In China, hot researches on shale oil were raised by the important breakthrough of shale oil in America. Obviously, the first important issue is the actual shale oil resource potential of China, and the selection of t...In China, hot researches on shale oil were raised by the important breakthrough of shale oil in America. Obviously, the first important issue is the actual shale oil resource potential of China, and the selection of the key appraisement parameter is vital to the shale oil resource amount. Among the appraisement parameters, the oil content parameter(S1) is the key one, but the evaluation result is generally lower because of light hydrocarbon losing and heavy hydrocarbon handling. And the more important thing is that the light hydrocarbon with small molecular weight is more recoverable, and therefore its amount is important to the total shale oil yields. Based on pyrolysis experiments and the kinetic model of hydrocarbon generation, correction factors and a model of light hydrocarbon losing and heavy hydrocarbon handling were established. The results show that the correction factor of heavy hydrocarbon handling is 3.2, and that of light hydrocarbon losing is controlled by kerogen type, maturity and hydrocarbon generation environment(closed or open).展开更多
In order to verify whether any special gas component exists in outburst samples or not, coal samples from both outburst coal seams and non-outburst coal seams were collected. Some gases were extracted from the samples...In order to verify whether any special gas component exists in outburst samples or not, coal samples from both outburst coal seams and non-outburst coal seams were collected. Some gases were extracted from the samples and analyzed qualitatively and quantitatively on chromatogram-mass spectrograph. The qualitative analysis show that there is no special gases in coal seams. And the quantitative analysis indicates that the heavy hydrocarbon content in coal samples from outburst coal seams is apparently higher than that from non-outburst district ones, which reflects the damage of geological tectonic movement to coal body in history. Therefore, the heavy hydrocarbon content of coal sample can be used as an index to predict coal outburst.展开更多
Coalbed gas (CBG) in Enhong syncline, eastern Yunnan China, is character- ized by high concentration of heavy hydrocarbon with the highest content of ethane, which is more than 30%. Some previous investigators pai...Coalbed gas (CBG) in Enhong syncline, eastern Yunnan China, is character- ized by high concentration of heavy hydrocarbon with the highest content of ethane, which is more than 30%. Some previous investigators paid much attention to the abnormal concentration of heavy hydrocar- bon in the CBG of Enhong, but few have researched on its origin. This article describes the characteristics of abnormal high concentration of heavy hydrocarbon in Enhong syncline and analyzes its reason from the aspects of origin and evolution of heavy hydrocarbon by carbon isotope, coal petrography, and coal rank. Features of gas carbon isotope composition display that there is no inorganic gas or off components in the CBG, which is classified to thermogenetic gas produced by humic material, with characteristic of secondary biogenic gas in shallow coal seam. The concentration of heavy hydrocarbon in Enhong syncline increases with the increase of vitrinite, vitrinite/inertinite ratio, and hydrogen/carbon ratio and decreases with the increase of inertinite, so hydrogen-rich vitrinite may be a very important factor resulting in the abnormal concentration of heavy hydrocarbon. It also increases with the increase of degree of coalifica-tion of coking to lean coals during which the peak of heavy hydrocarbon generation is reached. Therefore, we think that high concentration of heavy hydrocarbon originated from the coupling effect of higher content of the hydrogen-rich vitrinite in the coal and the coal rank of coking to lean coals.展开更多
16.6%Co/γ-Al2O3 catalysts prepared by incipient wetness impregnation method were used for Fischer-Tropsch synthesis. The support was pre-treated with different concentration of NH4NO3 aqueous solution. The effect of ...16.6%Co/γ-Al2O3 catalysts prepared by incipient wetness impregnation method were used for Fischer-Tropsch synthesis. The support was pre-treated with different concentration of NH4NO3 aqueous solution. The effect of support pre-treatment on the properties of support and performance of supportedcobalt-based catalysts was investigated. To treat the support with NH4NO3 aqueous solution enlarged the pore of γ-Al2O3, decreased the impurity Na2O content, and weakened the surface acidity of γ-Al2O3. The change in the properties of the support decreased the interaction between cobalt species and support, enhanced the CO hydrogenation rate and the C5+ selectivity. For all catalysts, increasing the reaction temperature increased the CO hydrogenation rate or the CO conversion, slightly decreased the total hydrocarbon selectivity, and favored the formation of methane and light hydrocarbons, while the chain growth probability decreased. For 16.6%Co/γ-Al2O3 catalysts, prepared with the support treated with 100 g/L NH4NO3 aqueous solution, the CO conversion, the CH4 selectivity, and the C5+ selectivity were 83.13%, 6.86% and 82.75% respectively, and the chain growth probability was 0.83 under the condition of 493 K, 1.5 MPa, 500 h-1 and the molar ratio of H2 to CO being 2.0 in feed.展开更多
It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity ...It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity and various chemical features.The central part of southern margin of Junggar Basin, NW China is such an example where there are condensates, light oils, normal density oils, heavy crude oils and natural gases. The formation mechanism of condensates has been seriously debated for long time;however, no study has integrated it with genetic types of waxy and heavy oils. Taking the central part of southern margin of Junggar Basin as a case, this study employs geological and geochemical methods to determine the formation mechanism of condensates,waxy and heavy oils in a complicated petroliferous area, and reveals the causes and geochemical processes of the co-occurrence of different types of crude oils in this region. Based on detailed geochemical analyses of more than 40 normal crude oils, light oils,condensates and heavy oils, it is found that the condensates are dominated by low carbon number n-alkanes and enriched in light