正构二十四烷裂解成气碳同位素动力学模拟及其地质意义

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正构二十四烷裂解成气碳同位素动力学模拟及其地质意义

靳永斌

中国科学院广州地球化学研究所广州 510640

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A Kinetic Model of Stable Carbon Isotope Ratios in Gaseous Hydrocarbons Generated from Thermal Cracking of ntetracosane and Its Geological Significance

JIN Yongbin

State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan Guangzhou 510640

摘要

摘要: 以甲烷的量子化模型及正构二十四烷(nC24)金管限定体系裂解成气实验为基础，从理论上进一步论述了量子化模型应用于重烃气体（乙烷和丙烷）碳同位素动力学模拟的适应性，计算了甲烷、乙烷及丙烷生烃动力学与碳同位素动力学参数, 重点探讨了δ13C2与δ13C3变化的主控因素。研究结果表明, nC24裂解生成的气态烃碳同位素与早期报道的nC18、nC25及原油裂解生成的气态烃碳同位素具有可比性，可应用于地质条件下解释原油裂解气的某些地球化学特征。nC24生烃地质模型表明，其在150～160℃是稳定的，主要裂解温度介于180～200℃之间，与目前所报道的原油裂解地质模型吻合。随热解程度的增加，δ13C2与δ13C3体现了比δ13C1更明显的变化。气藏充注历史控制的同位素累积效应对天然气碳同位素有很大的影响，与累积聚集气相比，阶段聚集气的δ13C变重，并在更大程度上影响了演化曲线的分异。在此基础上，应用nC24裂解成气碳同位素分馏地质模型探讨了塔里木盆地某些油气藏天然气碳同位素值变化的原因。
- 正构二十四烷 /
- 裂解成气 /
- 重烃气体 /
- 碳同位素动力学
Abstract: Based on quantitative modeling and experimental data on ntetracosane cracking to generate gaseous hydrocarbons in a confined system, we calculated the generation kinetics and carbon isotope kinetics of methane, ethane and propane and determined the main controlling factors influencing the variation of δ13C2 and δ13C3. The carbon isotope of gaseous hydrocarbons from nC24 cracking to gas are comparable to those from crude oil reported recently, and they can be used to investigate the geochemical characteristics of crude oil cracking to gas under geological conditions. The geological model of nC24 cracking suggests it is stable at 150～160℃ and its cracking temperature ranges 180℃ to 200℃, consistent with geological models of crude oil cracking currently reported. With increasing degree of thermal stress, the changes in δ13C2 and δ13C3 are larger than that of δ13C1. It is shown that isotope accumulation controlled by the recharging history of a reservoir has a considerable impact on the carbon isotope distribution of natural gas. Compared to that of cumulative gas, the carbon isotope ratio of partly accumulation gas is heavier and influences the fractionation of the δ13C2 and δ13C3 curves to a greater extent. The geological model of nC24 cracking to gas has been used to interpret the origin of carbon isotopic variation of natural gas in some reservoirs in the Tarim basin.
- ntetracosane /
- crude oil cracking gas /
- heavy hydrocarbon gas /
- carbon isotopic kinetics

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[1]	马冬晨, 王文军, 张婷, 李立武, 王作栋, 钱宇, 敖添, 符印, 王丹, 贾星亮. 正构烷烃单体碳同位素组成差异分析以塔河油田奥陶系原油为例 . 沉积学报, 2024, 42(4): 1411-1421. doi: 10.14027/j.issn.1000-0550.2022.098
[2]	王泽唐, 王超勇, 董再田, 朱昱璇. 四川盆地晚奥陶世—早志留世碳硫同位素分馏动力学模型构建 . 沉积学报, 2024, 42(6): 2054-2065. doi: 10.14027/j.issn.1000-0550.2023.036
[3]	. 柴达木盆地北缘原油中单体正构烷烃的碳、氢同位素组成研究 . 沉积学报, 2012, 30(5): 983-990.
[4]	. 原油裂解成气动力学参数及其应用研究 . 沉积学报, 2012, 30(6): 1156-1164.
[5]	. 有机质碳同位素热力学分馏与天然气碳同位素组成 . 沉积学报, 2012, 30(3): 588-593.
[6]	沈平. 我国生物气藏碳、氢同位素特征、形成途径及意义 . 沉积学报, 2010, 28(1): 183-187.
[7]	段毅. 煤层气碳同位素阶段演化的模拟实验研究及其应用 . 沉积学报, 2010, 28(2): 401-404.
[8]	卢双舫. 评价生物气生成量、生成期的碳同位素平衡法及其应用 . 沉积学报, 2008, 26(2): 308-313.
[9]	米敬奎, 刘新华, 杨孟达, 杨荣丰. 利用生烃动力学和碳同位素生烃动力学探索油气田气体来源 . 沉积学报, 2005, 23(3): 537-541.
[10]	卢鸿, 柴平霞, 孙永革, 彭平安. 轮南14井原油正构烷烃和类异戊二烯单体碳同位素研究 . 沉积学报, 2002, 20(3): 477-504.
[11]	田春志, 卢双舫, 李启明, 付晓泰, 薛海涛. 塔里木盆地原油高压条件下裂解成气的化学动力学模型及其意义 . 沉积学报, 2002, 20(3): 488-492.
[12]	孙明良. 天然气中稀有气体同位素的分析技术 . 沉积学报, 2001, 19(2): 271-272.
[13]	熊永强, 耿安松, 盛国英, 傅家谟. 生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义 . 沉积学报, 2001, 19(3): 469-473.
[14]	郑建京, 吉利明, 孟仟祥. 天然气碳同位素部分反序与乙烷碳同位素特征的模拟研究 . 沉积学报, 1999, 17(S1): 811-814.
[15]	沈忠民, 周光甲, 洪志华. 陆相低成熟烃源岩有机硫与热解成烃动力学关系初探 . 沉积学报, 1998, 16(4): 133-139.
[16]	彭林, 沈平, 文启彬. 利用正构烷烃单分子碳同位素组成对兰州大气污染源的探讨 . 沉积学报, 1998, 16(4): 158-162.
[17]	陈践发, 陈振岩, 季东民, 于深, 赵长虹, 王先彬. 辽河盆地天然气中重烃异常富集重碳同位素的成因探讨 . 沉积学报, 1998, 16(2): 5-8.
[18]	卢双舫, 陈昕, 付晓泰. 台北凹陷煤中有机质的成烃动力学模型及其初步应用 . 沉积学报, 1997, 15(2): 126-129.
[19]	张文正, 昝川莉. 烃源岩残留沥青中正构烷烃分子的碳同位素研究 . 沉积学报, 1997, 15(2): 212-215.
[20]	卢双舫, 王子文, 付晓泰, 王振平. 镜质体成烃反应动力学模型的标定及其在热史恢复中的应用 . 沉积学报, 1996, 14(4): 24-30.

