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01915 Supercritical-phase process for selective synthesis of heavy hydrocarbons from syngas on cobalt catalysts
02
Liquid fuels (derived liquid fuels)
also been determined. A comparison is made between the activities of the alumina supported salts and the corresponding commercially available alumina-supported bimetallic catalysts. Review of the fundamental research on coliquefac99lO1910 tion of coal with waste plastics Wang, L. et al. Meitan Zhuanhua, 1998, 21, (3), 24-28. (In Chinese) As a promising new method of co-processing, the co-liquefaction of coal with waste plastics is an attractive way to utilize organic wastes and coal, effectively. The research status, current problems and obtained achievements concerning coal co-liquefaction with waste plastics are reviewed in this work. The multi-significance of developing coal co-liquefaction with waste plastics in China was also proposed. Separation and use of phenolic compounds in 99101911 liquid products of coal pyrolysis at low temperature Ge, Y. Meitan Zhuanhua, 1997, 20, (2), 49-56. (In Chinese) This review talks about the separation of phenolic compounds (low boilingpoint phenolic compounds, naphthols, etc.). This takes place in liquid products of coal pyrolysis at low temperature and their use as the intermediates and end-products of synthesis is discussed. Separation of m-cresol from neutral oils with 99101912 liquid-liquid extraction Venter, D. L. and Nieuwoudt, I. Ind. Eng. Chem. Res., 1998, 37, (lo), 4099-4106.
The liquors obtained from coal pyrolysis are a major source of valuable phenolic compounds. In this study, the separation of m-cresol from neutral oils by means of liquid-liquid extraction is investigated. Liquid-liquid equilibrium for the systems m-cresol + o-toluonitrile + hexane + water + tetraethylene glycol + undecane + dodecane and m-cresol + o-toluonitrile + hexane + water + tetraethylene glycol have been determined at 313.15 K in order to evaluate the suitability of tetraethylene glycol as a high-boiling solvent for the separation of m-cresol from neutral oils. The effect of parameters such as solvent ratios on the desired separation were investigated. These are illustrated on the basis of separation factors, percentage of feed o-toluonitrile remaining in the solvent phase and percentage recovery of m-cresol. It was concluded from the results that tetraethylene glycol is suitable for the proposed separation. The nonrandom two-liquid model fitted the experimental data satisfactorily. The model was used in the simulation of a multistage extraction column. Predictions were made of m-cresol recoveries of greater than 97% and mcresol purity of greater than 99.5%. Shenhua direct liquefaction plant 99101913 Comolli, A. G. et al. Prepr. Symp. Am. Chem. Sot., Div. Fuel Chem., 1998, 43, (3), 441-446. With HTI’s advanced liquefaction technology, GelCat and at proven reactor operating conditions, coals can be processed in excess of 92% conversion. The products from coal liquefaction should meet or exceed SINOPEC standards for gasoline and diesel fuel products, using commercially proven refinery techniques for product upgrading. Using liquefaction yields demonstrated with Shenhua #3 coal, a conceptual design for a commercial stand-alone grassroots facility has been completed for a coal feed rate of 12,000 Mtons/day. Study on interaction between coal and model 99101914 plastics during liquid-phase catalytic coliquefaction Yamaguchi, H. et al. Prepr. Symp. Am. Chem. Sot., Div. Fuel Chem., 1998, 43, (3), 707-711. In this study, the coliquefaction of Tanitoharum coal with PP, PS and highdensity PE was carried out at 430°C for 60 min under 7 MPa inital pressure of hydrogen and using red mud plus sulfur as the catalyst. An almost linear relationship existed between the coal concentration in coal/plastics mixture and the conversion to THF-soluble (THFS) or oil yield for the mixture of coal/PP, coal/PS or coal/PE in case of tetralin. The oil yield was observed at 75% of coal concentration for any coal/plastics mixture and this was slightly larger than that calculated. The use of decalin gave lower values of conversion yields of THFS in vacuum residue (VR) and oil, particularly at a coal concentration of 75% for the coal/PE mixture, compared to those calculated, while a similar tendency as to interaction in respect of conversion yields of THFS in VR, oil and gas was observed for the mixture of coal/PP and coal/PS. However, when the coal was reacted