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02521 Method and apparatus for manufacture of hydrogen and carbon monoxide mixed gas
03
Gaseous fuels (derived
gaseous
fuels)
two superimposed tiers. In almost 8000 h of plant operation up to September 1995, the filter operated well. A permanent clean gas dust content of <3 mg/m”(STP) was obtained, compared with the design value of 5 mg/m’(STP). Using dry gas cleaning at increased temperatures resulted in a simplified, more cost-efficient plant technology and improved efficiency in advanced power plant processes, such as integrated gasification combinedcycle power plants. This was considerably more effective than conventional wet gas clean-up processes. There are also advantages in servicing and maintenance. The two-tier filter was converted to a three-tier type, ensuring that this design principle can be transferred to very large-scale units.
Heat exchange reformers for manufacture of hydrogen-rich synthesis gases
99102514
Matsumoto, T. et al. Jpn. Kokai Tokkyo Koho JP 10 273,678 [98 273,678], (Cl. ClOG11/20), 13 Ott 1998, Appl. 97/94,756, 28 Mar 1997, 15 pp. (In Japanese) In the heat exchange reformer there exists a shell-shaped catalyst bed supported at its peripheral. The catalyst bed can be used at high temperature. The reformers are for manufacture of synthesis gas in the manufacture of MeOH and NHJ.
Heat exchange reformers 99/02515 Matsumoto, T. ef al. Jpn. Kokai Tokkyo Koho JP 10 273,303 [98 273,303], (Cl. COlB3/38), 13 Ott 1998, Appl. 97/94,757, 28 Mar 1997, 16 pp. (In Japanese) The title autothermal reformers are designed to enable high-temperature operation on a large scale and to enable easy maintenance. Long-term production of synthesis gas used in the manufacture of MeOH and NH3 is achieved. Higher alcohols from synthesis gas using carbon99102516 supported doped molybdenum-based catalysts Li, X. et al. Ind. Eng. Chem. Res., 1998, 37, (lo), 3853-3863. Incipient wetness impregnation was used to prepare a series of carbonsupported molybdenum-based catalysts. The materials, when promoted with potassium and additionally with cobalt, were screened for the selective production of mixed higher-molecular-weight alcohols from syngas. The effects of catalyst preparation parameters and of reaction conditions (temperature and space velocity) were studied. The screening procedure consisted of ramping the temperature steadily from 200 to 400°C and back again. The addition of potassium resulted in a maximum in the space-time yield (STY) of total alcohols and the ratio of higher alcohols to methanol. Increasing the reaction temperature resulted in a monotonic increase in the STY of hydrocarbons, a monotonic decrease in the selectivity toward alcohols, and a maximum in the STY of alcohols. Increasing the space velocity increased the STY and selectivity to alcohols while decreasing the STY of hydrocarbons.
Hot dechlorination and hot desulfuriration of reducing gases with lime pellets
99102517
Fusch, Y. and Schwerdtfeger, K. High Temp. Gas Clean., [Pap. Inr. Symp. Exhib. Gas Clean. High Temp.], 3rd, 1996, 426-438. Edited by Schmidt, E., Institut fur Mechanische Verfahrenstechnik und Mechanik der Universitaet Karlsruhe, Karlsruhe, Germany Hydrogen chloride (HCI) as well as hydrogen suifide (HzS) are produced during coal gasification in modern integrated-coal-gasification-combinedcycle (ICGCC) power plants. Both H2S and HCI are corrosive and are harmful to the environment, and should therefore be removed from coal gas. In this paper, coal gas dry cleaning at high temperatures is contrasted to the more typical wet gas purification. Losses of energy occurring when cooling down and reheating the gas can be avoided, the total efficiency of the energy conversion can be increased and the formation of the wet slurry is avoided. The specific methods of dry cleaning under investigation in this project are dechlorination and desulfurization at temperatures up to 700°C with dry adsorbents, such as calcium carbonate (CaCOs) and calcium oxide (CaO). In addition to thermogravimetric experiments to clarify the reaction kinetics and the mechanisms of the binding reactions, experiments were carried out using a laboratory scale fixed bed reactor. The results show that over a large temperature range (300-700°C) lime-based adsorbent can be used to bind HCI from Hz-HCI gas and HsS from Hz-HsS gas. The simultaneous removal of HCI and H2S from Hz-HCI-H$3 gas was studied utilizing the findings of these experiments,.
