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02456 A precipitated iron Fischer—Tropsch catalyst for synthesis gas conversion to liquid fuels
02
Liquid fuels (transport,
refining,
quality,
storage)
99102445 Developments in Fischer-Tropsch technology Jager, B. Slud. Surf Sci. Catal., 1998, 119, (Natural Gas Conversion V), 25-34. Recent developments in Fischer-Tropsch (F-T) technology are reviewed in this paper. These, together with optimization of the integration of F-T technology with natural gas reforming, have considerably reduced the capital and operating costs associated with the production of liquid fuels from natural gas. The possible coproduction of chemicals is also discussed.
99102446 Fischer-Tropsch manufacture of Cg+ hydrocarbons from synthesis gas derived from natural gas with cryogenic nitrogen removal from the natural gas upstream of the synthesis gas generation Alexion, D. C. and Coulaloglou, C. A. PCT Int. Appl. WO 98 50,326, (Cl. CO7Cl/O4), 12 Nov 1998, US Appl. 851,867, 6 May 1997, 20 pp. In this Cs+ hydrocarbon synthesis process nitrogen is cryogenically removed from natural gas before it is converted into a synthesis gas. The resultant synthesis gas is substantially free of Fischer-Tropsch catalyst-deactivating nitrogen compounds such as NH1 and HCN. This increases the lifetime and reduces the need for rejuvenation of the hydrocarbon-synthesis catalyst. During the cryogenic separation, C z+ hydrocarbons are separated from the natural gas. Additionally, to increase the yield of synthesis gas, all or a portion of the separated Cl_., hydrocarbons are added to the methane feed before it is converted into synthesis gas. All or a portion of the separated C2_3 hydrocarbons may be removed as liquefied petroleum gases. 99102447 Flow improver additives for fuel oils Nakada, Y. et al. Jpn. Kokai Tokkyo Koho JP 10 237,469 [98 237,469], (Cl. ClOLI/l4), 8 Sep 1998, Appl. 97158,319, 25 Feb 1997, 8 pp. (In Japanese) Contained in low-temperature flow improvers for fuel oils are 21 of (A) oartial esters of (al) polvols having 13 valence with (a2) ClZ_3n fatty acids, ?B) partial esters of alkylene oxid; adducts of (al) with (a2), (C) alkylene oxide adducts of (A) and (D) graft adducts of unsaturated dicarboxylic acid esters and ethylene-saturated carboxylic vinyl ester copolymers.
Gas purification technology for 200,000 t/a methanol installation
99102448
Tang, Y. Shanghai Hungong, 1997, 22, (5), 14-18. (In Chinese) Desulfurization and decarbonization at the 200,000 t/a methanol installation in Shanghai Coking and Chemical Corporation is done using low temperature methanol washing technology. This technology is presented in this paper with a evaluation of its trial operation with respect to the performance of the technology and equipment. It was found that the methanol synthesis catalyst was well protected and the gas quality was excellent after washing. It can be concluded that the technique is successful in gas purification for methanol production using coal as raw material. 99102449
Gas to liquid conversion.
Basic features
and
competitors
Chaumette, P. Per. Tech., 1998, 415, 83-85. Gas-to-liquids conversion (GTL) via a three-step process including synthesis gas generation, Fischer-Tropsch synthesis and hydroisomerization of Fischer-Tropsch effluents is reviewed.
Gas to liquids technology: current developments and strategic implications for the energy industry
99102450
Weick, L. Per. Tech., 1998, 415, 98-102. Fischer-Tropsch synthesis is a route to gas to liquid conversion. This article reviews economical gas to liquids (GTL) technology, via F-T, which start with remote and substandard gas reserves.