with mixed plastics of PP, PS and PE at coal concentration of 50%, the interaction observed for the coal/PE mixture disappeared and higher oil yield than expected was obtained. The results suggested interaction between PE and the other plastics is larger than that between coal and PE. The results also suggest that radicals from PP cracking were used for stabilization of radicals from the coal and PP. instead of hydrogen donated from gas and solvent. Higher values of conversion and oil yield for the use of decalin were obtained, compared to tetralin. The results indicated that a good hydrogen donor solvent would not be necessary. Supercritlcal-phase process for selective synthesis 99101915 of heavy hydrocarbons from syngas on cobalt catalysts Yan, S. et al. Appl. Catal., A, 1998, 171, (2), 247-254. Over ColSiOz catalysts, supercritical-phase Fischer-Tropsch synthesis cofed with 1-tetradecene was carried out. A supercritical fluid could extract the product from the catalyst bed efficiently and as a result, the mass
196
Fuel and Energy Abstracts
May 1999
transfers for both reactants and products were enhanced. I-tetradecene added as a chain initiator could participate in the chain growth process. This consequently increased the rate of formation of hydrocarbons larger than Cl4 significantly and decreased the yield of C,-CI1 hydrocarbons, leading to a flatter carbon number distribution of product than that obtained without olefin addition In addition, wax composition analysis also showed that the average molecular weight and degree of saturation of wax increased due to addition of 1-tetradecene. Also investigated were the effects of catalyst pore size, concentration of co-fed I-olefin and CO/H2 ratio of syngas. Synthesis of high quality liquid fuels from carbon 99101916 resources Fujimoto, K. Petrotech. (Tokyo), 1998, 21, (8), 775-777. (In Japanese) A review is given of the catalytic synthesis of high-quality liquid fuels by hydro-thermal cracking and transfer hydrocracking of ultra heavy oils and by syngas conversion, including coal and oil coprocessing, Fischer-Tropsch reaction, methane reforming and methanol synthesis. Thermal decomposition of waste plastics for re99101917 covery of fuel oil Murata, K. et al. Jpn. Kokai Tokkyo Koho JP 10 251,656 [98 251,656] (Cl. ClOGlIlO), 22 Sep 1998, Appl. 97161,225, 14 Mar 1997, 8 pp. (In Japanese) Silica-micelle composites obtained by reaction of silica-containing substances and alkyl-containing surfactants are dried and fired to prepare mesoporous silica. The mesoporous silica is then used in the thermal decomposition of waste plastics, which is carried out rapidly, with prevention of gasification. Thermal degradation of naphthenic jet fuels in the 99101916 pyrolytic regime and effects of hydrotreating Andresen, J. M. et al. Prepr. Am. Chem. Sot., Div. Pet. Chem., 1998, 43, (3). 412-414. Hydrotreating light cycle oil produces a jet fuel rich in cycloalkanes and low in aromatic hvdrocarbons and alkanes. The thermal stability at 450°F of this fuel is comparable to those of a coal-derived or petroleum-derived JP-8 jet fuels and exceeds them at 480-900°F. Toxicology of synthetic fuels - a mini review 99101919 Poon, R. and Ih, C. Prepr. Symp. Am. Chem. Sot., Div. Fuel Chem., 1998, 43, (3), 451-455. The observations that higher boiling fractions and blends of synthetic fuels are more toxic have been confirmed by recent analysis and toxicology studies. It has also been reported that the toxic effects of synfuels are related to the polycyclic aromatic hydrocarbon (PAH) content, including nitrogen containing and polar PAHs. Although carcinogenicity and mutagenicity are the main health concern of higher boiling synthetic fuels, it is important not to overlook the systemic toxicity. The marked thymic atrophy and perturbation of immune cells of PAH-treated animals suggest that these fractions are immuno-suppressive. The lower-boiling fractions possess relatively weak carcinogenicity, mutagenicity and systemic toxicity, but their dermal irritant effects are still of concern in occupational settings. In the fractions and blends studied, the benzo(a)pyrene level is an indicator of their PAH content and hence toxicity. However, it is also clear that different composition of PAH mixture in the high boiling fractions produce interactive effects that leads to complex toxic and biochemical manifestations. This article reviews recent mammalian toxicity data of various synfuels and sheds some light on their potential human health hazards.
