As compared to the device developed by our predecessors, the newly developed adsorbed gas degasification-collection device has a series of advantages such as wide sample application range, large sample inlet, high vac...As compared to the device developed by our predecessors, the newly developed adsorbed gas degasification-collection device has a series of advantages such as wide sample application range, large sample inlet, high vacuum, short-time sample smashing, low crushing temperature and water-free gas collection, which ensure the geochemical characteristics of acquired adsorbed gas samples to be the same as those of the adsorbed gases on corresponding hydrocarbon-source rocks. The results showed that the acquired adsorbed gases are composed mainly of hydrocarbon gas and carbon dioxide gas, with the hydrocarbon gas accounting for more than 80%, and can be measured reliably for their δ13C1-δ13C3 data, even δ13C4-δ13C5 data. The results of carbon isotope test and analysis satisfy the needs for the geochemical study and application of adsorbed gases. The above new techniques of experimental geochemistry are helpful for establishing the new direct natural gas-source correlation method, proving that the previous usual method of indirect natural gas-source correlation is scientific and authentic, thus providing the experimental basis for the study and application of adsorbed gases on hydrocarbon-source rocks.展开更多
Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mecha...Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mechanism of carbon isotopes and the causes of abnormal carbon isotopic compositions of natural gas.At the heating rates of 2℃/h(slow)and 20℃/h(rapid),the low maturity coal samples of the Ordos Basin had the maximum yields of alkane gas of 302.74 mL/g and 230.16 mL/g,theδ13C1 ranges of-34.8‰to-23.6‰and-35.5‰to-24.0‰;δ13C2 ranges of-28.0‰to-9.0‰and-28.9‰to-8.3‰;andδ13C3 ranges of-25.8‰to-14.7‰and-26.4‰to-13.2‰,respectively.Alkane gas in the thermal simulation products of rapid temperature rise process showed obvious partial reversal of carbon isotope series at 550℃,and at other temperatures showed positive carbon isotope series.In the two heating processes,theδ13C1 turned lighter first and then heavier,and the non-monotonic variation of theδ13C1 values is because the early CH4 is from different parent materials resulted from heterogeneity of organic matter or the carbon isotope fractionation formed by activation energy difference of early enriched 12CH4 and late enriched 13CH4.The reversal of carbon isotope values of heavy hydrocarbon gas can occur not only in high to over mature shale gas(oil-type gas),but also in coal-derived gas.Through thermal simulation experiment of toluene,it is confirmed that the carbon isotope value of heavy hydrocarbon gas can be reversed and inversed at high to over mature stage.The isotope fractionation effect caused by demethylation and methyl linkage of aromatic hydrocarbons may be an important reason for carbon isotope inversion and reversal of alkane gas at the high to over mature stage.展开更多
Carbon isotopic compositions of atmospheric Non-methane Hydrocarbons(NMHCs) in the urban areas of Taiyuan and Lanzhou in summer were reported and the sources of NMHCs are discussed.Carbon isotopic ratios(δ 13C) of ve...Carbon isotopic compositions of atmospheric Non-methane Hydrocarbons(NMHCs) in the urban areas of Taiyuan and Lanzhou in summer were reported and the sources of NMHCs are discussed.Carbon isotopic ratios(δ 13C) of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust were also measured with thermal desorption-gas chromatography-isotope ratio-mass spectrometry(TD-GC-IR-MS).δ 13C values of NMHCs in the urban areas of Lanzhou and Taiyuan range from-32.3‰ to-22.3‰ and from-32.8‰ to-18.1‰.δ 13C values of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust are-32.6‰―-21.7‰,-24.5‰―-22.3‰,-32.5‰―-27.4‰ and-31.6‰―-24.5‰,respectively.The data indicate that vehicle exhaust and cooking exhaust make a significant contribution to the atmospheric NMHCs.Therefore,to reduce emissions of vehicle exhaust and cook-ing exhaust is critical for controlling atmospheric NMHCs pollution in summer.展开更多
The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abun...The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abundant CO2 in the pyrolysates has a remarkable effect on the determination of CH4δ13C. Running cryogenically with an initial temperature of -40℃ can effectively eliminate the effect. In addition, it conduces to measuring the δ13C of C2+ hydrocarbons by increasing the injection volume and/or absorbing CO2 with the solution of sodium hydroxide. The above measures will help to get the carbon isotopic composition of C1-C7 components, which is of great significance for gas/source rock correlation and for study on the genesis of natural gas.展开更多
The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed ...The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed in gold tube in a limited system. The experimental results indicated that oil asphaltene from Lunnan area had relatively high generation potential of methane. However, the molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons in the hydrocarbon generation of oil asphaltene exhibited different characteristics from that of gas hydrocarbons by primary cracking of kerogen and secondary cracking of oil. Based on kinetic simulation with paleo-geothermal data of oil reservoir, the methane produced by cracking of oil asphatene was characterized by relatively light carbon isotopic compositions. This result could not explain relatively heavy carbon isotopic compositions of natural gas from Lunnan area. Pyrolysis of kerogen from source rocks under very high temperature展开更多
基金financially supported jointly by the National Natural Science Foundation of China (No. 41102090)the National Key Basic Research Planning Project (No.2012CB214801)the Important National Oil & Gas Special Project (No. 2011ZX05005-001)
文摘As compared to the device developed by our predecessors, the newly developed adsorbed gas degasification-collection device has a series of advantages such as wide sample application range, large sample inlet, high vacuum, short-time sample smashing, low crushing temperature and water-free gas collection, which ensure the geochemical characteristics of acquired adsorbed gas samples to be the same as those of the adsorbed gases on corresponding hydrocarbon-source rocks. The results showed that the acquired adsorbed gases are composed mainly of hydrocarbon gas and carbon dioxide gas, with the hydrocarbon gas accounting for more than 80%, and can be measured reliably for their δ13C1-δ13C3 data, even δ13C4-δ13C5 data. The results of carbon isotope test and analysis satisfy the needs for the geochemical study and application of adsorbed gases. The above new techniques of experimental geochemistry are helpful for establishing the new direct natural gas-source correlation method, proving that the previous usual method of indirect natural gas-source correlation is scientific and authentic, thus providing the experimental basis for the study and application of adsorbed gases on hydrocarbon-source rocks.
