels from brown coals of the Moscow Basin containing up to 50% ash and 8% sulfur, hydrogenation in a mixture with other brown coals, e.g. from Kansk-Achinsk Basin, was necessary. One of brown coals did not require catalyst addition.
97102706 Hydrogenationldehydrogenation of polycyclic aromatic hydrocarbons using ammonium tetrathiomolybdate as catalyst precursor Dutta, R. P. and Schobert, H. H. C‘utal. Today, 1996, 31, (l-2) 6.5-77. Naphthalene, phenanthrene, and pyrcne were investigated for their hydrogenation and dehydrogenation behaviour, using ammonium tetrathiomolyhdate as a catalyst precursor. The factors used were product distribution and kinetic/thermodynamic parameters. Hydrogenation reactions were carried out in microautoclave reactors at 350, 400, and 4SO’C for various times up to equilibrium conditions. A lumped kinetic model was used to determine forward and reverse rate constants, which were then used to determine Arrhenius parameters. Enthalpy data were obtained and compared to calculated values in the literature. With increasing ring size, the favourahle temperature for dehydrogenation of hydroaromatics over hydrogenation reactions decreased, which was also shown by an increasing thermodynamic control over the reactions.
97102709 Hydroliquefaction of subbituminous A coal of Fushun, China Wang, S. and Li, S. Meitan Zhuanhuu, 1996, 19, (4). 7Y-84. (In Chinese) The process and its specific this paper.
97102710 behavior
The
qualities
influence
relating
to this coal are presented
of solvents
on
coal
in
liquefaction
Zheng, J. Meitarz Zhuunhua, 1996, 19, (4), 73-78. (In Chinese) Hydrogenated solvent, de-crystallized anthracene oil, and recycled solvent were investigated for their influence on the liquefaction hehaviour of coal. Hydrogenated solvents gave higher oil yield and required lower hydrogen consumption than the other solvents studied. The liquefaction ability of recycled solvents was between those of the hydrogenated solvents and the de-crystallized anthracene oil.
97lQ27ll bitumen
Kinetics
of
high-conversion
hydrocracking
of
Nagaishi, H. et al. Energy Fuels, 1997, I I, (2) 4022410. Bitumen and bitumen fractions were reacted in a I-L CSTR in a multipass operation in an attempt to determine the kinetics of residue conversion and yields of distillates at very high conversions. Products from the first pass was collected, then run through the reactor again and the process repeated. Experiments were conducted both with NiiMo on ?-alumina hydrocracking catalyst and without added catalyst. Products were analysed hy distillation, elemental analysis, microcarbon residue content, and “C NMR. Decreasing rate constants for residue conversion were witnessed, which correlated with the fraction of aromatic carbon in the residue fraction, both with and without added catalyst. Sulfur conversion kinetics in the presence of a catalyst were consistent with a simple model for converston of thiophenic species into sulfides.
Fuel and Energy Abstracts
July 1997
223