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02353 NMR and DSC studies of base oils
02 liquid
fuels (sources, properties,
recovery,)
A thermogravimetric investigation took place into the influences of amount and conditions of the colloid disperse phase, such as asphaltenes and resinous substances on boiling behaviour and evaporation enthalpy important for the design of distillation apparatuses, by heating rates of 5, 10 and 20 Wmin. Measurements are executed on reduced crude, short residue and visbreaker residue with and without various portions of asphaltenes to show their influence. The results are discussed on the basis of an Arrhenius approach considering the influence of heating intensity and activation energy on sampling gravimetric material loss. It is shown that the presence of colloids is needed even for the evaporation enthalpy. 00102351 Investigation of oil-shale pyrolysis processing conditions using thermogravimetric analysis Williams, P. T. and Ahmad, N. Applied Energy. 2000. 66. (2). 113-133. Four oil-shale samples from two regions of Pakistan have been pyrolysed in a thermogravimetric analyser (TGA) in relation to heating rate and temperature using non-isothermal and isothermal analysis, ryspectively. to a final The heating rates investigated in the TGA were 5-40 K min temperature of 950°C. The main region of weight loss corresponding to hydrocarbon oil and gas release was between 200 and 62O’C and at higher temperatures, significant weight loss was attributed to carbonate decomposition. It was found that for the oil-shale samples analysed in the TGA, increasing the heating rate shifted the reaction to higher temperatures. The final temperature of the pyrolysis was investigated using the iso-thermal TGA. The temperature range studied was from 350 to 485°C. The data were analysed to determine the kinetic parameters of activation energy and frequency factor using two methods, the Arrhenius and Coats-Redfern analyses. The order of reaction was determined as unity. There was no clear relationship between activation energy and heating rate. The CoatsRedfern method of analysis gave consistently lower values of activation energy compared with the Arrhenius method. Isothermal analysis gave similar results to those obtained using the non-isothermal analysis. Measurement of specific heat capacity at low 00/02352 temperature of gasoline fractions with DSC Fang, W. et (II. Timranyi Hucrgong, 1999, 24, (I), 55-60. (In Chtnese) Measurements of the specific heat capacities of five gasoline fractions were taken at temperatures from 243 K to 299 K by a differential scanning calorimeter (DSC). The experimental data were compared with the prediction results of specific heat capacity from some calculation models often used in foreign engine design. The enthalpies at the corresponding temperatures estimated from the data of specific heat capacity for these gasoline fractions were also presented and they were in satisfactory agreement with those measured at high temperatures by a dropping copper-block calorimeter. 00102353 NMR and DSC studies of base oils Adhvaryu, A. ef al. TrihoTrsl, 1999, 5, (3). 313-320. An indication of the behaviour of a base oil matrix in a dynamic system is given by the effect of its composition on additive response. In this paper, a novel method involving quantifiable ‘H and 13C NMR to explain the molecular chemical of base oil is used. Oxidative degradation of base oils (neat as well as additive-containing) was studied by using DSC. In order to get a clear understanding of additive response in a matrix of different hydrocarbon oils the results are explained in terms of molecular composition of the different base stocks. 00/02354 Organic fuels: composition and formation enthalpy. Part II-resins, charcoal, pitch, gilsonite, and waxes Meyerriecks, W. J. P.vrurech, 1999, 9, I-19. A review is given of the composition and thermodynamic and thermochemical properties of pyrotechnic fuels that are ill-defined mixtures or have unknown or variable chemical formulas that make them difficult to be evaluated by molecular formula-based free-energy-minimization-type computer programmes (e.g. to determine combustion enthalpies). A number of organic fuels used in pyrotechnics were evaluated from the perspective of establishing useful chemical formulas and formation enthalpies. Oxidative desulfurization of liquids containing 00/02355 organic sulfur compounds Kabe, T. Jpn. Kokai Tokkyo Koho JP 11 140,462 [99 140,462] (Cl. ClOG271 12), 25 May 1999, Appl. 971322,109, 7 Nov 1997. 