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04514 Influence of zinc dithiophosphate on antioxidant properties of motor oils containing different detergent additives
02
Liquid fuels (transport, refining, quality, storage)
such as thiophenes. Beneficially, the process also removes other heteroatoms (nitrogen and oxygen) and metals (vanadium, iron. nickel) and reduces asphaltene content (n-heptane insolubles), microcarbon residue, coke. 975°F fractions. TGA fixed carbon. average molecular weight, density and viscosity.
Coprocessing 97104511 with Hondo Oil
of New Mexico
subbituminous
coal
Lee, T. L. K. rf rrl. froc. Annrr. Inr. Pittshur@ Coul Cor$.. 1996. 13, (I), 292-297. At Hydrocarbon Technologies, Incl., novel processing concepts in catalytic coal/oil coprocessing are being evaluated in continuous process units. The new ideas explored in this programme include the studies of the effects of the effects of a combined system of adding hydroaromatic solvents, dispersed/supported catalysts, and the effects of temperature staging on coal/oil coprocessing. Improvements are realized in terms of residuum conversion, distillate yield and quality. The best results have been achieved using a combination of HTI’s iron catalyst and commercial Mo catalyst in the first stage and a supported catalyst in the second stage. Two aromatic oils were used in this programme, a coal-derived oil and FCC decanted oil; both show a similar small negative impact on residuum conversion and overall distillate yield and no impact on coal conversion. Low/high temperature staging, as opposed to operating the reactors at equal temperatures, results in an improvement in coal conversion, residuum conversion and total distillate yield. The comparison of coal/oil coprocessing to oil-only hydrocracking operation shows improvements in process performance due to the presence of coal, especially in reducing heteroatoms and metal contents in the products. The successful demonstration of HTI’s coprocessing technology may lead directly to improved economic and to potential commercialization.
97104512 catalysts
DRIFTS
studies
on
Co/TiOz
Fischer-Tropsch
Mothebe, B. el al. Stud. Surf: Sci. Caral.. 1997. 1117, (Natural Gas Conversion IV), 1X7-lY2. Details of a DRIFTS study of CO on Co/Ti02 (10% Co) are given. Highly reduced cobalt shows a strong v(C0) absorption at -2010 cm-’ while a partially reduced sample absorbs strongly at -2060 cm-‘. The effect of pressure and temperature on the spectra give predictable results: absorption intensity increases with pressure and v(C0) absorptions move to higher wavenumber with temperature, presumably due to surface oxidation through CO decomposition. DRIFTS studies were also performed over the variously reduced Co/TiOz catalysts by reaction of the catalysts with CO/H2 For the more highly reduced catalyst, higher hydrocarbon yields, as detected by v(CH:) and v(CH,) absorptions, were detected.
Evaluation of polyolefin elastomers produced by 97104513 constrained geometry catalyst chemistry as viscosity modifiers for engine oil McGirk. R. H. et ~1. Sot,. Automat. Eng., /Spcc. Puhl.l SP, 1997. SP-1271, (Understanding Engine Oil Rheology and Tribology), 4.5-53. The development Constrained Geometry Catalysts (CGC) for polyolefina production permits the manufacture of new polyolefins in a solution process. CGC have a single active site for polymerization and the bridged nature of the monocyclopentadienyl titanium complex allows ea\y incorporation of alpha olefins into random ethylene copolymers characterized by narrow molecular weight distributions and narrow co-monomer distributions. This paper describes olefin copolymers (OCPs) of ethylene with propylene and octene co-monomers produced with constrained geometry catalysts. Their behaviour as viscosity index improvers in oil solutions is also assessed. Crystallinity was measured by DSC, and molecular weights (Mw) were determined by GPC. Thickening efficiency and shear stability were measured as I wtc/r polymer solutions in oil, and the effects of Mw and crystallinity on these oil solution properties w’ere analysed by regression analysis. Several conventional OCPs also were compared as 1 wt% solutions with CGC polymers. A scanning Brookfield viscometer was used to study low temperature properties of oil solutions as a function of polymer composition. For optimum performance, amorphous polymers must contain less than I 5b crystallinity, and semi-crystallized polymers must have crystallinity hetween about IO and 16%. Results from GF-2 bench tests on fully formulated oils indicate that polymers made with CGC are suitable as VI improvers in engine oils.
