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04506 Pyrolysis analysis of crude oils and their fractions
02 Hydrocarbon 97/04500 cules in coal Pan, L. er al.
generation
capacity
of small
mole-
Chon@#trtrr Di,_hi Xnevucrn X11rhno, 199h, 26, (3). 356-3.59.
(In Chinese) Analysis of chemical composition and structure led to the discovery of small organic molecules in coal. Their origin, evolution and hydrocarbon generating capacity are discussed. These compounds are important materials for oil generation.
Hydrocoprocessing of scrap automotive tires and 97104501 coal. Analysis of oils from autoclave coprocessing Anderson, L. L. et al. Itnf. Eng. Chemicd Res., 1997, 36. (I I), 4763-4767. A magnetically stirred autoclave was the site of hydrocoprocessing of scrap automotive tyres and a low-rank coal. Reaction temperature (4Oo’C) and time (30 min) were kept constant while pressure was varied. An iron-hased catalyst was used to improve yields. Derived oils were analysed by GC-MS and TLC-FID. In terms of yields, a synergism between these two materials was discovered, although it can only be observed working at low hydrogen pressure. The oils obtained in the coprocessing showed a more aromatic nature than those obtained when both materials are processed alone. They also display higher boiling points, suggesting that radicals from rubber and coal react hetween each other instead of reacting with hydrogen radicals.
Influence of oxygen-containing 97104502 the separation of olefinlparaffin mixtures transport
hydrocarbons on using facilitated
van Zyl, A. J. and Linkov. V. M. J. Me&r. Sci. 1907, 133, (I). 15-26. The separation of olcfiniparaffin mixtures by means of silver-based facilitated transport of olefins was investigated using perfluorosulfonated innomer (PSI) membranes. Pentene and pentane were used as model compounds and separation factors as high as 33 were obtained. The influence of linear Cl_,,-alcohols and ketones on the separation of the pentene/pentane mixtures was investigated. The presence of oxygenates increased the fluxes of olefins and paraffins. resulting in lower selectivity for hydrocarbon separation.
97104503 activation
Kinetic analysis energy approach
of crude oils by a weighted
mean
Kok. M. V. and Okandan, E. J. T/term. Analysis, 1997, 48. (2), 343-34X. The reactivity and combustibility of crude petroleums via simultaneous thermogravimetry and differential thermogravimetry were described with the aid of a weighted mean activation energy method. Thermal experiments were conducted with a non-isothermal method at a heating rate of 1O’Cimin in excess air. Three distinct reaction regions were discovered when the rate data were fitted to an Arrhcnius equation. Weighted mean activation energies of the crude petroleums were calculated and linear correlations were established between this and API gravity and peak temperatures during high-temperature oxidation.
Liquid chromatographic separation of sediment, 97/04504 rock, and coal extracts and crude oil into compound classes Willsch. H. et (I/. Anulysis Chemical, 1997, 69, (2O), 4203-4209. The paper presents a method for rapid fractionation of sediment, rock, coal extracts and crude oils into compound classes. It was based on combined polarity and affinity chromatography of soluble organic matter. Five heterocompound fractions were obtained in addition to the conventional saturated and aromatic hydrocarbon fractions and model compound studies showed they were chemically well-defined. A North Sea crude petroleum and solvent extracts of Posidonia shale, coal, and Recent lake sediment samples were analysed. In general, reproducibilities and linearities were satisfactory, with total recoveries of 57-760/r, depending on sample type. The method was well-suited for the bulk compositional characterization of soluble organic matter. Separations can he performed on both the analysis and the semi-preparative scales. Isolated fractions were amenable directly or after derivation to qualitative and quantitative analysis by gas chromatography and gas chromatography-mass spectrometry.
Physico-chemical 97/04505 shale formations
modelling
of wellbore
stability
in
Osisanya, S. 0. and Chenevert, M. E. J. Can. Pet. Technol., 1996, 35. (2) 53-63. Due to the complex compositions of native shale, quantitative prediction of swelling pressure of shale in terms of all chemical (compositional) and mechanical factors is complicated. Physical and chemical interactions do occur between the shale constituents and fluids. A physicochemical model that incorporates the mechanics and chemical of shale/drilling fluid interaction under conditions of elevated temperature and pressure was developed. It is based on the total pressure concept and on thermodynamics to predict shale swelling pressures. A small-scale laboratory arrangement with an innovative testing procedure under downhole conditions was developed to validate the model. The model and the experimental apparatus are used to determine the effects of well bore pressure. confining pressure. temperature and drilling fluid composition on the swelling hehaviour of shales. This study provides a greatly improved understanding of shale/drilling fluid interaction and is useful for drilling fluid design optimization and total drilling costs minimization.