4. (In Japanese) In this process, the desulfurization involves (1) adding oxidizers into liquid containing organic sulfur compounds and then heating to catalytically oxidize the sulfur compound to sulfoxides or sulfones, and (2) separating and removing the sulfoxides or sulfones, wherein the oxidizers selected from organic peroxides, organic hypochloric acid compounds; and organic hypobromic acid compounds are added at an amount equal to or larger than the stoichiometrically required amount. The oxidation is carried in the presence of solid catalysts at a temperature equal to or above a room temperature below the thermal decomposition temperature of the oxidizers. The method is applicable for (hydrodesulfurized) fossil fuels. 00/02356 Pyrolysis of the Moroccan (Tarfaya) oil shales under microwave irradiation El harfi, K. Fuel, 2000, 79, (7). 733-742. The pyrolysis studies of the Tarfaya (Morocco) oil shales were performed using an installation specially adapted to the pyrolysis of oil shale under microwave irradiation. The microwave cavity and the reactor were designed
268
Fuel and Energy Abstracts
September
2000
to assure a good transfer of the microwave energy to the material and, to study the pyrolysis of the oil shales. The results obtained revealed that this process can be efficiently used for the purpose. The formation of oil seems related to the dehydration of the shale and to the relaxation of pyrite and the products of the degradation of the kerogen. In addition, the obtained oil has interesting characteristics. It is more maltenic, less polar and contains less sulfur and nitrogen than the oils obtained by conventional pyrolysis. 00/02357 Solvent effect on the extraction of Beypazari oil shale Olukcu, N. er al. Energy Fwls. 1999, 13, (4), X95-902. Supercritical flutd extraction with water and toluene separation of Beypazari oil shale is presented. SCW (supercritical water) gave a higher conversion degree of kerogen in oil shale than SCT (supercritical toluene), whereas oil yield in SCT was 41% more than that in SCW. From SCW the oils obtained had a greater percentage of ashphaltenic and polar in SCT oils with compounds, Although the polar contents decreased increasing temperature, they increased in SCW oils. Non-alkenes-1 were observed in the aliphatic fraction of SCW extraction oil. The temperature affected the isomerization of aliphatics in SCT oils. The temperature of both supercritical fluids affected the molecular weight of the oils. 00102358 Structure analysis of oil shale and the of fuel production technology. Sate, S. h’mrro o~vohi Nnd~o, 1999. 66, (2), 99-105. (In The results of the hydrodenitrogenation (HDN) reaction Condor crude shale oil and Arabian light middle distillates in this report. The removal rates of nitrogen from oil shale of the type of nitrogen, such as basic or non-basic.
development Japanese) of 1:l mixture of are summarized are independent
00102359 Supercritical fluid extraction of Moroccan (Timahdit) oil shale with water El Harfi, K. et al. J. And. Appl. Pydysis, 1999, SO, (2) 163-174. Supercritical water extraction was performed on Timahdit oil shale. The results reveal significant differences in oil yields and composition when compared with those obtained from conventional pyrolysis. In addition, the effect of temperature and residence time on the supercritical water extraction of oil was investigated in a set of three experiments. As the temperature increased from 380 to 400°C the yield and the fraction of aromatic and paraffins increased while the asphaltenes decreased. The yield and the fraction of asphaltenes and polar compounds were affected by the residence time. 00/02360 Systematic wettability alteration by aging sandstone and carbonate rock in crude oil Graue, A. Journul of Pe/roleum Science und Engineering, 1999, 24, (2-4), 85-97. A reproducible method for selectively altering the wettability of outcrop chalk has been established to obtain stable wettability conditions in the range from strongly water-wet to near-neutral-wet. Ageing in different oils and the response to ageing in different rocks are reported. The influence of different initial water saturations on the role of wettability alterations has been evaluated. Core plugs were aged in oil, at 9o”C, for different time periods in duplicate sets. Oil recovery by spontaneous room temperature imbibition, followed by a waterflood, was studied for aged cores, to obtain Amott-Harvey wettability index to water. The procedure was also performed on cores containing aged crude oil, on cores where the aged crude otl was exchanged with fresh crude oil after ageing was completed, but before imbibition testing and for cores where the crude oil was exchanged with