naphthenics and aromatic hydrocarbons. Heptane values of these condensates range from 19% to 21%, isoheptane values from1.9 to 2.1, and toluene/n-heptane ratios from 1.5 to 2.0. The distribution of n-alkanes in the condensates presents a mirror image with high density waxy crude oils and heavy oils. Combined with the oil and gas-source correlations of the crude oils, condensates and natural gas, it is found that the condensates are product of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils which were derived from mature Cretaceous lacustrine source rocks in the relatively early stage. The waxy oils are the intermediate products of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils, while the heavy oils are in-situ residuals. Therefore, evaporative fractionation and/or phase-controlled fractionation would account for the formation of the condensate, light oil, waxy oil and heavy oil in the central part of southern margin of Junggar Basin, resulting in a great change of the content in terms of light alkanes, naphthenics and aromatics in condensates, followed by great uncertainties of toluene/n-heptane ratios due to migration and re-accumulation. The results suggest that the origin of the condensate cannot be simply concluded by its ratios of toluene/n-heptane and n-heptane/methylcyclohexane on the Thompson's cross-plot, it should be comprehensively determined by the aspects of geological background, thermal history of source rocks and petroleum generation,physical and chemical features of various crude oils and natural gas, vertical and lateral distribution of various crude oils in the study area.展开更多
Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite seconda...Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using co-templates of gemini surfactant[C18H37N(CH3)2(CH2)3-N(CH3)2C18H37]2+(18-3-18)and triethanolamine(TEA).X-ray Diffraction(XRD)patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed.Transmission Electron Microscopy(TEM)images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25Å.Compared with the conventionally synthesized MCM-48,the as-synthesized MCM-48 sample showed an adsorption band at 520–600 cm-1 in its FT-IR spectrum,which was assigned to five-membered ring vibration from zeolite structure.This suggested the presence of zeolite building units in the pore wall.N2 adsorption data showed that the material had a much higher specific surface area(1200 m2/g)than the conventional MCM-48(1100 m2/g).Finally,the cat-alytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons.Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the con-ventional MCM-48 catalyst.The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules.展开更多
基金supported by "the Fundamental Research Funds for the Central Universities" (14CX05017A)the Natural Science Foundation of China (41330313)+1 种基金Program for New Century Excellent Talents in Heilongjiang Provincial University (1252-NCET-012)CNPC Innovation Foundation (2011D-5006-0101)
文摘In China, hot researches on shale oil were raised by the important breakthrough of shale oil in America. Obviously, the first important issue is the actual shale oil resource potential of China, and the selection of the key appraisement parameter is vital to the shale oil resource amount. Among the appraisement parameters, the oil content parameter(S1) is the key one, but the evaluation result is generally lower because of light hydrocarbon losing and heavy hydrocarbon handling. And the more important thing is that the light hydrocarbon with small molecular weight is more recoverable, and therefore its amount is important to the total shale oil yields. Based on pyrolysis experiments and the kinetic model of hydrocarbon generation, correction factors and a model of light hydrocarbon losing and heavy hydrocarbon handling were established. The results show that the correction factor of heavy hydrocarbon handling is 3.2, and that of light hydrocarbon losing is controlled by kerogen type, maturity and hydrocarbon generation environment(closed or open).
文摘In order to verify whether any special gas component exists in outburst samples or not, coal samples from both outburst coal seams and non-outburst coal seams were collected. Some gases were extracted from the samples and analyzed qualitatively and quantitatively on chromatogram-mass spectrograph. The qualitative analysis show that there is no special gases in coal seams. And the quantitative analysis indicates that the heavy hydrocarbon content in coal samples from outburst coal seams is apparently higher than that from non-outburst district ones, which reflects the damage of geological tectonic movement to coal body in history. Therefore, the heavy hydrocarbon content of coal sample can be used as an index to predict coal outburst.
基金supported by the National Natural Science Foundation of China (No.40730422)the National Science and Technology Key Special Project of China (No.2011ZX05034)the Fundamental Research Funds for the Central Universities of China (No.2010QNA51)
文摘Coalbed gas (CBG) in Enhong syncline, eastern Yunnan China, is character- ized by high concentration of heavy hydrocarbon with the highest content of ethane, which is more than 30%. Some previous investigators paid much attention to the abnormal concentration of heavy hydrocar- bon in the CBG of Enhong, but few have researched on its origin. This article describes the characteristics of abnormal high concentration of heavy hydrocarbon in Enhong syncline and analyzes its reason from the aspects of origin and evolution of heavy hydrocarbon by carbon isotope, coal petrography, and coal rank. Features of gas carbon isotope composition display that there is no inorganic gas or off components in the CBG, which is classified to thermogenetic gas produced by humic material, with characteristic of secondary biogenic gas in shallow coal seam. The concentration of heavy hydrocarbon in Enhong syncline increases with the increase of vitrinite, vitrinite/inertinite ratio, and hydrogen/carbon ratio and decreases with the increase of inertinite, so hydrogen-rich vitrinite may be a very important factor resulting in the abnormal concentration of heavy hydrocarbon. It also increases with the increase of degree of coalifica-tion of coking to lean coals during which the peak of heavy hydrocarbon generation is reached. Therefore, we think that high concentration of heavy hydrocarbon originated from the coupling effect of higher content of the hydrogen-rich vitrinite in the coal and the coal rank of coking to lean coals.