Injection of gaseous oxldant for enhanced methane 99102516 recovery from coal seams Riese, W. C. and Brass, S. V. Ger. Offen. DE 19,817,110, (Cl. E21B43/ 295), 5 Nov 1998, US Appl. 846,994, 30 Apr 1997, 10 pp. (In German) A method of increasing methane recovery from underground coal seams is proposed. A gaseous oxidant, typically oxygen or ozone, is injected into the coal seam to stimulate formation of oxidation centres in the coal. Air or oxygen-enriched air, 30-50 ~01% oxygen, can also be used. After being allowed to react with the coal seam for a predetermined time gases with increased methane content are recovered through one or more production wells. Furthermore, permeability of the coal seam is increased allowing easier drilling of additional wells.
264
Fuel and Energy Absttwts
July 1999
99102519 lsobutanol synthesis from syngas Falter, W. e? al. Stud. Surf, Sci. Cutal., 1998, 119, (Natural Gas Conversion V), 465-471. Syngas conversion using a zirconium/zinc/manganese/potassium/palladium catalyst yielding 700-750 g/l h of isobutanol is described. The experimental conditions were; 400-45O”C, 250 bar and 20,000 GHSV/h-‘. A comparison was made between using a tubular fixed bed and a CSTR reactor system.
99102520 Mechanistic study of carbon dioxide reforming with methane over supported nickel catalysts Yan, Z-F. er aI. Energy Fuels, 1998, 12, (6) 1114-1120. In this paper, carbon dioxide reforming with methane to synthesis gas, using supported nickel, cobalt and iron catalysts, has been investigated. Particular consideration is given to the effects of active metal loading, feed ratio and reaction temperature on catalyst activity and stability. To help explain the reaction mechanism, temperature-programmed desorption, temperatureprogrammed surface reaction and XPS experiments were conducted. It was observed that it is likely that the direct disassociation of methane without the involvement of adsorbed or gas-phase carbon dioxide occurs and that the key step for the reforming reaction is the formation of hydrogen and surface carbon species, which are both primary products of the decomposition of methane. The secondary product may be carbon monoxide formed by interaction between surface carbon species and gas-phase or adsorbed carbon dioxide. Varying mobility, thermal stability and reactivity was shown by the three surface carbon species, C,,, C,, and C’, which are produced by the decomposition of methane. The residual parttal oxidative NiO, species that were not thoroughly reduced could not migrate on the catalyst surface and were therefore not reduced during the reaction.
Method and apparatus for manufacture of hydrogen and carbon monoxide mixed gas
99102521
Kiso, F. et al. Jpn. Kokai Tokkyo Koho JP 10 259,384 [98 259,384], (Cl. ClOJ3/02), 29 Sep 1998, Appl. 97/66,153, 19 Mar 1997, 7 pp. (In Japanese) In this paper, a method and its apparatus for the manufacture of hydrogencarbon monoxide mixed gas as raw material for synthesis of MeOH or diMe ether is presented. Biomass and steam are fed into a reactor from an upper burner to form a biomass gasification zone. Meanwhile, natural gas, oxygen and steam are fed to the reactor from a lower burner in a rotary flow of the raw material to form a high-temperature combustion zone. The heat and carbon dioxide generated from the lower combustion zone are in contact with the biomass to enable gasification in the upper gasification zone. The hydrogen-carbon monoxide mixed gas is discharged from the centre of rotary flow. The feeding ratio of the raw material can be adjusted to control the ratio of hydrogen to carbon monoxide.