97lO4506
Pyrolysis
Liquid fuels (transport, refining, quality, storage)
analysis
of crude oils and their fractions
Karacan, 0. and Kok, M. V. Enera Fuels, 19Y7, I I. (2). 385-391. The pyrolysis behaviour of crude oils and their fractions was studied using differential scanning calorimetry and thermogravimctry. Experiments were performed at IO”C/min heating rate under nitrogen atmosphere. An examination of the fractions of crude oils shows that pyrolysis mechanisms depend on the chemical nature of the constituents. The weight loss properties of SABA constituents suggests that each fraction in whole crude oil follows its own reaction (distillation and cracking) pathway independent of the presence of other fractions.
97104507 Suppressed vitrinite reflectance and its effect on thermal history modelling in the Barrow and Dampier sub-basins Kaiko, A. R. and Tingate, P. R. APPEA J., 1996. 36, (I), 428-443. Major oil discoveries associated with Triassic to Cretaceous reservoirs and source rocks are located at the Barrow and Dampier Sub-hasins. They form an important offshore petroleum province. Difficulties in assessing thermal maturity using vitrinite reflectance data has hampered attempts to constrain the timing of oil generation and migration within the suh-hasins. JurassicCretaceous formations of predominantly marine origin yield vitrinite reflectance values that are often lower than expected compared to the present day thermal conditions. The two main explanations put forward hy workers for this situation are that: (1) a recent increase in thermal gradients has occurred; or (2) the vitrinite reflectance is suppressed, and this suppression is related to the marine environment of deposition. Thermal history analysis of 65 wells throughout the Barrow and Dampier Sub-basins has confirmed. using multiple maturity parameters, that vitrinitc reflectance data are suppressed over large parts of the study area. Thermal history modelling and the confirmation of vitrinite reflectance suppression has enahled revised estimates of present maturity to he made.
Systematic assessment of combustion characteristics of biofuels and emulsions with water for use as diesel engine fuels 97lO4508
Crookes, R. .I. et ul. Enew Cortrer.~. Mgmr, lY97. 3X. (1.5-17). 17X5-17YS. The combustion performance of hiofuel oils, hlends with diesel fuel and emulsions with water has been investigated using a variety of experimental techniques. Photographic examination of single droplets demonstrated similar burning rates to diesel fuel. High speed records revealed the explosive combustion of oil-water emulsion droplets. Spray-flame photography showed up the poor combustion efficiency at atmospheric pressure of the seed oils compared with diesel fuel. Combustion of sprays at elevated pressure, in a steady-flow combustor, of fuels. hlends and emulsions showed improved combustion under these conditions though still poorer for vegetable oil than for diesel fuel. Soot formation levels were also higher. though these were reduced hy emulsification with water. Under the more extreme conditions of the environment in a diesel engine combustion chamber, the performance of a commercially available hiofucl matched more closely that of diesel fuel. In single-cylinder engine tests at relatively low power and speed, the ignition delay was longer for the hiofuel. The difference became less at higher loads and speeds and also in a production line multi-cylinder engine under normal operating conditions. Soot levels were generally higher than for diesel fuel and oxides of nitrogen lower. Unlike most operating modifications which result in a trade-off hetween these species, emulsification of the hiofuel with water reduced levels of both soot and oxides of nitrogen.
Transport,
Refining,
Quality,
Storage
97104509 Cobalt-based ultrafine catalysts to synthesize longchain hydrocarbons-effect of reduction temperature Zhang, Y. et crl. Fmzi Cuihun, 1997, 11, (3). 203-208. (In Chinese) Ultrafine catalysts of aerogel SiOz powder, ZrOz-SiOz ultrafine complex oxide and CoiZrOa-SiOz were prepared. Effect of reduction temperature on F-T synthesis properties of the catalyst was investigated. The most suitable reduction temperature for CoiZrOzSiO? to synthesize Ci+ products was 400°C.
Continuous using aqueous base
97104510
in-situ process for upgrading
heavy oil
Brons, G. B. and Myers R. D. Can. Pat. Appl. CA 2,174,463 (Cl. ClOGlY/ 02) 3 Nov 1996. US Appl. 433,907, 2 May 1995, 20 pp. This innovation is a continuous in-situ process for the removal of organically bound sulfur in the form of mercaptans, sulfides and thiophenes. heteroatoms from heavy oils. The process involves contacting a heavy oil with aqueous sodium hydroxide at 3X0-450°C for a time sufficient to form sodium sulfide. The sodium sulfide is then contacted with water and a transition metal for a time and at a temperature sufficient to form transition metal sulfide, sodium hydroxide, hydrogen and impurities and the sodium hydroxide is recycled to the beginning of the process. The transition metal sulfide and the impurities wherein the impurities are iron, vanadium and nickel, are removed. Molecular hydrogen may optionally be added in the first step. The present invention is useful in removing organically-bound sulfur that has been recognized to he difficult to remove,
Fuel and Energy Abstracts
November
1997
391
generation
capacity
of small
mole-
Chon@#trtrr Di,_hi Xnevucrn X11rhno, 199h, 26, (3). 356-3.59.