GTL outlook 99102451 lowering costs
1. GTL technologies
focus on
Corke, M. J. Oil Gas J., 1998, 96, (38), 71-73, 76-77. There have been considerable technology improvements in the FischerTropsch conversion of natural gas-to-liquid (GTL) hydrocarbons. This, combined with the present difficulties in natural gas production projects and the limitations imposed by saturated markets for LNG or pipeline gas, has meant that GLT has become a viable gas utilization approach. In the first part of this two-part series, technology developments which have led to todays situation are reviewed. The second part examines the economics of GTL conversion. 99102452
Induced biochemical conversions of heavy crude
oils
Premuzic, E. T. and Lin, M. S. J. ofPet. Sci. & kg., 1999, 22, (l-3), 171180. Products formed during multiple interactions of microorganisms with oils fall into two major categories: those formed due to the action of indigenous microorganisms under reservoir conditions over geological periods of time and those products which are generated by the action of introduced organisms. The extreme end product of the first category is the production of heavy ‘biodegraded’ crudes. The extreme end product of the second category is the production of reduced sulfates due to the introduction of sulfate-reducing bacteria which may lead to the souring of a field. There is, however, a select group of microorganisms whose action on the crudes is beneficial. The interactions between such microorganisms and different crude oils occur through complex biochemical and chemical reactions.
258
Fuel and Energy Abstracts
July 1999
These reactions depend on multiple variables within and at the interface of a multicomponent system consisting of organic, aqueous and inorganic components. Studies, carried out in this laboratory (BNL) of biochemical and chemical reactions in crude oils which involve extremophilic organisms (organisms which thrive in extreme environments). have shown that the reactions are not random and follow distinct trends. These trends can be categorized. The use of a group of characteristic chemical markers, such as mass spectrometric fragmentation patterns of light and heavy hydrocarbons, heterocyclic and organometallic compounds, as well as total trace metal and heteroatom contents of crude oils before and after the biochemical treatment allows to follow the type and the extent of chemical changes which occur during the biochemical conversion of heavy crude oils by microorganisms. The bioconversion involves multiple, simultaneous and/or concurrent chemical reactions in which the microorganisms serve as biocatalysts. In this sense, the biocatalysts are active in a reaction medium which depends on the chemical composition of the crude and the selectivity of the biocatalyst. Thus, the bioconversion of the crude depends on the relative distribution of saturates, aromatics, resins and asphaltenes and the distribution of polar compounds containing the heteroatoms (N, S, 0) and trace metals. The role of these constituents in the bioconversion of crudes will be briefly reviewed in this paper.
Interrelation of the preparation method and activity 99102453 of Co-RulSiOa catalysts
Niemela, M. el al. Srud. Surf Sci. Catal., 1998, 118, (Preparation of Catalvsts VII). 229-236. A st;dy of ~&bony1 catalyst precursors is presented, with the aim of determining the effect of catalyst preparation method on its performance in Fischer-Tropsch synthesis. The Co-Ru/SiOz catalyst prepared by ionic adsorption displayed a selectivity that is unique in Fischer-Tropsch synthesis.
The low temperature oxidation of Athabasca oil sand asphaltene observed from 13C, “F, and pulsed field gradient spin-echo proton n.m.r. spectra
99102454
Desando, M. A. ef al. Fuel, 78, (l), 31-45. Carbon-13 and fluorine-19 nuclear magnetic resonance spectra of chemically derivatized, by phase transfer methylation and trilluornacetylation, Athabasca oil sand asphaltene, reveal a broad site distribution of different types of hydroxyl-containing functional groups, carboxylic acids, phenols and alcohols. The low temperature air oxidation of asphaltene, at around 130°C for 3 days, generates a few additional carboxyl and phenolic groups. These results are consistent with a mechanism in which diary1 methylene and ether moieties react with oxygen. Self-diffusion coefficients, from the pulsed field gradient spin-echo proton magnetic resonance technique, suggest that low temperature oxidation does not appreciably alter the average particle size and diffusion properties of asnhaltene in deuterochloroform.
Mechanochemical catalysts in conversions of C, molecules (syntheses of methanol and methyl formate, FischerTropsch synthesis, and water-gas shift reaction)
99102455
Lin, C. I. et al. Kinet. Coral., 1998, 39, (4). 577-583. Catalysts based on copper, zinc, aluminium and chromium oxides were prepared by mechanochemical treatment of solid components. Their performance was assessed in methanol preparation, in methanol dehydrogenation to form methyl formate, in the Fischer-Tropsch process and in the water-gas shift reaction. The mechanochemical catalysts exhibited a high specific activity and their efficiency was comparable with that of catalysts prepared by coprecipitation.