97104514
properties
Influence of zinc dithiophosphate on antioxidant of motor oils containing different detergent additives
Vipper, A. B. Pet. Coctl, 1906, 38, (3). 13-14. The author studied the co-operative influence of zinc dithiaphosphate and detergents on oxidation stability of motor oils. Oxidation stability depended on detergent type. Calcium phenate and salicylate were more effective antioxidants in the presence of copper than calcium sulfonate. The role of copper in the stability and synergism is also discussed.
392
Fuel and Energy Abstracts
November
1997
97104515 process
Lead
distribution
during
crude
oil
distillation
Sikora, Z. cf ul. Per Coo/, 1996. 38, (3). 38-39. The paper gives details of an investigation into the lead content in crude oil distillation fractions. Crude oil contains naturally occurring lead compounds and tetra-Et lead (TEL). It has been found out that lead from TEL does not contaminate gasoline or oil fractions, but accumulates in heavy ends.
97104516
Oil agglomeration
using water jets
Carbini, P. et al. Changing Scopes Miner. Process., Pm.. Ini. Mirw. P~mss. Symp., 6fh, 1996, 693-698. Edited by Kemal, M., Balkemn. Rotterdam, The Netherlands. A newly designed separator where oil emulsion and coal particle agglomeration take place due to the action of water jets is reported. Beneficiation results ih terms of ash removal rate, energy recovery and ash content of the clean product, under variable experimental conditions are discussed. Recovery can be increased through the addition of finely dispersed air bubbles, with the further advantage of reducing the water pressure and thus the energy involved. 97104517
catalysts
Potassium-promoted titania-supported for Fischer-Tropsch synthesis
nickel-iron
Van De Loosdrecht, J. et al. Stud. Surf. Sci. C‘rrrrrl.. lYY7. 107. (Natural Gas Conversion IV), 201-206. A study into the influence of potassium on the activity and selectivity of titania-supported nickel-iron catalysts in Fischer-Tropsch synthesis has been conducted. Small amounts of potassium increase the selectivity towards higher hydrocarbons. but decrease the CO conversion. This results from the presence of potassium on the surface of the nickel-iron alloy, which affects the adsorption and dissociation of CO and decreases the amount of active sites. 97104518
catalysts
Preparation and for Fischer-Tropsch
properties synthesis
of supported
cobalt
van de Loosdrecht, .I. cf al. Appl. Carol.. A. lYY7. 150. (2). 365-376. In order to study their influence on the ultimate metal particle \ize. alumina-supported cobalt catalysts were prepared from different cobalt precursors. The effect of the particle size on the catalytic performance during Fischer-Tropsch synthesis was also investigated. The preparation of low-loaded cobalt catalysts by incipient wetness impregnation using cobalt(Il) EDTA and ammonium cobalt(ll) citrate precursors resulted initially in very small cobalt oxide particles, as determined by XPS. The small oxide particles reacted during thermal treatment in a reducing gas flow with the alumina support to cobalt aluminate (CoAIzOJ). which was neither active nor selective during Fischer-Tropsch synthesis. The catalysts prepared with CO(NO~)~(~H~O) had larger particles that could be easily reduced to metallic cobalt. These catalysts were active under reaction conditions. High-loaded cobalt catalysts (5.0 wt(/r) prepared using ammonium cobalt(Il) citrate showed a larger particle size than the lowloaded catalyst prepared from the citrate precursor. The extent of reduction to metallic cobalt that could be achieved wzith the high-loaded catalyst was significantly higher than that with the low-loaded catalyst, as shown by magnetic measurements. Accordingly. the high-loaded catalyst exhibited a reasonable activity and, in addition. an interesting and remarkably high selectivity toward higher hydrocarbons.