(In Chinese) Analysis of chemical composition and structure led to the discovery of small organic molecules in coal. Their origin, evolution and hydrocarbon generating capacity are discussed. These compounds are important materials for oil generation.
Hydrocoprocessing of scrap automotive tires and 97104501 coal. Analysis of oils from autoclave coprocessing Anderson, L. L. et al. Itnf. Eng. Chemicd Res., 1997, 36. (I I), 4763-4767. A magnetically stirred autoclave was the site of hydrocoprocessing of scrap automotive tyres and a low-rank coal. Reaction temperature (4Oo’C) and time (30 min) were kept constant while pressure was varied. An iron-hased catalyst was used to improve yields. Derived oils were analysed by GC-MS and TLC-FID. In terms of yields, a synergism between these two materials was discovered, although it can only be observed working at low hydrogen pressure. The oils obtained in the coprocessing showed a more aromatic nature than those obtained when both materials are processed alone. They also display higher boiling points, suggesting that radicals from rubber and coal react hetween each other instead of reacting with hydrogen radicals.
Influence of oxygen-containing 97104502 the separation of olefinlparaffin mixtures transport
hydrocarbons on using facilitated
van Zyl, A. J. and Linkov. V. M. J. Me&r. Sci. 1907, 133, (I). 15-26. The separation of olcfiniparaffin mixtures by means of silver-based facilitated transport of olefins was investigated using perfluorosulfonated innomer (PSI) membranes. Pentene and pentane were used as model compounds and separation factors as high as 33 were obtained. The influence of linear Cl_,,-alcohols and ketones on the separation of the pentene/pentane mixtures was investigated. The presence of oxygenates increased the fluxes of olefins and paraffins. resulting in lower selectivity for hydrocarbon separation.
97104503 activation
Kinetic analysis energy approach
of crude oils by a weighted
mean
Kok. M. V. and Okandan, E. J. T/term. Analysis, 1997, 48. (2), 343-34X. The reactivity and combustibility of crude petroleums via simultaneous thermogravimetry and differential thermogravimetry were described with the aid of a weighted mean activation energy method. Thermal experiments were conducted with a non-isothermal method at a heating rate of 1O’Cimin in excess air. Three distinct reaction regions were discovered when the rate data were fitted to an Arrhcnius equation. Weighted mean activation energies of the crude petroleums were calculated and linear correlations were established between this and API gravity and peak temperatures during high-temperature oxidation.
Liquid chromatographic separation of sediment, 97/04504 rock, and coal extracts and crude oil into compound classes Willsch. H. et (I/. Anulysis Chemical, 1997, 69, (2O), 4203-4209. The paper presents a method for rapid fractionation of sediment, rock, coal extracts and crude oils into compound classes. It was based on combined polarity and affinity chromatography of soluble organic matter. Five heterocompound fractions were obtained in addition to the conventional saturated and aromatic hydrocarbon fractions and model compound studies showed they were chemically well-defined. A North Sea crude petroleum and solvent extracts of Posidonia shale, coal, and Recent lake sediment samples were analysed. In general, reproducibilities and linearities were satisfactory, with total recoveries of 57-760/r, depending on sample type. The method was well-suited for the bulk compositional characterization of soluble organic matter. Separations can he performed on both the analysis and the semi-preparative scales. Isolated fractions were amenable directly or after derivation to qualitative and quantitative analysis by gas chromatography and gas chromatography-mass spectrometry.
Physico-chemical 97/04505 shale formations
modelling
of wellbore
stability
in
Osisanya, S. 0. and Chenevert, M. E. J. Can. Pet. Technol., 1996, 35. (2) 53-63. Due to the complex compositions of native shale, quantitative prediction of swelling pressure of shale in terms of all chemical (compositional) and mechanical factors is complicated. Physical and chemical interactions do occur between the shale constituents and fluids. A physicochemical model that incorporates the mechanics and chemical of shale/drilling fluid interaction under conditions of elevated temperature and pressure was developed. It is based on the total pressure concept and on thermodynamics to predict shale swelling pressures. A small-scale laboratory arrangement with an innovative testing procedure under downhole conditions was developed to validate the model. The model and the experimental apparatus are used to determine the effects of well bore pressure. confining pressure. temperature and drilling fluid composition on the swelling hehaviour of shales. This study provides a greatly improved understanding of shale/drilling fluid interaction and is useful for drilling fluid design optimization and total drilling costs minimization.