A precipitated iron Fischer-Tropsch 99102456 svnthesis aas conversion to liauid fuels
catalyst for
Bbkur, D. B-and Lang, X. Stud. S&f&i. Catal., 1998, 119, (Natural Gas Conversion V), 113-118. A precipitated iron Fischer-Tropsch (F-T) catalyst with nominal composition 100 Fe/3 Cu/4 K/16 SiOZ (in parts by weight) was tested in a stirred tank slurry reactor. These tests showed that the performance of this catalyst (activity and selectivity) under baseline activation (Hz reduction at 240°C for 2 h) and process conditions (26O”C, 1.48 MPa, 1.4 Nlig-cat/h, Hz/CO = 2/3) compared favourably to that of the best state-of-the-art iron F-T catalysts. The ability to repeat this performance was demonstrated by conducting multiple tests on the catalyst from the same preparation batch, while the reproducibility of the catalyst preparation procedure shown by testing the catalyst from different batches. Catalyst productivity (i.e. reactor space-time-yield) was increased by 40% (relative to baseline process conditions) by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while simultaneously increasing gas space velocity in order to maintain a constant contact time in the reactor. By using different pretreatment procedures the intrinsic activity of the catalyst was increased by up to 75%. The catalyst productivity in run SA-2186 at 26o”C, 2.17 MPa, 3.4 Nl/g-cat/h and HZ/CO = 2/3 was 0.86 (g hydrocarbons/g-iron/h) at syngas conversion of 79%. methane selectivity of 3% (weight percent of total hydrocarbons produced) and C,+ hydrocarbon selectivity of 83 wt%. This represents a 75% increase in catalyst productivity. The liquid and wax hydrocarbons in different tests on this catalyst yielded SO-89%, and the Anderson-SchulzFlory parameter was 0.92-0.94 (high alpha catalyst). The catalyst is ideally suited for producing high quality diesel fuels via hydrocracking of the F-T wax product.
Liquid fuels (transport,
refining,
quality,
storage)
99102445 Developments in Fischer-Tropsch technology Jager, B. Slud. Surf Sci. Catal., 1998, 119, (Natural Gas Conversion V), 25-34. Recent developments in Fischer-Tropsch (F-T) technology are reviewed in this paper. These, together with optimization of the integration of F-T technology with natural gas reforming, have considerably reduced the capital and operating costs associated with the production of liquid fuels from natural gas. The possible coproduction of chemicals is also discussed.
99102446 Fischer-Tropsch manufacture of Cg+ hydrocarbons from synthesis gas derived from natural gas with cryogenic nitrogen removal from the natural gas upstream of the synthesis gas generation Alexion, D. C. and Coulaloglou, C. A. PCT Int. Appl. WO 98 50,326, (Cl. CO7Cl/O4), 12 Nov 1998, US Appl. 851,867, 6 May 1997, 20 pp. In this Cs+ hydrocarbon synthesis process nitrogen is cryogenically removed from natural gas before it is converted into a synthesis gas. The resultant synthesis gas is substantially free of Fischer-Tropsch catalyst-deactivating nitrogen compounds such as NH1 and HCN. This increases the lifetime and reduces the need for rejuvenation of the hydrocarbon-synthesis catalyst. During the cryogenic separation, C z+ hydrocarbons are separated from the natural gas. Additionally, to increase the yield of synthesis gas, all or a portion of the separated Cl_., hydrocarbons are added to the methane feed before it is converted into synthesis gas. All or a portion of the separated C2_3 hydrocarbons may be removed as liquefied petroleum gases. 99102447 Flow improver additives for fuel oils Nakada, Y. et al. Jpn. Kokai Tokkyo Koho JP 10 237,469 [98 237,469], (Cl. ClOLI/l4), 8 Sep 1998, Appl. 97158,319, 25 Feb 1997, 8 pp. (In Japanese) Contained in low-temperature flow improvers for fuel oils are 21 of (A) oartial esters of (al) polvols having 13 valence with (a2) ClZ_3n fatty acids, ?B) partial esters of alkylene oxid; adducts of (al) with (a2), (C) alkylene oxide adducts of (A) and (D) graft adducts of unsaturated dicarboxylic acid esters and ethylene-saturated carboxylic vinyl ester copolymers.