decahydronaphthalene which was then displaced by ndecane. Imbibition in water-wet cores with n-decane was used as the baseline experiment. A consistent and reproducible change in wettability, from.strongly water-wet to a near-neutral-wet state, with increased ageing time was observed for five dtfferent outcrop chalks. The altered wettability was stable over several flooding cycles but when the aged crude oil was exchanged by fresh crude oil or decane after ageing but before imbibition, results exhibited different but consistent Amott indices. Exchanging crude oil at temperature with decalin, which in turn was exchanged with decane, was found to be the best procedure for reproducible and stable wettability alteration. gO/VT61
The Tazhong
hybrid petroleum
system,
Tarim Basin,
Xiao, X. Marine und Perroktrm Geology, 2000, 17, (I), I-12. The Tazhong petroleum system is geographically located in the central Tarim Basin, including the Tazhong Uplift, the North Slope and the southern area of the Manjiaer Depression. The total thickness of early Palaeozoic to Cenozoic sediments reaches 6500-9500 m. The Manjiaer Depression and the North Slope are the two major petroleum source areas with three sets of source rocks: Cambrian black shales and Ordovician dark carbonates of the Manjiaer Depression and Ordovician argillaceous limestones of the North Slope. There are three sets of reservoir-cap rock combinations in this petroleum system. The main periods for oil generation from these source rocks occurred during the middle Silurian to Early Devonian, late Carboniferous to Early Triassic and Tertiary. There were three corresponding phases of petroleum migration. Well-developed thrust faults and unconformity surfaces in this area provided the main pathways for petroleum migration. As some of the faults cut through all the lower Palaeozoic strata, the oil in any given reservoir rock may be actually a mixture of oils from different sources, complicating the origin and
fuels (sources, properties,
recovery,)
A thermogravimetric investigation took place into the influences of amount and conditions of the colloid disperse phase, such as asphaltenes and resinous substances on boiling behaviour and evaporation enthalpy important for the design of distillation apparatuses, by heating rates of 5, 10 and 20 Wmin. Measurements are executed on reduced crude, short residue and visbreaker residue with and without various portions of asphaltenes to show their influence. The results are discussed on the basis of an Arrhenius approach considering the influence of heating intensity and activation energy on sampling gravimetric material loss. It is shown that the presence of colloids is needed even for the evaporation enthalpy. 00102351 Investigation of oil-shale pyrolysis processing conditions using thermogravimetric analysis Williams, P. T. and Ahmad, N. Applied Energy. 2000. 66. (2). 113-133. Four oil-shale samples from two regions of Pakistan have been pyrolysed in a thermogravimetric analyser (TGA) in relation to heating rate and temperature using non-isothermal and isothermal analysis, ryspectively. to a final The heating rates investigated in the TGA were 5-40 K min temperature of 950°C. The main region of weight loss corresponding to hydrocarbon oil and gas release was between 200 and 62O’C and at higher temperatures, significant weight loss was attributed to carbonate decomposition. It was found that for the oil-shale samples analysed in the TGA, increasing the heating rate shifted the reaction to higher temperatures. The final temperature of the pyrolysis was investigated using the iso-thermal TGA. The temperature range studied was from 350 to 485°C. The data were analysed to determine the kinetic parameters of activation energy and frequency factor using two methods, the Arrhenius and Coats-Redfern analyses. The order of reaction was determined as unity. There was no clear relationship between activation energy and heating rate. The CoatsRedfern method of analysis gave consistently lower values of activation energy compared with the Arrhenius method. Isothermal analysis gave similar results to those obtained using the non-isothermal analysis. Measurement of specific heat capacity at low 00/02352 temperature of gasoline fractions with DSC Fang, W. et (II. Timranyi Hucrgong, 1999, 24, (I), 55-60. (In Chtnese) Measurements of the specific heat capacities of five gasoline fractions were taken at temperatures from 243 K to 299 K by a differential scanning calorimeter (DSC). The experimental data were compared with the prediction results of specific heat capacity from some calculation models often used in foreign engine design. The enthalpies at the corresponding temperatures estimated from the data of specific heat capacity for these gasoline fractions were also presented and they were in satisfactory agreement with those measured at high temperatures by a dropping copper-block calorimeter. 