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02709 Thermochemical sulphate reduction (TSR):experimental determination of reaction kinetics and implications of the observed reaction rates for petroleum reservoirs
02 Liquid fuels (transport, refining, quafity, storage) and oil-discharging sections communicated with lower- and upperportions of the storage space, respectively, and an oil-absorption mat arranged between the introduction section and the water-discharging section. The above-stated oil can be waste oils, e.g. of fuel oil, lubricating oil, hydrocarbon oil, etc.
04•02703 Performance of composite catalysts in palm oil cracking for the production of liquid fuels and chemicals Twaiq, F. A. A. et al. Fuel Processing Technology, 2004, 85, (11), 12831300. A composite material containing zeolite ZSM-5 and mesoporous molecular sieve was prepared by coating ZSM-5 crystals with a layer of mesoporous molecular sieve using cetyltrimethylammonium chloride as template. The ratio of mesophase was varied from 10 to 40 wt% and the alumina content in the mesophase was varied from 0 to 15 wt%. The synthesized composite materials were characterized using nitrogen adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM) and acidity. The surface area was found to vary in the range of 350-500 m2/g when ZSM-5 coated with siliceous mesophase and varied from 140 to 350 m2/g when aluminosilicate coating was used. The composite materials were used as catalysts in the palm oil cracking process and their performance was compared with those obtained fi'om HZSM-5 and MCM-41 materials. Palm oil conversion of 80-100 wt% and yield of gasoline fraction of 38-47 wt% were obtained from the composite catalysts. The catalysts were selective towards the formation of aromatics in the organic liquid product (OLP).
04•02704 Revamping of diesel hydrodesulfurizers: options available and future research needs Bej, S. K. Fuel Processing Technology, 2004, 85, (13), 1503 1517. The legislative pressure is being increased to reduce maximum allowable sulfur content in diesel to 50 wppm and lower. Existing hydrodesulfurizers currently reducing sulfur level to 500 wppm will not be able to meet this future requirement. Some improvements can be made in these existing units by switching over to new generation of catalysts and changing the levels of various process variables. Installation of a second reactor to accommodate additional catalyst volume will probalbly be inevitable for meeting this requirement of new sulfur specification. In this article, the various issues related to the second reactor, such as selection of a proper catalyst, optimum level of process conditions, location and operating mode of the reactor are discussed. Various process configurations based on the location of the second reactor have been analysed. Different options for operating the second reactor under a lean atmosphere of H2S have also been discussed. All these process configurations differ in terms of capital investment, operating cost and desulfurization efficiencies. Future studies are required to take the optimum decision.
04•02705 Shear mixing for preparation of stable fuel emulsions of internal-combustion fuels by multiple in-line blending stations for adding additives and water Coleman, G. N. et al. U.S. US 6,607,566 (C1. 44-301; C10L1/32), 19 Aug 2003, Appl. 1108,875. Water-continuous stable fuel emulsions for internal-combustion engines are prepared by: (1) blending a flow of additive(s) with a flow of a petroleum distillate fuel in an in-line blending station to form a fist composition, (2) hlending this first composition with a flow of purified w a t e r in a second blending station, to form a second composition, (3) ageing the second composition in a container, and (4) passing the second (aged) composition through a shear pump to form the fuel emulsion. Suitable hydrocarbon distillates include diesel fuel, kerosene, naphtha, aliphatic hydrocarbons, and paraffin oils. Suitable surfactants include ethoxylated alkylphenols, alcohols, fatty acids, and alkyl amines; other additives include lubrications, alkanolamine neutralizers, corrosion inhibitors, ignition delay modifiers, cetane improvers, stabilizers, biocides, foam inhibitors, rheological modifiers, and hydrotropes. 'The process can incorporate a third blending station for mixing of an antifreeze component.
04•02707 Texas refiner achieves fast column turnaround with combination treatment Hatton, A. et al. Oil & Gas Journal, 2003, 10l, (26), 58-61. In this paper, experiences in the cleaning of a refinery's gas plant to remove deposits and contaminants are reported. A combination of circulating fluid and steam was used that contained a surfactantenzyme mixture, a high flash-point solvent, and oxidizing chemicals to remove benzene, H2S and to render the column safe for human entry and service.