Gas purification technology for 200,000 t/a methanol installation
99102448
Tang, Y. Shanghai Hungong, 1997, 22, (5), 14-18. (In Chinese) Desulfurization and decarbonization at the 200,000 t/a methanol installation in Shanghai Coking and Chemical Corporation is done using low temperature methanol washing technology. This technology is presented in this paper with a evaluation of its trial operation with respect to the performance of the technology and equipment. It was found that the methanol synthesis catalyst was well protected and the gas quality was excellent after washing. It can be concluded that the technique is successful in gas purification for methanol production using coal as raw material. 99102449
Gas to liquid conversion.
Basic features
and
competitors
Chaumette, P. Per. Tech., 1998, 415, 83-85. Gas-to-liquids conversion (GTL) via a three-step process including synthesis gas generation, Fischer-Tropsch synthesis and hydroisomerization of Fischer-Tropsch effluents is reviewed.
Gas to liquids technology: current developments and strategic implications for the energy industry
99102450
Weick, L. Per. Tech., 1998, 415, 98-102. Fischer-Tropsch synthesis is a route to gas to liquid conversion. This article reviews economical gas to liquids (GTL) technology, via F-T, which start with remote and substandard gas reserves.
GTL outlook 99102451 lowering costs
1. GTL technologies
focus on
Corke, M. J. Oil Gas J., 1998, 96, (38), 71-73, 76-77. There have been considerable technology improvements in the FischerTropsch conversion of natural gas-to-liquid (GTL) hydrocarbons. This, combined with the present difficulties in natural gas production projects and the limitations imposed by saturated markets for LNG or pipeline gas, has meant that GLT has become a viable gas utilization approach. In the first part of this two-part series, technology developments which have led to todays situation are reviewed. The second part examines the economics of GTL conversion. 99102452
Induced biochemical conversions of heavy crude
oils
Premuzic, E. T. and Lin, M. S. J. ofPet. Sci. & kg., 1999, 22, (l-3), 171180. Products formed during multiple interactions of microorganisms with oils fall into two major categories: those formed due to the action of indigenous microorganisms under reservoir conditions over geological periods of time and those products which are generated by the action of introduced organisms. The extreme end product of the first category is the production of heavy ‘biodegraded’ crudes. The extreme end product of the second category is the production of reduced sulfates due to the introduction of sulfate-reducing bacteria which may lead to the souring of a field. There is, however, a select group of microorganisms whose action on the crudes is beneficial. The interactions between such microorganisms and different crude oils occur through complex biochemical and chemical reactions.
258
Fuel and Energy Abstracts
July 1999
These reactions depend on multiple variables within and at the interface of a multicomponent system consisting of organic, aqueous and inorganic components. Studies, carried out in this laboratory (BNL) of biochemical and chemical reactions in crude oils which involve extremophilic organisms (organisms which thrive in extreme environments). have shown that the reactions are not random and follow distinct trends. These trends can be categorized. The use of a group of characteristic chemical markers, such as mass spectrometric fragmentation patterns of light and heavy hydrocarbons, heterocyclic and organometallic compounds, as well as total trace metal and heteroatom contents of crude oils before and after the biochemical treatment allows to follow the type and the extent of chemical changes which occur during the biochemical conversion of heavy crude oils by microorganisms. The bioconversion involves multiple, simultaneous and/or concurrent chemical reactions in which the microorganisms serve as biocatalysts. In this sense, the biocatalysts are active in a reaction medium which depends on the chemical composition of the crude and the selectivity of the biocatalyst. Thus, the bioconversion of the crude depends on the relative distribution of saturates, aromatics, resins and asphaltenes and the distribution of polar compounds containing the heteroatoms (N, S, 0) and trace metals. The role of these constituents in the bioconversion of crudes will be briefly reviewed in this paper.