Method of and means for generating combustible gases from low grade solid fuel
99102522
Israeli IL 101,424, (Cl. ClOB53/00), 22 Ormat Turbines (1965) Ltd., Israel Feb 1998, Appl. 101,424, 30 Mar 1992, 26 pp. A method for producing combustible gases from solid fuel is described. The method consists of; pyrolysing a portion of the fuel in a pyrolyser to produce combustible gases and carbonaceous material. The carbonaceous material is then added to a furnace with a further portion of the solid fuel to combust the carbonaceous material and solid fuel. Amongst the resultant combustion products are hot flue gases and ash particulate. The combustion products are separated into two streams, one of which contains coarse ash and the other of which contains flue gases and fine ash. Ash is directed from the coarse ash stream into the aforementioned pyrolyser. And finally, a fuel is added to the furnace to maintain the required temperature.
Nonequilibrium plasma reforming of green-house gases to synthesis gas
99102523
Zhou, L. M. et al. Energy Fuels, 1998, 12, (6), 1191-1199. In this article, it is demonstrated that dielectric-barrier discharges (DBDs) are an effective tool at converting the greenhouse gases CHd and CO2 to synthesis gas at low temperature and ambient pressure. The synthesis gas produced in this system can have an arbitrary Hz/CO ratio, mainly depending on the mixing ratio of CH&Oz in the feed gas. Syngas composition is influenced very little by specific electric energy, gas pressure, and temperature. The amount of syngas produced strongly depends on the electric energy input. COz-rich mixtures prevent carbon and wax formation. At fixed specific input energies, the maximum amount of syngas with low H2/CO molar ratio is produced from a mixture of CHd:COs of 2O:SO. In this mixture as many as 52 mol of Hs and 14 mol of CO have been obtained from 100 mol of feed gas at a specific input energy of 87 kW h/(N m”). CH4 conversion reaches 64% and CO2 conversion is 54%.
Operating experience at North America’s commercial black liquor gasification plant
99102524
first
Brown, C. A. and Hunter, W. D. Int. Chem. Recovery Conf., 1998, 2,655662. In December 1996, the first commercial black liquor gasification plant in North America started at Weyerhaeuser’s pulp mill in New Bern, North Carolina. Since the start-up of the a new fibre-line at the facility in September of 1997, the CHEMRECTM gasifier was instrumental in satisfying the mill’s increased production requirements. The plant design and the operating experience since start-up is presented. As a new technology, the gasifier presented many technical challenges, and how these are currently being overcome is discussed.
Gaseous fuels (derived
gaseous
fuels)
two superimposed tiers. In almost 8000 h of plant operation up to September 1995, the filter operated well. A permanent clean gas dust content of <3 mg/m”(STP) was obtained, compared with the design value of 5 mg/m’(STP). Using dry gas cleaning at increased temperatures resulted in a simplified, more cost-efficient plant technology and improved efficiency in advanced power plant processes, such as integrated gasification combinedcycle power plants. This was considerably more effective than conventional wet gas clean-up processes. There are also advantages in servicing and maintenance. The two-tier filter was converted to a three-tier type, ensuring that this design principle can be transferred to very large-scale units.
Heat exchange reformers for manufacture of hydrogen-rich synthesis gases
99102514
Matsumoto, T. et al. Jpn. Kokai Tokkyo Koho JP 10 273,678 [98 273,678], (Cl. ClOG11/20), 13 Ott 1998, Appl. 97/94,756, 28 Mar 1997, 15 pp. (In Japanese) In the heat exchange reformer there exists a shell-shaped catalyst bed supported at its peripheral. The catalyst bed can be used at high temperature. The reformers are for manufacture of synthesis gas in the manufacture of MeOH and NHJ.
Heat exchange reformers 99/02515 Matsumoto, T. ef al. Jpn. Kokai Tokkyo Koho JP 10 273,303 [98 273,303], (Cl. COlB3/38), 13 Ott 1998, Appl. 97/94,757, 28 Mar 1997, 16 pp. (In Japanese) The title autothermal reformers are designed to enable high-temperature operation on a large scale and to enable easy maintenance. Long-term production of synthesis gas used in the manufacture of MeOH and NH3 is achieved. Higher alcohols from synthesis gas using carbon99102516 supported doped molybdenum-based catalysts Li, X. et al. Ind. Eng. Chem. Res., 1998, 37, (lo), 3853-3863. Incipient wetness impregnation was used to prepare a series of carbonsupported molybdenum-based catalysts. The materials, when promoted with potassium and additionally with cobalt, were screened for the selective production of mixed higher-molecular-weight alcohols from syngas. The effects of catalyst preparation parameters and of reaction conditions (temperature and space velocity) were studied. The screening procedure consisted of ramping the temperature steadily from 200 to 400°C and back again. The addition of potassium resulted in a maximum in the space-time yield (STY) of total alcohols and the ratio of higher alcohols to methanol. Increasing the reaction temperature resulted in a monotonic increase in the STY of hydrocarbons, a monotonic decrease in the selectivity toward alcohols, and a maximum in the STY of alcohols. Increasing the space velocity increased the STY and selectivity to alcohols while decreasing the STY of hydrocarbons.