97lO4506
Pyrolysis
Liquid fuels (transport, refining, quality, storage)
analysis
of crude oils and their fractions
Karacan, 0. and Kok, M. V. Enera Fuels, 19Y7, I I. (2). 385-391. The pyrolysis behaviour of crude oils and their fractions was studied using differential scanning calorimetry and thermogravimctry. Experiments were performed at IO”C/min heating rate under nitrogen atmosphere. An examination of the fractions of crude oils shows that pyrolysis mechanisms depend on the chemical nature of the constituents. The weight loss properties of SABA constituents suggests that each fraction in whole crude oil follows its own reaction (distillation and cracking) pathway independent of the presence of other fractions.
97104507 Suppressed vitrinite reflectance and its effect on thermal history modelling in the Barrow and Dampier sub-basins Kaiko, A. R. and Tingate, P. R. APPEA J., 1996. 36, (I), 428-443. Major oil discoveries associated with Triassic to Cretaceous reservoirs and source rocks are located at the Barrow and Dampier Sub-hasins. They form an important offshore petroleum province. Difficulties in assessing thermal maturity using vitrinite reflectance data has hampered attempts to constrain the timing of oil generation and migration within the suh-hasins. JurassicCretaceous formations of predominantly marine origin yield vitrinite reflectance values that are often lower than expected compared to the present day thermal conditions. The two main explanations put forward hy workers for this situation are that: (1) a recent increase in thermal gradients has occurred; or (2) the vitrinite reflectance is suppressed, and this suppression is related to the marine environment of deposition. Thermal history analysis of 65 wells throughout the Barrow and Dampier Sub-basins has confirmed. using multiple maturity parameters, that vitrinitc reflectance data are suppressed over large parts of the study area. Thermal history modelling and the confirmation of vitrinite reflectance suppression has enahled revised estimates of present maturity to he made.
Systematic assessment of combustion characteristics of biofuels and emulsions with water for use as diesel engine fuels 97lO4508
Crookes, R. .I. et ul. Enew Cortrer.~. Mgmr, lY97. 3X. (1.5-17). 17X5-17YS. The combustion performance of hiofuel oils, hlends with diesel fuel and emulsions with water has been investigated using a variety of experimental techniques. Photographic examination of single droplets demonstrated similar burning rates to diesel fuel. High speed records revealed the explosive combustion of oil-water emulsion droplets. Spray-flame photography showed up the poor combustion efficiency at atmospheric pressure of the seed oils compared with diesel fuel. Combustion of sprays at elevated pressure, in a steady-flow combustor, of fuels. hlends and emulsions showed improved combustion under these conditions though still poorer for vegetable oil than for diesel fuel. Soot formation levels were also higher. though these were reduced hy emulsification with water. Under the more extreme conditions of the environment in a diesel engine combustion chamber, the performance of a commercially available hiofucl matched more closely that of diesel fuel. In single-cylinder engine tests at relatively low power and speed, the ignition delay was longer for the hiofuel. The difference became less at higher loads and speeds and also in a production line multi-cylinder engine under normal operating conditions. Soot levels were generally higher than for diesel fuel and oxides of nitrogen lower. Unlike most operating modifications which result in a trade-off hetween these species, emulsification of the hiofuel with water reduced levels of both soot and oxides of nitrogen.
Transport,
Refining,
Quality,
Storage
97104509 Cobalt-based ultrafine catalysts to synthesize longchain hydrocarbons-effect of reduction temperature Zhang, Y. et crl. Fmzi Cuihun, 1997, 11, (3). 203-208. (In Chinese) Ultrafine catalysts of aerogel SiOz powder, ZrOz-SiOz ultrafine complex oxide and CoiZrOa-SiOz were prepared. Effect of reduction temperature on F-T synthesis properties of the catalyst was investigated. The most suitable reduction temperature for CoiZrOzSiO? to synthesize Ci+ products was 400°C.
Continuous using aqueous base
97104510
in-situ process for upgrading
heavy oil
Brons, G. B. and Myers R. D. Can. Pat. Appl. CA 2,174,463 (Cl. ClOGlY/ 02) 3 Nov 1996. US Appl. 433,907, 2 May 1995, 20 pp. This innovation is a continuous in-situ process for the removal of organically bound sulfur in the form of mercaptans, sulfides and thiophenes. heteroatoms from heavy oils. The process involves contacting a heavy oil with aqueous sodium hydroxide at 3X0-450°C for a time sufficient to form sodium sulfide. The sodium sulfide is then contacted with water and a transition metal for a time and at a temperature sufficient to form transition metal sulfide, sodium hydroxide, hydrogen and impurities and the sodium hydroxide is recycled to the beginning of the process. The transition metal sulfide and the impurities wherein the impurities are iron, vanadium and nickel, are removed. Molecular hydrogen may optionally be added in the first step. The present invention is useful in removing organically-bound sulfur that has been recognized to he difficult to remove,
Fuel and Energy Abstracts
November
1997
391