04•02708 The structure of gas-liquid flow in a horizontal pipe with abrupt area contraction Bertola, V. Experimental Thermal and Fluid Science, 2004, 28, (6), 505 512. In this study, single fibre optical probes were used to measure the cross-sectional void fraction distribution for air-water flow in a horizontal test section with sudden area contraction. The local void fraction was plotted as a function of its two spatial co-ordinates, so that a representation of the time average gas distribution over the crosssection could be obtained. The cross-sectional average void fraction was obtained by numerical integration of the local values; the contraction was shown to considerably alter the distribution of the phases, so that the correlations for straight pipes appear no longer suitable.
04•02709 Thermochemical sulphate reduction (TSR): experimental determination of reaction kinetics and implications of the observed reaction rates for petroleum reservoirs Cross, M. M. et al. Organic Geochemisto,, 2004, 35, (41), 393-404. Thermochemical sulphate reduction (TSR), responsible for substantial quantities (10-80%) of H2S in some high temperature petroleum accumulations, has been simulated in gold-titanium reaction vessels at 280-350°C and 250-500 bars and in-situ pH values between 5.2 and 6.8 using on-line fluid sampling and analysis to monitor continuous reaction progress. The calculated activation energy of TSR is 142 kJ/ tool with a half life of aqueous sulphate in the presence of aqueous acetate and elemental sulphur of 1650 years at 150°C and 372000 years at 100°C. The continuing co-existence of sulphate minerals and petroleum in many reservoirs, filled millions of years ago, thus cannot be controlled by the rate of reduction. The experiments also show that neither pressure nor pH significantly affect the rate of TSR when they are limited to a range of realistic subsurface values. The experiments coincidentally revealed that the rate of acetate decarboxylation is strongly pressure dependent with elevated pressure leading to a decreased rate of reaction. This must be because decarboxylation involves a positive volume change and provides evidence that all organic breakdown processes that lead to a net volume increase, e.g. kerogen breakdown, will be relatively retarded in over-pressured reservoirs.
04•02710 Upgrading of primary Fischer-Tropsch products by dewaxing and hydrofinishing for manufacture of lowpour-point diesel fuel and lubricating base oils Johnson, D. R. et al. U.S. Pat. Appl. Publ. US 2003 150,777 (C1. 208 97; C10G69/02), 14 Aug 2003, Appl. 68,927. In this study, low-pour-point hydrocarbons fractions from a FischerTropsch reaction, boiling point >150 °, are produced from a Cs+-Fischer-Tropsch primary product. This was carried out by: (1) dewaxing the Cs+ syncrude feedstock in a catalytic dewaxing zone, to produce a C5+ fraction with a decreased pour point, (3) hydrofinishing the C5+ fraction from step (2), and (4) collecting from the UVstabilized Cs+ product (from step (3)) a low-pour-point fraction boiling point >150 ° (e.g. as separate diesel fuel and lubricating base oil feedstocks). The dewaxing (especially hydrocracking-hydroisomerization) catalyst is an intermediate-pore SAPO zeolite, selected from SAPO-11, SAPO-31, and SAPO-41, or an intermediate-pore zeolite, selected from SSZ-32, ZSM-22, ZSM-23, ZSM-35, and ZSM-48, optionally in the presence of an active metal (Pd or Pt, preferably Pt). Hydrofinishing is carried out at 200-3000 psig (preferably 5002000 psig).
04•02706 Study on nickel and vanadium removal in thermal conversion of oil sludge and oil shale sludge
04•02711 Vapor-liquid equilibrium of octane-enhancing additives in gasolines
Sobral, L. G. et al. Journal de Physique IV." Proceedings, 2003, 107, (2), 1255-1258. Petroleum refining processes and oil shale industrialization generate solid and semi-solid residues. In these residues, heavy metals are present in concentrations that vary according to the production sector. Destination of those residues encourages researchers to look for new methods to maintain organism specifications and for industrial applications. This work showed heavy metals concentrations in petroleum oily solid residues and in oil shale, treated by low temperature thennat conversion, in both cases resulted in Ni and V concentrations <1 ppm and <5 ppm, respectively.