Hot dechlorination and hot desulfuriration of reducing gases with lime pellets
99102517
Fusch, Y. and Schwerdtfeger, K. High Temp. Gas Clean., [Pap. Inr. Symp. Exhib. Gas Clean. High Temp.], 3rd, 1996, 426-438. Edited by Schmidt, E., Institut fur Mechanische Verfahrenstechnik und Mechanik der Universitaet Karlsruhe, Karlsruhe, Germany Hydrogen chloride (HCI) as well as hydrogen suifide (HzS) are produced during coal gasification in modern integrated-coal-gasification-combinedcycle (ICGCC) power plants. Both H2S and HCI are corrosive and are harmful to the environment, and should therefore be removed from coal gas. In this paper, coal gas dry cleaning at high temperatures is contrasted to the more typical wet gas purification. Losses of energy occurring when cooling down and reheating the gas can be avoided, the total efficiency of the energy conversion can be increased and the formation of the wet slurry is avoided. The specific methods of dry cleaning under investigation in this project are dechlorination and desulfurization at temperatures up to 700°C with dry adsorbents, such as calcium carbonate (CaCOs) and calcium oxide (CaO). In addition to thermogravimetric experiments to clarify the reaction kinetics and the mechanisms of the binding reactions, experiments were carried out using a laboratory scale fixed bed reactor. The results show that over a large temperature range (300-700°C) lime-based adsorbent can be used to bind HCI from Hz-HCI gas and HsS from Hz-HsS gas. The simultaneous removal of HCI and H2S from Hz-HCI-H$3 gas was studied utilizing the findings of these experiments,.
Injection of gaseous oxldant for enhanced methane 99102516 recovery from coal seams Riese, W. C. and Brass, S. V. Ger. Offen. DE 19,817,110, (Cl. E21B43/ 295), 5 Nov 1998, US Appl. 846,994, 30 Apr 1997, 10 pp. (In German) A method of increasing methane recovery from underground coal seams is proposed. A gaseous oxidant, typically oxygen or ozone, is injected into the coal seam to stimulate formation of oxidation centres in the coal. Air or oxygen-enriched air, 30-50 ~01% oxygen, can also be used. After being allowed to react with the coal seam for a predetermined time gases with increased methane content are recovered through one or more production wells. Furthermore, permeability of the coal seam is increased allowing easier drilling of additional wells.
264
Fuel and Energy Absttwts
July 1999
99102519 lsobutanol synthesis from syngas Falter, W. e? al. Stud. Surf, Sci. Cutal., 1998, 119, (Natural Gas Conversion V), 465-471. Syngas conversion using a zirconium/zinc/manganese/potassium/palladium catalyst yielding 700-750 g/l h of isobutanol is described. The experimental conditions were; 400-45O”C, 250 bar and 20,000 GHSV/h-‘. A comparison was made between using a tubular fixed bed and a CSTR reactor system.