99101920
TPD studies on copper-based catalysts for methanol synthesis Yang, Y. et al. Tianranqi Huagong, 1998, 23, (2) 5-9. (In Chinese) The possible sites and adsorption behaviour for methanol synthesis from syngas on ZnO, ZnO/A120s, CuOiZnOiAlzOs and CuO/ZnO/AlzOs/CeOz were comparatively investigated by using Hz-TPD and CO-TPD, respectively.
99101921 Two-stage catalytic coliquefaction of coal and waste tire Sharma, R. K. et al. Energy Fuels, 1998, 12, (6), 1245-1255. A study of the two-stage catalytic liquefaction of coal and waste tyres, using two bituminous coals (Blind Canyon and Illinois No. 6) and a subbituminous coal (Wyodak). Waste and recycled tyres formed the tyre sample. In the first stage, the tyre was liquefied separately at 350 or 400°C under N2 or Ha to obtain tyre oil. In the second stage, each coal was liquefied with tyre oil at 350450°C and 1000 psi (cold) Hz. This was done using various tyre oil-coal ratios. A few second-stage runs (including some catalytic runs using a ferric sulfide-based catalyst impregnated in-situ in the coal) were carried out with coal and vacuum-pyrolysed tyre oil. It was found that in general, the use of tyre oil improved coal conversion. The presence of catalyst was found to effect the coal conversion. In the absence of catalyst, the effects were similar with tyre oils prepared under different conditions. With the catalyst, the increase upon adding tyre oil was greatest when the tyre oil was prepared at 400°C in Hz. Overall, improvements were most pronounced at the higher temperatures of the second stage and at higher ratios of tyre oil to coal.
Liquid fuels (derived liquid fuels)
also been determined. A comparison is made between the activities of the alumina supported salts and the corresponding commercially available alumina-supported bimetallic catalysts. Review of the fundamental research on coliquefac99lO1910 tion of coal with waste plastics Wang, L. et al. Meitan Zhuanhua, 1998, 21, (3), 24-28. (In Chinese) As a promising new method of co-processing, the co-liquefaction of coal with waste plastics is an attractive way to utilize organic wastes and coal, effectively. The research status, current problems and obtained achievements concerning coal co-liquefaction with waste plastics are reviewed in this work. The multi-significance of developing coal co-liquefaction with waste plastics in China was also proposed. Separation and use of phenolic compounds in 99101911 liquid products of coal pyrolysis at low temperature Ge, Y. Meitan Zhuanhua, 1997, 20, (2), 49-56. (In Chinese) This review talks about the separation of phenolic compounds (low boilingpoint phenolic compounds, naphthols, etc.). This takes place in liquid products of coal pyrolysis at low temperature and their use as the intermediates and end-products of synthesis is discussed. Separation of m-cresol from neutral oils with 99101912 liquid-liquid extraction Venter, D. L. and Nieuwoudt, I. Ind. Eng. Chem. Res., 1998, 37, (lo), 4099-4106.