00102353 NMR and DSC studies of base oils Adhvaryu, A. ef al. TrihoTrsl, 1999, 5, (3). 313-320. An indication of the behaviour of a base oil matrix in a dynamic system is given by the effect of its composition on additive response. In this paper, a novel method involving quantifiable ‘H and 13C NMR to explain the molecular chemical of base oil is used. Oxidative degradation of base oils (neat as well as additive-containing) was studied by using DSC. In order to get a clear understanding of additive response in a matrix of different hydrocarbon oils the results are explained in terms of molecular composition of the different base stocks. 00/02354 Organic fuels: composition and formation enthalpy. Part II-resins, charcoal, pitch, gilsonite, and waxes Meyerriecks, W. J. P.vrurech, 1999, 9, I-19. A review is given of the composition and thermodynamic and thermochemical properties of pyrotechnic fuels that are ill-defined mixtures or have unknown or variable chemical formulas that make them difficult to be evaluated by molecular formula-based free-energy-minimization-type computer programmes (e.g. to determine combustion enthalpies). A number of organic fuels used in pyrotechnics were evaluated from the perspective of establishing useful chemical formulas and formation enthalpies. Oxidative desulfurization of liquids containing 00/02355 organic sulfur compounds Kabe, T. Jpn. Kokai Tokkyo Koho JP 11 140,462 [99 140,462] (Cl. ClOG271 12), 25 May 1999, Appl. 971322,109, 7 Nov 1997. 4. (In Japanese) In this process, the desulfurization involves (1) adding oxidizers into liquid containing organic sulfur compounds and then heating to catalytically oxidize the sulfur compound to sulfoxides or sulfones, and (2) separating and removing the sulfoxides or sulfones, wherein the oxidizers selected from organic peroxides, organic hypochloric acid compounds; and organic hypobromic acid compounds are added at an amount equal to or larger than the stoichiometrically required amount. The oxidation is carried in the presence of solid catalysts at a temperature equal to or above a room temperature below the thermal decomposition temperature of the oxidizers. The method is applicable for (hydrodesulfurized) fossil fuels. 00/02356 Pyrolysis of the Moroccan (Tarfaya) oil shales under microwave irradiation El harfi, K. Fuel, 2000, 79, (7). 733-742. The pyrolysis studies of the Tarfaya (Morocco) oil shales were performed using an installation specially adapted to the pyrolysis of oil shale under microwave irradiation. The microwave cavity and the reactor were designed
268
Fuel and Energy Abstracts
September
2000
to assure a good transfer of the microwave energy to the material and, to study the pyrolysis of the oil shales. The results obtained revealed that this process can be efficiently used for the purpose. The formation of oil seems related to the dehydration of the shale and to the relaxation of pyrite and the products of the degradation of the kerogen. In addition, the obtained oil has interesting characteristics. It is more maltenic, less polar and contains less sulfur and nitrogen than the oils obtained by conventional pyrolysis. 00/02357 Solvent effect on the extraction of Beypazari oil shale Olukcu, N. er al. Energy Fwls. 1999, 13, (4), X95-902. Supercritical flutd extraction with water and toluene separation of Beypazari oil shale is presented. SCW (supercritical water) gave a higher conversion degree of kerogen in oil shale than SCT (supercritical toluene), whereas oil yield in SCT was 41% more than that in SCW. From SCW the oils obtained had a greater percentage of ashphaltenic and polar in SCT oils with compounds, Although the polar contents decreased increasing temperature, they increased in SCW oils. Non-alkenes-1 were observed in the aliphatic fraction of SCW extraction oil. The temperature affected the isomerization of aliphatics in SCT oils. The temperature of both supercritical fluids affected the molecular weight of the oils. 00102358 Structure analysis of oil shale and the of fuel production technology. Sate, S. h’mrro o~vohi Nnd~o, 1999. 66, (2), 99-105. (In The results of the hydrodenitrogenation (HDN) reaction Condor crude shale oil and Arabian light middle distillates in this report. The removal rates of nitrogen from oil shale of the type of nitrogen, such as basic or non-basic.