97104519 Production of oxygenated products by hydroformylation of Fischer-Tropsch derived olefinic products Betts, M. J. et crl. PCT Int. Appl. WO 97 01.521 (Cl. CO7CliO4). I6 Jan 1997, ZA Appl. 9515,405. 29 Jun IYYS, 45 pp. The paper presents a process for producing oxygenated product\ from an olefin-rich feedstock. It comprise\ reacting, in a hydroformylation stage, a Fischer-Tropsch derived olefinic product with carbon monoxide and hydrogen in the presence of a catalytically effective quantity of a hydroformylation catalyst and under hydroformylation reaction condition\. to produce oxygenated products comprising aldehydes and/or alcohols. The Fischer-Tropsch derived olefinic product is that obtained hy suhjectlng a synthesis gas comprising carbon monoxide and hydrogen to FischerTropsch reaction conditions in the presence of an iron-based. a cobaltbased or an iron/cobalt-based Fischer-Tropsch catalyst. Fischer-Tropsch reaction of syngas over a fused iron catalyst containing K?O and SiOL, and hydroformylation of I-octene fraction using [Rh(OzCCH1)z]J and PPh, gave Cs aldehydes with Yh”/r conversion and IOO? selectivity.
97104520 Promotion effect Tropsch synthesis performance
of manganese on Fischerof ultrafine COIZrOz catalyst
Xiang, H. ef al. Fenzi Cuihucc, 1997, I I. (3). 196-202. (In Chinese) The preparation of aero-gel ZrO? supported Co/ZrOz and Co-Mn!ZrOz catalysts is presented along with tests on their texture, structure, reduction. desorption and F-T reaction performance after adding mangancsc promoter. A suitable catalyst for long-chain hydrocarbons synthesis wa’r 15% Co-4.7% MnZrOz.
97104521 Property correlation Fischer-Tropsch liquids for process Marano, J. J. 1996, 331 pp. Avail. UMI, Divs. Ahsrr. Inl., B., IYYR, S8, (S8), 201 I.
and characterization modelling Order
No. DAY72XhYX.
of From
Liquid fuels (transport, refining, quality, storage)
such as thiophenes. Beneficially, the process also removes other heteroatoms (nitrogen and oxygen) and metals (vanadium, iron. nickel) and reduces asphaltene content (n-heptane insolubles), microcarbon residue, coke. 975°F fractions. TGA fixed carbon. average molecular weight, density and viscosity.
Coprocessing 97104511 with Hondo Oil
of New Mexico
subbituminous
coal
Lee, T. L. K. rf rrl. froc. Annrr. Inr. Pittshur@ Coul Cor$.. 1996. 13, (I), 292-297. At Hydrocarbon Technologies, Incl., novel processing concepts in catalytic coal/oil coprocessing are being evaluated in continuous process units. The new ideas explored in this programme include the studies of the effects of the effects of a combined system of adding hydroaromatic solvents, dispersed/supported catalysts, and the effects of temperature staging on coal/oil coprocessing. Improvements are realized in terms of residuum conversion, distillate yield and quality. The best results have been achieved using a combination of HTI’s iron catalyst and commercial Mo catalyst in the first stage and a supported catalyst in the second stage. Two aromatic oils were used in this programme, a coal-derived oil and FCC decanted oil; both show a similar small negative impact on residuum conversion and overall distillate yield and no impact on coal conversion. Low/high temperature staging, as opposed to operating the reactors at equal temperatures, results in an improvement in coal conversion, residuum conversion and total distillate yield. The comparison of coal/oil coprocessing to oil-only hydrocracking operation shows improvements in process performance due to the presence of coal, especially in reducing heteroatoms and metal contents in the products. The successful demonstration of HTI’s coprocessing technology may lead directly to improved economic and to potential commercialization.