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正构二十四烷裂解成气碳同位素动力学模拟及其地质意义

中国科学院广州地球化学研究所广州 510640

收稿日期: 1900-01-01

修回日期: 1900-01-01

刊出日期: 2009-06-10

关键词:

摘要: 以甲烷的量子化模型及正构二十四烷(nC24)金管限定体系裂解成气实验为基础，从理论上进一步论述了量子化模型应用于重烃气体（乙烷和丙烷）碳同位素动力学模拟的适应性，计算了甲烷、乙烷及丙烷生烃动力学与碳同位素动力学参数, 重点探讨了δ13C2与δ13C3变化的主控因素。研究结果表明, nC24裂解生成的气态烃碳同位素与早期报道的nC18、nC25及原油裂解生成的气态烃碳同位素具有可比性，可应用于地质条件下解释原油裂解气的某些地球化学特征。nC24生烃地质模型表明，其在150～160℃是稳定的，主要裂解温度介于180～200℃之间，与目前所报道的原油裂解地质模型吻合。随热解程度的增加，δ13C2与δ13C3体现了比δ13C1更明显的变化。气藏充注历史控制的同位素累积效应对天然气碳同位素有很大的影响，与累积聚集气相比，阶段聚集气的δ13C变重，并在更大程度上影响了演化曲线的分异。在此基础上，应用nC24裂解成气碳同位素分馏地质模型探讨了塔里木盆地某些油气藏天然气碳同位素值变化的原因。

A Kinetic Model of Stable Carbon Isotope Ratios in Gaseous Hydrocarbons Generated from Thermal Cracking of ntetracosane and Its Geological Significance

State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan Guangzhou 510640

Received Date: 1900-01-01

Rev Recd Date: 1900-01-01

Publish Date: 2009-06-10

Keywords:

Abstract: Based on quantitative modeling and experimental data on ntetracosane cracking to generate gaseous hydrocarbons in a confined system, we calculated the generation kinetics and carbon isotope kinetics of methane, ethane and propane and determined the main controlling factors influencing the variation of δ13C2 and δ13C3. The carbon isotope of gaseous hydrocarbons from nC24 cracking to gas are comparable to those from crude oil reported recently, and they can be used to investigate the geochemical characteristics of crude oil cracking to gas under geological conditions. The geological model of nC24 cracking suggests it is stable at 150～160℃ and its cracking temperature ranges 180℃ to 200℃, consistent with geological models of crude oil cracking currently reported. With increasing degree of thermal stress, the changes in δ13C2 and δ13C3 are larger than that of δ13C1. It is shown that isotope accumulation controlled by the recharging history of a reservoir has a considerable impact on the carbon isotope distribution of natural gas. Compared to that of cumulative gas, the carbon isotope ratio of partly accumulation gas is heavier and influences the fractionation of the δ13C2 and δ13C3 curves to a greater extent. The geological model of nC24 cracking to gas has been used to interpret the origin of carbon isotopic variation of natural gas in some reservoirs in the Tarim basin.

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正构二十四烷裂解成气碳同位素动力学模拟及其地质意义

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A Kinetic Model of Stable Carbon Isotope Ratios in Gaseous Hydrocarbons Generated from Thermal Cracking of ntetracosane and Its Geological Significance

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正构二十四烷裂解成气碳同位素动力学模拟及其地质意义

中国科学院广州地球化学研究所广州 510640

English Abstract

A Kinetic Model of Stable Carbon Isotope Ratios in Gaseous Hydrocarbons Generated from Thermal Cracking of ntetracosane and Its Geological Significance

State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan Guangzhou 510640

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A Kinetic Model of Stable Carbon Isotope Ratios in Gaseous Hydrocarbons Generated from Thermal Cracking of ntetracosane and Its Geological Significance

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正构二十四烷裂解成气碳同位素动力学模拟及其地质意义

中国科学院广州地球化学研究所 广州 510640

English Abstract

A Kinetic Model of Stable Carbon Isotope Ratios in Gaseous Hydrocarbons Generated from Thermal Cracking of ntetracosane and Its Geological Significance

State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan Guangzhou 510640

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中国科学院广州地球化学研究所广州 510640