Alonso, C. et al. Fluid Phase Equilibria, 2004, 217, (2), 157 164. Experimental isothermal P - x data at T - 3 1 3 . 1 5 K for the binary systems 1, l-dimethylethyl methyl ether (MTBE)+ n-hexane and methanol + n-hexane, and the ternary system MTBE + methanol + n-hexane are re~orted. Data reduction by Barker's raethod provides correlations for G using the Margules equation for the binary systems and the Wohl expansion for the ternary system. Wilson, N R T L and U N I Q U A C models have been applied successfully to both the binary and the ternary systems. Moreover, the study compares the experimental results for these binary mixtures to the prediction of the U N I F A C ( D o m n u n d ) model. Experimental results have been com-
Fuel and Energy Abstracts
November 2004 385
04•02703 Performance of composite catalysts in palm oil cracking for the production of liquid fuels and chemicals Twaiq, F. A. A. et al. Fuel Processing Technology, 2004, 85, (11), 12831300. A composite material containing zeolite ZSM-5 and mesoporous molecular sieve was prepared by coating ZSM-5 crystals with a layer of mesoporous molecular sieve using cetyltrimethylammonium chloride as template. The ratio of mesophase was varied from 10 to 40 wt% and the alumina content in the mesophase was varied from 0 to 15 wt%. The synthesized composite materials were characterized using nitrogen adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM) and acidity. The surface area was found to vary in the range of 350-500 m2/g when ZSM-5 coated with siliceous mesophase and varied from 140 to 350 m2/g when aluminosilicate coating was used. The composite materials were used as catalysts in the palm oil cracking process and their performance was compared with those obtained fi'om HZSM-5 and MCM-41 materials. Palm oil conversion of 80-100 wt% and yield of gasoline fraction of 38-47 wt% were obtained from the composite catalysts. The catalysts were selective towards the formation of aromatics in the organic liquid product (OLP).
04•02704 Revamping of diesel hydrodesulfurizers: options available and future research needs Bej, S. K. Fuel Processing Technology, 2004, 85, (13), 1503 1517. The legislative pressure is being increased to reduce maximum allowable sulfur content in diesel to 50 wppm and lower. Existing hydrodesulfurizers currently reducing sulfur level to 500 wppm will not be able to meet this future requirement. Some improvements can be made in these existing units by switching over to new generation of catalysts and changing the levels of various process variables. Installation of a second reactor to accommodate additional catalyst volume will probalbly be inevitable for meeting this requirement of new sulfur specification. In this article, the various issues related to the second reactor, such as selection of a proper catalyst, optimum level of process conditions, location and operating mode of the reactor are discussed. Various process configurations based on the location of the second reactor have been analysed. Different options for operating the second reactor under a lean atmosphere of H2S have also been discussed. All these process configurations differ in terms of capital investment, operating cost and desulfurization efficiencies. Future studies are required to take the optimum decision.
04•02705 Shear mixing for preparation of stable fuel emulsions of internal-combustion fuels by multiple in-line blending stations for adding additives and water Coleman, G. N. et al. U.S. US 6,607,566 (C1. 44-301; C10L1/32), 19 Aug 2003, Appl. 1108,875. Water-continuous stable fuel emulsions for internal-combustion engines are prepared by: (1) blending a flow of additive(s) with a flow of a petroleum distillate fuel in an in-line blending station to form a fist composition, (2) hlending this first composition with a flow of purified w a t e r in a second blending station, to form a second composition, (3) ageing the second composition in a container, and (4) passing the second (aged) composition through a shear pump to form the fuel emulsion. Suitable hydrocarbon distillates include diesel fuel, kerosene, naphtha, aliphatic hydrocarbons, and paraffin oils. Suitable surfactants include ethoxylated alkylphenols, alcohols, fatty acids, and alkyl amines; other additives include lubrications, alkanolamine neutralizers, corrosion inhibitors, ignition delay modifiers, cetane improvers, stabilizers, biocides, foam inhibitors, rheological modifiers, and hydrotropes. 'The process can incorporate a third blending station for mixing of an antifreeze component.
04•02707 Texas refiner achieves fast column turnaround with combination treatment Hatton, A. et al. Oil & Gas Journal, 2003, 10l, (26), 58-61. In this paper, experiences in the cleaning of a refinery's gas plant to remove deposits and contaminants are reported. A combination of circulating fluid and steam was used that contained a surfactantenzyme mixture, a high flash-point solvent, and oxidizing chemicals to remove benzene, H2S and to render the column safe for human entry and service.
04•02708 The structure of gas-liquid flow in a horizontal pipe with abrupt area contraction Bertola, V. Experimental Thermal and Fluid Science, 2004, 28, (6), 505 512. In this study, single fibre optical probes were used to measure the cross-sectional void fraction distribution for air-water flow in a horizontal test section with sudden area contraction. The local void fraction was plotted as a function of its two spatial co-ordinates, so that a representation of the time average gas distribution over the crosssection could be obtained. The cross-sectional average void fraction was obtained by numerical integration of the local values; the contraction was shown to considerably alter the distribution of the phases, so that the correlations for straight pipes appear no longer suitable.
