Mechanisms of carbon isotopic fractionation in the process of natural gas generation: Geochemical evidence from thermal simulation experiment

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.

Thermal simulation experiment of organic matter-rich shale and implication for organic pore formation and evolution

A thermal simulation experiment of diagenesis,hydrocarbon generation and evolution of the organic matter-rich shale was carried out to investigate formation and evolution of organic pores under the constraint from immature,low mature,mature,high mature to overmature geological conditions.The argon ion polishingefield emission scanning electron microscope was used to analyze microscopic features of original samples and simulated samples of various evolution stages.Results showed organic pores could be formed during hydrocarbon generation from biochemical and hypothermal processes in the immature and low mature stages,and the shale shallow-buried depth might be favorable for preservation of organic pores;the generation and evolution of organic pores were of heterogeneity,and the maturity was not a decisive factor which controlled formation and development of organic pores,while the difference in physiochemical structure of organic matter played an important role in formation and evolution of organic pores;the organic pore development was obviously related with the retained oil,and the organic pores formed in the oil generation stage were easily filled by pyrolysis asphalt;organic contraction fractures/organic marginal pores might be important storage spaces for shale gas occurrence,and their development was mainly controlled by the physiochemical structure and evolution degree of organic matters when the chemical adsorbed organic matter was converted into the physical adsorbed organic matter and the free organic matter.

Assessment of recoverable oil and gas resources by in-situ conversion of shale——Case study of extracting the Chang 7_(3) shale in the Ordos Basin

The purpose of this study is to investigate the entire evolution process of shales with various total organic contents(TOC)in order to build models for quantitative evaluation of oil and gas yields and establish methods for assessing recoverable oil and gas resources from in-situ conversion of organic matters in shale.Thermal simulation experiments under in-situ conversion conditions were conducted on Chang 7_(3) shales from the Ordos Basin in a semi-open system with large capacity.The results showed that TOC and R_(o) were the key factors affecting the in-situ transformation potential of shale.The remaining oil and gas yields increased linearly with TOC but inconsistently with R_(o).R_(o) ranged 0.75%—1.25%and 1.05%—2.3%,respectively,corresponding to the main oil generation stage and gas generation stage of shale in-situ transformation.Thus a model to evaluate the remaining oil/gas yield with TOC and R_(o) was obtained.The TOC of shale suitable for in-situ conversion should be greater than 6%,whereas its R_(o) should be less than 1.0%.Shales with 0.75%(R_(o))could obtain the best economic benefit.The results provided a theoretical basis and evaluation methodology for predicting the hydrocarbon resources from in-situ conversion of shale and for the identification of the optimum“sweet spots”.The assessment of the Chang 7_(3) shale in the Ordos Basin indicated that the recoverable oil and gas resources from in-situ conversion of organic matters in shale are substantial,with oil and gas resources reaching approximately 450×10^(8) t and 30×10^(12)m^(3),respectively,from an area of 4.27×10^(4) km^(2).

Pyrolysis of coal measure source rocks at highly to over mature stage and its geological implications

The influence of water on gas generation from humic type organic matter at highly to over mature stage was investigated with thermal simulation experiments at high temperature and pressure.The result of the experiments indicates that the effect of water on gas generation was controlled by the thermal maturity of organic matter.Water could enhance gas generation and increase hydrocarbon gas yields significantly at over mature stage of humic type organic matter.Hydrogen isotopic compositions of coal-derived gases generated at highly to over mature stage were mainly controlled by thermal maturity of source rocks,but also affected by formation water.Highly and over mature coal measure source rocks are widely distributed in China.The hydrocarbon gas generation capacity of coal measure source rocks and resource potential of coal-derived gases in deep formations would be significantly enhanced assuming that formation water could be involved in the thermal cracking of highly to over mature organic matter in real geological settings.