The liquors obtained from coal pyrolysis are a major source of valuable phenolic compounds. In this study, the separation of m-cresol from neutral oils by means of liquid-liquid extraction is investigated. Liquid-liquid equilibrium for the systems m-cresol + o-toluonitrile + hexane + water + tetraethylene glycol + undecane + dodecane and m-cresol + o-toluonitrile + hexane + water + tetraethylene glycol have been determined at 313.15 K in order to evaluate the suitability of tetraethylene glycol as a high-boiling solvent for the separation of m-cresol from neutral oils. The effect of parameters such as solvent ratios on the desired separation were investigated. These are illustrated on the basis of separation factors, percentage of feed o-toluonitrile remaining in the solvent phase and percentage recovery of m-cresol. It was concluded from the results that tetraethylene glycol is suitable for the proposed separation. The nonrandom two-liquid model fitted the experimental data satisfactorily. The model was used in the simulation of a multistage extraction column. Predictions were made of m-cresol recoveries of greater than 97% and mcresol purity of greater than 99.5%. Shenhua direct liquefaction plant 99101913 Comolli, A. G. et al. Prepr. Symp. Am. Chem. Sot., Div. Fuel Chem., 1998, 43, (3), 441-446. With HTI’s advanced liquefaction technology, GelCat and at proven reactor operating conditions, coals can be processed in excess of 92% conversion. The products from coal liquefaction should meet or exceed SINOPEC standards for gasoline and diesel fuel products, using commercially proven refinery techniques for product upgrading. Using liquefaction yields demonstrated with Shenhua #3 coal, a conceptual design for a commercial stand-alone grassroots facility has been completed for a coal feed rate of 12,000 Mtons/day. Study on interaction between coal and model 99101914 plastics during liquid-phase catalytic coliquefaction Yamaguchi, H. et al. Prepr. Symp. Am. Chem. Sot., Div. Fuel Chem., 1998, 43, (3), 707-711. In this study, the coliquefaction of Tanitoharum coal with PP, PS and highdensity PE was carried out at 430°C for 60 min under 7 MPa inital pressure of hydrogen and using red mud plus sulfur as the catalyst. An almost linear relationship existed between the coal concentration in coal/plastics mixture and the conversion to THF-soluble (THFS) or oil yield for the mixture of coal/PP, coal/PS or coal/PE in case of tetralin. The oil yield was observed at 75% of coal concentration for any coal/plastics mixture and this was slightly larger than that calculated. The use of decalin gave lower values of conversion yields of THFS in vacuum residue (VR) and oil, particularly at a coal concentration of 75% for the coal/PE mixture, compared to those calculated, while a similar tendency as to interaction in respect of conversion yields of THFS in VR, oil and gas was observed for the mixture of coal/PP and coal/PS. However, when the coal was reacted with mixed plastics of PP, PS and PE at coal concentration of 50%, the interaction observed for the coal/PE mixture disappeared and higher oil yield than expected was obtained. The results suggested interaction between PE and the other plastics is larger than that between coal and PE. The results also suggest that radicals from PP cracking were used for stabilization of radicals from the coal and PP. instead of hydrogen donated from gas and solvent. Higher values of conversion and oil yield for the use of decalin were obtained, compared to tetralin. The results indicated that a good hydrogen donor solvent would not be necessary. Supercritlcal-phase process for selective synthesis 99101915 of heavy hydrocarbons from syngas on cobalt catalysts Yan, S. et al. Appl. Catal., A, 1998, 171, (2), 247-254. Over ColSiOz catalysts, supercritical-phase Fischer-Tropsch synthesis cofed with 1-tetradecene was carried out. A supercritical fluid could extract the product from the catalyst bed efficiently and as a result, the mass
196
Fuel and Energy Abstracts
May 1999