97104512 catalysts
DRIFTS
studies
on
Co/TiOz
Fischer-Tropsch
Mothebe, B. el al. Stud. Surf: Sci. Caral.. 1997. 1117, (Natural Gas Conversion IV), 1X7-lY2. Details of a DRIFTS study of CO on Co/Ti02 (10% Co) are given. Highly reduced cobalt shows a strong v(C0) absorption at -2010 cm-’ while a partially reduced sample absorbs strongly at -2060 cm-‘. The effect of pressure and temperature on the spectra give predictable results: absorption intensity increases with pressure and v(C0) absorptions move to higher wavenumber with temperature, presumably due to surface oxidation through CO decomposition. DRIFTS studies were also performed over the variously reduced Co/TiOz catalysts by reaction of the catalysts with CO/H2 For the more highly reduced catalyst, higher hydrocarbon yields, as detected by v(CH:) and v(CH,) absorptions, were detected.
Evaluation of polyolefin elastomers produced by 97104513 constrained geometry catalyst chemistry as viscosity modifiers for engine oil McGirk. R. H. et ~1. Sot,. Automat. Eng., /Spcc. Puhl.l SP, 1997. SP-1271, (Understanding Engine Oil Rheology and Tribology), 4.5-53. The development Constrained Geometry Catalysts (CGC) for polyolefina production permits the manufacture of new polyolefins in a solution process. CGC have a single active site for polymerization and the bridged nature of the monocyclopentadienyl titanium complex allows ea\y incorporation of alpha olefins into random ethylene copolymers characterized by narrow molecular weight distributions and narrow co-monomer distributions. This paper describes olefin copolymers (OCPs) of ethylene with propylene and octene co-monomers produced with constrained geometry catalysts. Their behaviour as viscosity index improvers in oil solutions is also assessed. Crystallinity was measured by DSC, and molecular weights (Mw) were determined by GPC. Thickening efficiency and shear stability were measured as I wtc/r polymer solutions in oil, and the effects of Mw and crystallinity on these oil solution properties w’ere analysed by regression analysis. Several conventional OCPs also were compared as 1 wt% solutions with CGC polymers. A scanning Brookfield viscometer was used to study low temperature properties of oil solutions as a function of polymer composition. For optimum performance, amorphous polymers must contain less than I 5b crystallinity, and semi-crystallized polymers must have crystallinity hetween about IO and 16%. Results from GF-2 bench tests on fully formulated oils indicate that polymers made with CGC are suitable as VI improvers in engine oils.
97104514
properties
Influence of zinc dithiophosphate on antioxidant of motor oils containing different detergent additives
Vipper, A. B. Pet. Coctl, 1906, 38, (3). 13-14. The author studied the co-operative influence of zinc dithiaphosphate and detergents on oxidation stability of motor oils. Oxidation stability depended on detergent type. Calcium phenate and salicylate were more effective antioxidants in the presence of copper than calcium sulfonate. The role of copper in the stability and synergism is also discussed.
392
Fuel and Energy Abstracts
November
1997
97104515 process
Lead
distribution
during
crude
oil
distillation
Sikora, Z. cf ul. Per Coo/, 1996. 38, (3). 38-39. The paper gives details of an investigation into the lead content in crude oil distillation fractions. Crude oil contains naturally occurring lead compounds and tetra-Et lead (TEL). It has been found out that lead from TEL does not contaminate gasoline or oil fractions, but accumulates in heavy ends.