Interrelation of the preparation method and activity 99102453 of Co-RulSiOa catalysts
Niemela, M. el al. Srud. Surf Sci. Catal., 1998, 118, (Preparation of Catalvsts VII). 229-236. A st;dy of ~&bony1 catalyst precursors is presented, with the aim of determining the effect of catalyst preparation method on its performance in Fischer-Tropsch synthesis. The Co-Ru/SiOz catalyst prepared by ionic adsorption displayed a selectivity that is unique in Fischer-Tropsch synthesis.
The low temperature oxidation of Athabasca oil sand asphaltene observed from 13C, “F, and pulsed field gradient spin-echo proton n.m.r. spectra
99102454
Desando, M. A. ef al. Fuel, 78, (l), 31-45. Carbon-13 and fluorine-19 nuclear magnetic resonance spectra of chemically derivatized, by phase transfer methylation and trilluornacetylation, Athabasca oil sand asphaltene, reveal a broad site distribution of different types of hydroxyl-containing functional groups, carboxylic acids, phenols and alcohols. The low temperature air oxidation of asphaltene, at around 130°C for 3 days, generates a few additional carboxyl and phenolic groups. These results are consistent with a mechanism in which diary1 methylene and ether moieties react with oxygen. Self-diffusion coefficients, from the pulsed field gradient spin-echo proton magnetic resonance technique, suggest that low temperature oxidation does not appreciably alter the average particle size and diffusion properties of asnhaltene in deuterochloroform.
Mechanochemical catalysts in conversions of C, molecules (syntheses of methanol and methyl formate, FischerTropsch synthesis, and water-gas shift reaction)
99102455
Lin, C. I. et al. Kinet. Coral., 1998, 39, (4). 577-583. Catalysts based on copper, zinc, aluminium and chromium oxides were prepared by mechanochemical treatment of solid components. Their performance was assessed in methanol preparation, in methanol dehydrogenation to form methyl formate, in the Fischer-Tropsch process and in the water-gas shift reaction. The mechanochemical catalysts exhibited a high specific activity and their efficiency was comparable with that of catalysts prepared by coprecipitation.
A precipitated iron Fischer-Tropsch 99102456 svnthesis aas conversion to liauid fuels
catalyst for
Bbkur, D. B-and Lang, X. Stud. S&f&i. Catal., 1998, 119, (Natural Gas Conversion V), 113-118. A precipitated iron Fischer-Tropsch (F-T) catalyst with nominal composition 100 Fe/3 Cu/4 K/16 SiOZ (in parts by weight) was tested in a stirred tank slurry reactor. These tests showed that the performance of this catalyst (activity and selectivity) under baseline activation (Hz reduction at 240°C for 2 h) and process conditions (26O”C, 1.48 MPa, 1.4 Nlig-cat/h, Hz/CO = 2/3) compared favourably to that of the best state-of-the-art iron F-T catalysts. The ability to repeat this performance was demonstrated by conducting multiple tests on the catalyst from the same preparation batch, while the reproducibility of the catalyst preparation procedure shown by testing the catalyst from different batches. Catalyst productivity (i.e. reactor space-time-yield) was increased by 40% (relative to baseline process conditions) by increasing reaction pressure from 1.48 MPa to 2.17 MPa, while simultaneously increasing gas space velocity in order to maintain a constant contact time in the reactor. By using different pretreatment procedures the intrinsic activity of the catalyst was increased by up to 75%. The catalyst productivity in run SA-2186 at 26o”C, 2.17 MPa, 3.4 Nl/g-cat/h and HZ/CO = 2/3 was 0.86 (g hydrocarbons/g-iron/h) at syngas conversion of 79%. methane selectivity of 3% (weight percent of total hydrocarbons produced) and C,+ hydrocarbon selectivity of 83 wt%. This represents a 75% increase in catalyst productivity. The liquid and wax hydrocarbons in different tests on this catalyst yielded SO-89%, and the Anderson-SchulzFlory parameter was 0.92-0.94 (high alpha catalyst). The catalyst is ideally suited for producing high quality diesel fuels via hydrocracking of the F-T wax product.