transfers for both reactants and products were enhanced. I-tetradecene added as a chain initiator could participate in the chain growth process. This consequently increased the rate of formation of hydrocarbons larger than Cl4 significantly and decreased the yield of C,-CI1 hydrocarbons, leading to a flatter carbon number distribution of product than that obtained without olefin addition In addition, wax composition analysis also showed that the average molecular weight and degree of saturation of wax increased due to addition of 1-tetradecene. Also investigated were the effects of catalyst pore size, concentration of co-fed I-olefin and CO/H2 ratio of syngas. Synthesis of high quality liquid fuels from carbon 99101916 resources Fujimoto, K. Petrotech. (Tokyo), 1998, 21, (8), 775-777. (In Japanese) A review is given of the catalytic synthesis of high-quality liquid fuels by hydro-thermal cracking and transfer hydrocracking of ultra heavy oils and by syngas conversion, including coal and oil coprocessing, Fischer-Tropsch reaction, methane reforming and methanol synthesis. Thermal decomposition of waste plastics for re99101917 covery of fuel oil Murata, K. et al. Jpn. Kokai Tokkyo Koho JP 10 251,656 [98 251,656] (Cl. ClOGlIlO), 22 Sep 1998, Appl. 97161,225, 14 Mar 1997, 8 pp. (In Japanese) Silica-micelle composites obtained by reaction of silica-containing substances and alkyl-containing surfactants are dried and fired to prepare mesoporous silica. The mesoporous silica is then used in the thermal decomposition of waste plastics, which is carried out rapidly, with prevention of gasification. Thermal degradation of naphthenic jet fuels in the 99101916 pyrolytic regime and effects of hydrotreating Andresen, J. M. et al. Prepr. Am. Chem. Sot., Div. Pet. Chem., 1998, 43, (3). 412-414. Hydrotreating light cycle oil produces a jet fuel rich in cycloalkanes and low in aromatic hvdrocarbons and alkanes. The thermal stability at 450°F of this fuel is comparable to those of a coal-derived or petroleum-derived JP-8 jet fuels and exceeds them at 480-900°F. Toxicology of synthetic fuels - a mini review 99101919 Poon, R. and Ih, C. Prepr. Symp. Am. Chem. Sot., Div. Fuel Chem., 1998, 43, (3), 451-455. The observations that higher boiling fractions and blends of synthetic fuels are more toxic have been confirmed by recent analysis and toxicology studies. It has also been reported that the toxic effects of synfuels are related to the polycyclic aromatic hydrocarbon (PAH) content, including nitrogen containing and polar PAHs. Although carcinogenicity and mutagenicity are the main health concern of higher boiling synthetic fuels, it is important not to overlook the systemic toxicity. The marked thymic atrophy and perturbation of immune cells of PAH-treated animals suggest that these fractions are immuno-suppressive. The lower-boiling fractions possess relatively weak carcinogenicity, mutagenicity and systemic toxicity, but their dermal irritant effects are still of concern in occupational settings. In the fractions and blends studied, the benzo(a)pyrene level is an indicator of their PAH content and hence toxicity. However, it is also clear that different composition of PAH mixture in the high boiling fractions produce interactive effects that leads to complex toxic and biochemical manifestations. This article reviews recent mammalian toxicity data of various synfuels and sheds some light on their potential human health hazards.
99101920
TPD studies on copper-based catalysts for methanol synthesis Yang, Y. et al. Tianranqi Huagong, 1998, 23, (2) 5-9. (In Chinese) The possible sites and adsorption behaviour for methanol synthesis from syngas on ZnO, ZnO/A120s, CuOiZnOiAlzOs and CuO/ZnO/AlzOs/CeOz were comparatively investigated by using Hz-TPD and CO-TPD, respectively.
99101921 Two-stage catalytic coliquefaction of coal and waste tire Sharma, R. K. et al. Energy Fuels, 1998, 12, (6), 1245-1255. A study of the two-stage catalytic liquefaction of coal and waste tyres, using two bituminous coals (Blind Canyon and Illinois No. 6) and a subbituminous coal (Wyodak). Waste and recycled tyres formed the tyre sample. In the first stage, the tyre was liquefied separately at 350 or 400°C under N2 or Ha to obtain tyre oil. In the second stage, each coal was liquefied with tyre oil at 350450°C and 1000 psi (cold) Hz. This was done using various tyre oil-coal ratios. A few second-stage runs (including some catalytic runs using a ferric sulfide-based catalyst impregnated in-situ in the coal) were carried out with coal and vacuum-pyrolysed tyre oil. It was found that in general, the use of tyre oil improved coal conversion. The presence of catalyst was found to effect the coal conversion. In the absence of catalyst, the effects were similar with tyre oils prepared under different conditions. With the catalyst, the increase upon adding tyre oil was greatest when the tyre oil was prepared at 400°C in Hz. Overall, improvements were most pronounced at the higher temperatures of the second stage and at higher ratios of tyre oil to coal.