97104516
Oil agglomeration
using water jets
Carbini, P. et al. Changing Scopes Miner. Process., Pm.. Ini. Mirw. P~mss. Symp., 6fh, 1996, 693-698. Edited by Kemal, M., Balkemn. Rotterdam, The Netherlands. A newly designed separator where oil emulsion and coal particle agglomeration take place due to the action of water jets is reported. Beneficiation results ih terms of ash removal rate, energy recovery and ash content of the clean product, under variable experimental conditions are discussed. Recovery can be increased through the addition of finely dispersed air bubbles, with the further advantage of reducing the water pressure and thus the energy involved. 97104517
catalysts
Potassium-promoted titania-supported for Fischer-Tropsch synthesis
nickel-iron
Van De Loosdrecht, J. et al. Stud. Surf. Sci. C‘rrrrrl.. lYY7. 107. (Natural Gas Conversion IV), 201-206. A study into the influence of potassium on the activity and selectivity of titania-supported nickel-iron catalysts in Fischer-Tropsch synthesis has been conducted. Small amounts of potassium increase the selectivity towards higher hydrocarbons. but decrease the CO conversion. This results from the presence of potassium on the surface of the nickel-iron alloy, which affects the adsorption and dissociation of CO and decreases the amount of active sites. 97104518
catalysts
Preparation and for Fischer-Tropsch
properties synthesis
of supported
cobalt
van de Loosdrecht, .I. cf al. Appl. Carol.. A. lYY7. 150. (2). 365-376. In order to study their influence on the ultimate metal particle \ize. alumina-supported cobalt catalysts were prepared from different cobalt precursors. The effect of the particle size on the catalytic performance during Fischer-Tropsch synthesis was also investigated. The preparation of low-loaded cobalt catalysts by incipient wetness impregnation using cobalt(Il) EDTA and ammonium cobalt(ll) citrate precursors resulted initially in very small cobalt oxide particles, as determined by XPS. The small oxide particles reacted during thermal treatment in a reducing gas flow with the alumina support to cobalt aluminate (CoAIzOJ). which was neither active nor selective during Fischer-Tropsch synthesis. The catalysts prepared with CO(NO~)~(~H~O) had larger particles that could be easily reduced to metallic cobalt. These catalysts were active under reaction conditions. High-loaded cobalt catalysts (5.0 wt(/r) prepared using ammonium cobalt(Il) citrate showed a larger particle size than the lowloaded catalyst prepared from the citrate precursor. The extent of reduction to metallic cobalt that could be achieved wzith the high-loaded catalyst was significantly higher than that with the low-loaded catalyst, as shown by magnetic measurements. Accordingly. the high-loaded catalyst exhibited a reasonable activity and, in addition. an interesting and remarkably high selectivity toward higher hydrocarbons.
97104519 Production of oxygenated products by hydroformylation of Fischer-Tropsch derived olefinic products Betts, M. J. et crl. PCT Int. Appl. WO 97 01.521 (Cl. CO7CliO4). I6 Jan 1997, ZA Appl. 9515,405. 29 Jun IYYS, 45 pp. The paper presents a process for producing oxygenated product\ from an olefin-rich feedstock. It comprise\ reacting, in a hydroformylation stage, a Fischer-Tropsch derived olefinic product with carbon monoxide and hydrogen in the presence of a catalytically effective quantity of a hydroformylation catalyst and under hydroformylation reaction condition\. to produce oxygenated products comprising aldehydes and/or alcohols. The Fischer-Tropsch derived olefinic product is that obtained hy suhjectlng a synthesis gas comprising carbon monoxide and hydrogen to FischerTropsch reaction conditions in the presence of an iron-based. a cobaltbased or an iron/cobalt-based Fischer-Tropsch catalyst. Fischer-Tropsch reaction of syngas over a fused iron catalyst containing K?O and SiOL, and hydroformylation of I-octene fraction using [Rh(OzCCH1)z]J and PPh, gave Cs aldehydes with Yh”/r conversion and IOO? selectivity.
97104520 Promotion effect Tropsch synthesis performance
of manganese on Fischerof ultrafine COIZrOz catalyst
Xiang, H. ef al. Fenzi Cuihucc, 1997, I I. (3). 196-202. (In Chinese) The preparation of aero-gel ZrO? supported Co/ZrOz and Co-Mn!ZrOz catalysts is presented along with tests on their texture, structure, reduction. desorption and F-T reaction performance after adding mangancsc promoter. A suitable catalyst for long-chain hydrocarbons synthesis wa’r 15% Co-4.7% MnZrOz.
97104521 Property correlation Fischer-Tropsch liquids for process Marano, J. J. 1996, 331 pp. Avail. UMI, Divs. Ahsrr. Inl., B., IYYR, S8, (S8), 201 I.
and characterization modelling Order
No. DAY72XhYX.
of From