基金Supported by the National Natural Science Foundation of China(41902160,41625009)the China Postdoctoral Science Foundation(2019M650967,2020T130721)the China National Science and Technology Major Project(2016ZX05007-001)
文摘Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mechanism of carbon isotopes and the causes of abnormal carbon isotopic compositions of natural gas.At the heating rates of 2℃/h(slow)and 20℃/h(rapid),the low maturity coal samples of the Ordos Basin had the maximum yields of alkane gas of 302.74 mL/g and 230.16 mL/g,theδ13C1 ranges of-34.8‰to-23.6‰and-35.5‰to-24.0‰;δ13C2 ranges of-28.0‰to-9.0‰and-28.9‰to-8.3‰;andδ13C3 ranges of-25.8‰to-14.7‰and-26.4‰to-13.2‰,respectively.Alkane gas in the thermal simulation products of rapid temperature rise process showed obvious partial reversal of carbon isotope series at 550℃,and at other temperatures showed positive carbon isotope series.In the two heating processes,theδ13C1 turned lighter first and then heavier,and the non-monotonic variation of theδ13C1 values is because the early CH4 is from different parent materials resulted from heterogeneity of organic matter or the carbon isotope fractionation formed by activation energy difference of early enriched 12CH4 and late enriched 13CH4.The reversal of carbon isotope values of heavy hydrocarbon gas can occur not only in high to over mature shale gas(oil-type gas),but also in coal-derived gas.Through thermal simulation experiment of toluene,it is confirmed that the carbon isotope value of heavy hydrocarbon gas can be reversed and inversed at high to over mature stage.The isotope fractionation effect caused by demethylation and methyl linkage of aromatic hydrocarbons may be an important reason for carbon isotope inversion and reversal of alkane gas at the high to over mature stage.
基金Supported by National Natural Science Foundation of China (Grant No. 40673004)
文摘Carbon isotopic compositions of atmospheric Non-methane Hydrocarbons(NMHCs) in the urban areas of Taiyuan and Lanzhou in summer were reported and the sources of NMHCs are discussed.Carbon isotopic ratios(δ 13C) of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust were also measured with thermal desorption-gas chromatography-isotope ratio-mass spectrometry(TD-GC-IR-MS).δ 13C values of NMHCs in the urban areas of Lanzhou and Taiyuan range from-32.3‰ to-22.3‰ and from-32.8‰ to-18.1‰.δ 13C values of vehicle exhaust,coal-combustion exhaust,fuel volatiles and cooking exhaust are-32.6‰―-21.7‰,-24.5‰―-22.3‰,-32.5‰―-27.4‰ and-31.6‰―-24.5‰,respectively.The data indicate that vehicle exhaust and cooking exhaust make a significant contribution to the atmospheric NMHCs.Therefore,to reduce emissions of vehicle exhaust and cook-ing exhaust is critical for controlling atmospheric NMHCs pollution in summer.
文摘The carbon isotopic composition of individual light hydrocarbons generated from source rocks that had been pyrolysed in vacuum glass tube were determined by using the GC-IRMS techniques. The results indicate that abundant CO2 in the pyrolysates has a remarkable effect on the determination of CH4δ13C. Running cryogenically with an initial temperature of -40℃ can effectively eliminate the effect. In addition, it conduces to measuring the δ13C of C2+ hydrocarbons by increasing the injection volume and/or absorbing CO2 with the solution of sodium hydroxide. The above measures will help to get the carbon isotopic composition of C1-C7 components, which is of great significance for gas/source rock correlation and for study on the genesis of natural gas.
文摘The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed in gold tube in a limited system. The experimental results indicated that oil asphaltene from Lunnan area had relatively high generation potential of methane. However, the molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons in the hydrocarbon generation of oil asphaltene exhibited different characteristics from that of gas hydrocarbons by primary cracking of kerogen and secondary cracking of oil. Based on kinetic simulation with paleo-geothermal data of oil reservoir, the methane produced by cracking of oil asphatene was characterized by relatively light carbon isotopic compositions. This result could not explain relatively heavy carbon isotopic compositions of natural gas from Lunnan area. Pyrolysis of kerogen from source rocks under very high temperature