04•02709 Thermochemical sulphate reduction (TSR): experimental determination of reaction kinetics and implications of the observed reaction rates for petroleum reservoirs Cross, M. M. et al. Organic Geochemisto,, 2004, 35, (41), 393-404. Thermochemical sulphate reduction (TSR), responsible for substantial quantities (10-80%) of H2S in some high temperature petroleum accumulations, has been simulated in gold-titanium reaction vessels at 280-350°C and 250-500 bars and in-situ pH values between 5.2 and 6.8 using on-line fluid sampling and analysis to monitor continuous reaction progress. The calculated activation energy of TSR is 142 kJ/ tool with a half life of aqueous sulphate in the presence of aqueous acetate and elemental sulphur of 1650 years at 150°C and 372000 years at 100°C. The continuing co-existence of sulphate minerals and petroleum in many reservoirs, filled millions of years ago, thus cannot be controlled by the rate of reduction. The experiments also show that neither pressure nor pH significantly affect the rate of TSR when they are limited to a range of realistic subsurface values. The experiments coincidentally revealed that the rate of acetate decarboxylation is strongly pressure dependent with elevated pressure leading to a decreased rate of reaction. This must be because decarboxylation involves a positive volume change and provides evidence that all organic breakdown processes that lead to a net volume increase, e.g. kerogen breakdown, will be relatively retarded in over-pressured reservoirs.
04•02710 Upgrading of primary Fischer-Tropsch products by dewaxing and hydrofinishing for manufacture of lowpour-point diesel fuel and lubricating base oils Johnson, D. R. et al. U.S. Pat. Appl. Publ. US 2003 150,777 (C1. 208 97; C10G69/02), 14 Aug 2003, Appl. 68,927. In this study, low-pour-point hydrocarbons fractions from a FischerTropsch reaction, boiling point >150 °, are produced from a Cs+-Fischer-Tropsch primary product. This was carried out by: (1) dewaxing the Cs+ syncrude feedstock in a catalytic dewaxing zone, to produce a C5+ fraction with a decreased pour point, (3) hydrofinishing the C5+ fraction from step (2), and (4) collecting from the UVstabilized Cs+ product (from step (3)) a low-pour-point fraction boiling point >150 ° (e.g. as separate diesel fuel and lubricating base oil feedstocks). The dewaxing (especially hydrocracking-hydroisomerization) catalyst is an intermediate-pore SAPO zeolite, selected from SAPO-11, SAPO-31, and SAPO-41, or an intermediate-pore zeolite, selected from SSZ-32, ZSM-22, ZSM-23, ZSM-35, and ZSM-48, optionally in the presence of an active metal (Pd or Pt, preferably Pt). Hydrofinishing is carried out at 200-3000 psig (preferably 5002000 psig).
04•02706 Study on nickel and vanadium removal in thermal conversion of oil sludge and oil shale sludge
04•02711 Vapor-liquid equilibrium of octane-enhancing additives in gasolines
Sobral, L. G. et al. Journal de Physique IV." Proceedings, 2003, 107, (2), 1255-1258. Petroleum refining processes and oil shale industrialization generate solid and semi-solid residues. In these residues, heavy metals are present in concentrations that vary according to the production sector. Destination of those residues encourages researchers to look for new methods to maintain organism specifications and for industrial applications. This work showed heavy metals concentrations in petroleum oily solid residues and in oil shale, treated by low temperature thennat conversion, in both cases resulted in Ni and V concentrations <1 ppm and <5 ppm, respectively.
Alonso, C. et al. Fluid Phase Equilibria, 2004, 217, (2), 157 164. Experimental isothermal P - x data at T - 3 1 3 . 1 5 K for the binary systems 1, l-dimethylethyl methyl ether (MTBE)+ n-hexane and methanol + n-hexane, and the ternary system MTBE + methanol + n-hexane are re~orted. Data reduction by Barker's raethod provides correlations for G using the Margules equation for the binary systems and the Wohl expansion for the ternary system. Wilson, N R T L and U N I Q U A C models have been applied successfully to both the binary and the ternary systems. Moreover, the study compares the experimental results for these binary mixtures to the prediction of the U N I F A C ( D o m n u n d ) model. Experimental results have been com-
Fuel and Energy Abstracts
November 2004 385