development Japanese) of 1:l mixture of are summarized are independent
00102359 Supercritical fluid extraction of Moroccan (Timahdit) oil shale with water El Harfi, K. et al. J. And. Appl. Pydysis, 1999, SO, (2) 163-174. Supercritical water extraction was performed on Timahdit oil shale. The results reveal significant differences in oil yields and composition when compared with those obtained from conventional pyrolysis. In addition, the effect of temperature and residence time on the supercritical water extraction of oil was investigated in a set of three experiments. As the temperature increased from 380 to 400°C the yield and the fraction of aromatic and paraffins increased while the asphaltenes decreased. The yield and the fraction of asphaltenes and polar compounds were affected by the residence time. 00/02360 Systematic wettability alteration by aging sandstone and carbonate rock in crude oil Graue, A. Journul of Pe/roleum Science und Engineering, 1999, 24, (2-4), 85-97. A reproducible method for selectively altering the wettability of outcrop chalk has been established to obtain stable wettability conditions in the range from strongly water-wet to near-neutral-wet. Ageing in different oils and the response to ageing in different rocks are reported. The influence of different initial water saturations on the role of wettability alterations has been evaluated. Core plugs were aged in oil, at 9o”C, for different time periods in duplicate sets. Oil recovery by spontaneous room temperature imbibition, followed by a waterflood, was studied for aged cores, to obtain Amott-Harvey wettability index to water. The procedure was also performed on cores containing aged crude oil, on cores where the aged crude otl was exchanged with fresh crude oil after ageing was completed, but before imbibition testing and for cores where the crude oil was exchanged with decahydronaphthalene which was then displaced by ndecane. Imbibition in water-wet cores with n-decane was used as the baseline experiment. A consistent and reproducible change in wettability, from.strongly water-wet to a near-neutral-wet state, with increased ageing time was observed for five dtfferent outcrop chalks. The altered wettability was stable over several flooding cycles but when the aged crude oil was exchanged by fresh crude oil or decane after ageing but before imbibition, results exhibited different but consistent Amott indices. Exchanging crude oil at temperature with decalin, which in turn was exchanged with decane, was found to be the best procedure for reproducible and stable wettability alteration. gO/VT61
The Tazhong
hybrid petroleum
system,
Tarim Basin,
Xiao, X. Marine und Perroktrm Geology, 2000, 17, (I), I-12. The Tazhong petroleum system is geographically located in the central Tarim Basin, including the Tazhong Uplift, the North Slope and the southern area of the Manjiaer Depression. The total thickness of early Palaeozoic to Cenozoic sediments reaches 6500-9500 m. The Manjiaer Depression and the North Slope are the two major petroleum source areas with three sets of source rocks: Cambrian black shales and Ordovician dark carbonates of the Manjiaer Depression and Ordovician argillaceous limestones of the North Slope. There are three sets of reservoir-cap rock combinations in this petroleum system. The main periods for oil generation from these source rocks occurred during the middle Silurian to Early Devonian, late Carboniferous to Early Triassic and Tertiary. There were three corresponding phases of petroleum migration. Well-developed thrust faults and unconformity surfaces in this area provided the main pathways for petroleum migration. As some of the faults cut through all the lower Palaeozoic strata, the oil in any given reservoir rock may be actually a mixture of oils from different sources, complicating the origin and