99102520 Mechanistic study of carbon dioxide reforming with methane over supported nickel catalysts Yan, Z-F. er aI. Energy Fuels, 1998, 12, (6) 1114-1120. In this paper, carbon dioxide reforming with methane to synthesis gas, using supported nickel, cobalt and iron catalysts, has been investigated. Particular consideration is given to the effects of active metal loading, feed ratio and reaction temperature on catalyst activity and stability. To help explain the reaction mechanism, temperature-programmed desorption, temperatureprogrammed surface reaction and XPS experiments were conducted. It was observed that it is likely that the direct disassociation of methane without the involvement of adsorbed or gas-phase carbon dioxide occurs and that the key step for the reforming reaction is the formation of hydrogen and surface carbon species, which are both primary products of the decomposition of methane. The secondary product may be carbon monoxide formed by interaction between surface carbon species and gas-phase or adsorbed carbon dioxide. Varying mobility, thermal stability and reactivity was shown by the three surface carbon species, C,,, C,, and C’, which are produced by the decomposition of methane. The residual parttal oxidative NiO, species that were not thoroughly reduced could not migrate on the catalyst surface and were therefore not reduced during the reaction.
Method and apparatus for manufacture of hydrogen and carbon monoxide mixed gas
99102521
Kiso, F. et al. Jpn. Kokai Tokkyo Koho JP 10 259,384 [98 259,384], (Cl. ClOJ3/02), 29 Sep 1998, Appl. 97/66,153, 19 Mar 1997, 7 pp. (In Japanese) In this paper, a method and its apparatus for the manufacture of hydrogencarbon monoxide mixed gas as raw material for synthesis of MeOH or diMe ether is presented. Biomass and steam are fed into a reactor from an upper burner to form a biomass gasification zone. Meanwhile, natural gas, oxygen and steam are fed to the reactor from a lower burner in a rotary flow of the raw material to form a high-temperature combustion zone. The heat and carbon dioxide generated from the lower combustion zone are in contact with the biomass to enable gasification in the upper gasification zone. The hydrogen-carbon monoxide mixed gas is discharged from the centre of rotary flow. The feeding ratio of the raw material can be adjusted to control the ratio of hydrogen to carbon monoxide.
Method of and means for generating combustible gases from low grade solid fuel
99102522
Israeli IL 101,424, (Cl. ClOB53/00), 22 Ormat Turbines (1965) Ltd., Israel Feb 1998, Appl. 101,424, 30 Mar 1992, 26 pp. A method for producing combustible gases from solid fuel is described. The method consists of; pyrolysing a portion of the fuel in a pyrolyser to produce combustible gases and carbonaceous material. The carbonaceous material is then added to a furnace with a further portion of the solid fuel to combust the carbonaceous material and solid fuel. Amongst the resultant combustion products are hot flue gases and ash particulate. The combustion products are separated into two streams, one of which contains coarse ash and the other of which contains flue gases and fine ash. Ash is directed from the coarse ash stream into the aforementioned pyrolyser. And finally, a fuel is added to the furnace to maintain the required temperature.
Nonequilibrium plasma reforming of green-house gases to synthesis gas
99102523
Zhou, L. M. et al. Energy Fuels, 1998, 12, (6), 1191-1199. In this article, it is demonstrated that dielectric-barrier discharges (DBDs) are an effective tool at converting the greenhouse gases CHd and CO2 to synthesis gas at low temperature and ambient pressure. The synthesis gas produced in this system can have an arbitrary Hz/CO ratio, mainly depending on the mixing ratio of CH&Oz in the feed gas. Syngas composition is influenced very little by specific electric energy, gas pressure, and temperature. The amount of syngas produced strongly depends on the electric energy input. COz-rich mixtures prevent carbon and wax formation. At fixed specific input energies, the maximum amount of syngas with low H2/CO molar ratio is produced from a mixture of CHd:COs of 2O:SO. In this mixture as many as 52 mol of Hs and 14 mol of CO have been obtained from 100 mol of feed gas at a specific input energy of 87 kW h/(N m”). CH4 conversion reaches 64% and CO2 conversion is 54%.
Operating experience at North America’s commercial black liquor gasification plant
99102524
first
Brown, C. A. and Hunter, W. D. Int. Chem. Recovery Conf., 1998, 2,655662. In December 1996, the first commercial black liquor gasification plant in North America started at Weyerhaeuser’s pulp mill in New Bern, North Carolina. Since the start-up of the a new fibre-line at the facility in September of 1997, the CHEMRECTM gasifier was instrumental in satisfying the mill’s increased production requirements. The plant design and the operating experience since start-up is presented. As a new technology, the gasifier presented many technical challenges, and how these are currently being overcome is discussed.