基金This work was supported by the Doctoral Foundation of China(No.20050251006).
文摘16.6%Co/γ-Al2O3 catalysts prepared by incipient wetness impregnation method were used for Fischer-Tropsch synthesis. The support was pre-treated with different concentration of NH4NO3 aqueous solution. The effect of support pre-treatment on the properties of support and performance of supportedcobalt-based catalysts was investigated. To treat the support with NH4NO3 aqueous solution enlarged the pore of γ-Al2O3, decreased the impurity Na2O content, and weakened the surface acidity of γ-Al2O3. The change in the properties of the support decreased the interaction between cobalt species and support, enhanced the CO hydrogenation rate and the C5+ selectivity. For all catalysts, increasing the reaction temperature increased the CO hydrogenation rate or the CO conversion, slightly decreased the total hydrocarbon selectivity, and favored the formation of methane and light hydrocarbons, while the chain growth probability decreased. For 16.6%Co/γ-Al2O3 catalysts, prepared with the support treated with 100 g/L NH4NO3 aqueous solution, the CO conversion, the CH4 selectivity, and the C5+ selectivity were 83.13%, 6.86% and 82.75% respectively, and the chain growth probability was 0.83 under the condition of 493 K, 1.5 MPa, 500 h-1 and the molar ratio of H2 to CO being 2.0 in feed.
基金supported by the PetroChina Science and Technology Special Projects (Grant Nos. 06-10A-01-02, 2011A-0201, 2014A-0211 and 2016A-0202)
文摘It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity and various chemical features.The central part of southern margin of Junggar Basin, NW China is such an example where there are condensates, light oils, normal density oils, heavy crude oils and natural gases. The formation mechanism of condensates has been seriously debated for long time;however, no study has integrated it with genetic types of waxy and heavy oils. Taking the central part of southern margin of Junggar Basin as a case, this study employs geological and geochemical methods to determine the formation mechanism of condensates,waxy and heavy oils in a complicated petroliferous area, and reveals the causes and geochemical processes of the co-occurrence of different types of crude oils in this region. Based on detailed geochemical analyses of more than 40 normal crude oils, light oils,condensates and heavy oils, it is found that the condensates are dominated by low carbon number n-alkanes and enriched in light naphthenics and aromatic hydrocarbons. Heptane values of these condensates range from 19% to 21%, isoheptane values from1.9 to 2.1, and toluene/n-heptane ratios from 1.5 to 2.0. The distribution of n-alkanes in the condensates presents a mirror image with high density waxy crude oils and heavy oils. Combined with the oil and gas-source correlations of the crude oils, condensates and natural gas, it is found that the condensates are product of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils which were derived from mature Cretaceous lacustrine source rocks in the relatively early stage. The waxy oils are the intermediate products of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils, while the heavy oils are in-situ residuals. Therefore, evaporative fractionation and/or phase-controlled fractionation would account for the formation of the condensate, light oil, waxy oil and heavy oil in the central part of southern margin of Junggar Basin, resulting in a great change of the content in terms of light alkanes, naphthenics and aromatics in condensates, followed by great uncertainties of toluene/n-heptane ratios due to migration and re-accumulation. The results suggest that the origin of the condensate cannot be simply concluded by its ratios of toluene/n-heptane and n-heptane/methylcyclohexane on the Thompson's cross-plot, it should be comprehensively determined by the aspects of geological background, thermal history of source rocks and petroleum generation,physical and chemical features of various crude oils and natural gas, vertical and lateral distribution of various crude oils in the study area.
基金supported by National Basic Research Program of China(Grant No.2004CB217806)National Natural Science Foundation of China(Grant No.20476060)。
文摘Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using co-templates of gemini surfactant[C18H37N(CH3)2(CH2)3-N(CH3)2C18H37]2+(18-3-18)and triethanolamine(TEA).X-ray Diffraction(XRD)patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed.Transmission Electron Microscopy(TEM)images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25Å.Compared with the conventionally synthesized MCM-48,the as-synthesized MCM-48 sample showed an adsorption band at 520–600 cm-1 in its FT-IR spectrum,which was assigned to five-membered ring vibration from zeolite structure.This suggested the presence of zeolite building units in the pore wall.N2 adsorption data showed that the material had a much higher specific surface area(1200 m2/g)than the conventional MCM-48(1100 m2/g).Finally,the cat-alytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons.Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the con-ventional MCM-48 catalyst.The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules.