TSR对气态烃组分及碳同位素组成的影响——高温高压模拟实验的证据

Influences of TSR on gaseous hydrocarbon components and carbon isotopes：revelations from high-temperature and high-pressure simulation experiments

张建勇 刘文汇 腾格尔 王小芳 潘立银 吕玉珍 付小东 张敬艺 卿颖 刘金钟

Zhang Jianyong Liu Wenhui Tenger Wang Xiaofang Pan Liyin Lü Yuzhen Fu Xiaodong Zhang Jingyi Qing Ying Liu Jinzhong

中国石油杭州地质研究院, 杭州, 310023 2. 中国石油碳酸盐岩储层重点实验室, 杭州, 310023 3. 中国科学院地质与地球物理研究所兰州油气资源中心, 兰州, 73000 4. 中国石油化工股份有限公司石油勘探开发研究院, 北京, 100083 5. 中国石油化工股份有限公司石油勘探开发研究院无锡石油地质研究所, 无锡, 214126 6. 冀东油田勘探开发研究院, 唐山, 063004 7. 中国科学院广州地球化学研究所有机地球化学国家重点实验室, 广州, 510640

Hangzhou Research Institute of Petroleum Geology, Petro China, Hangzhou, Zhejiang 310023, China 2. Key Laboratory of Carbonate Reservoirs of CNPC, Hangzhou, Zhejiang 310023, China 3. Lanzhou Center for Oil and Gas Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, China 4. SINOPEC Exploration & Production Research Institute, Beijing 100083, China 5. Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi, Jiangsu 214126, China 6. Research Institute of Exploration and Development, Petro China Jidong Oilfield Company, Tangshan, Hebei 063004, China 7. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, Guangdong 510640, China

选用高含硫原油、Ⅱ型干酪根、Ⅲ型干酪根以及硫酸镁作为反应物,设计了3组共6个反应体系,以对比发生硫酸盐热还原作用(TSR)与否对烃类组分及碳同位素的影响。模拟实验利用黄金管—高压釜限定系统完成,6个反应体系具有完全相同的反应温度和压力,反应结果具有可对比性。模拟实验结果证实:①TSR反应导致气态产物中H2S和CO2含量的明显增加;②TSR反应导致气态天然气组分变干,即碳数越多的气态烃越容易发生TSR反应,甲烷很难作为反应物参与TSR反应;③TSR反应导致气态烃碳同位素变重,而CO2碳同位素变轻;④TSR导致甲烷碳同位素变重最多,乙烷、丙烷碳同位素变重相对较小,即δ13C2与δ13C1差值变小。TSR反应导致的天然气组分及碳同位素的变化影响了油气源对比的经验公式及判断指标,因此在高含硫天然气区进行气源对比时应考虑TSR的影响。

Crude oil rich in sulfur,kerogen of types Ⅱ and Ⅲ and magnesium sulfate were tested in 6 reaction systems(divided into 3 groups) so as to study the influences of thermochemical sulfate reduction(TSR) on gaseous hydrocarbon components and carbon isotopes.The tests were made in gold tube-autoclave system.The above-mentioned 6 reaction systems had the same temperature and pressure;hence their results were comparable.The modeling experiments have proved that: 1)TSR leads to the obvious increase of H2S and CO2 yields;2)TSR makes gaseous hydrocarbon become dryer,that is,the C2+ series are easier to react in TSR while CH4 seldom participates in TSR;3)TSR makes the carbon isotopes of gaseous hydrocarbon become heavier and that of CO2 become lighter;4) TSR makes much more obvious change of carbon isotopes in methane than in ethane and propane,that is,the value of δC2-δC1 decreases.The changes of gaseous hydrocarbon components and carbon isotopes caused by TSR influence the index and empirical formula of gas-source rock correlation,so the influences of TSR should be taken into consideration in gas-source rock correlation of natural gas rich in sulfur.

国家重点基础研究发展计划(973计划)项目(2001CB209102);中石化项目(P06006);中国科学院西部学子奖学金共同资助

https://doi.org/10.11781/sysydz201201066