石油勘探与开发 >

2020 , Vol. 47 >Issue 5: 972 - 983

DOI: https://doi.org/10.11698/PED.2020.05.11

油气勘探

天然气形成过程中碳同位素分馏机理——来自热模拟实验的地球化学证据

  • 彭威龙 ,
  • 刘全有 ,
  • 胡国艺 ,
  • 吕玥 ,
  • 朱东亚 ,
  • 孟庆强 ,
  • 郭丰涛 ,
  • 王若丽
展开
  • 1.页岩油气富集机理与有效开发国家重点实验室,北京 100083;
    2.中国石化石油勘探开发研究院,北京 100083;
    3.中国石油勘探开发研究院,北京 100083;
    4.中国石油长庆油田公司第十一采油厂,甘肃庆阳 745000
彭威龙(1988-),男,湖北武汉人,博士,中国石化石油勘探开发研究院助理研究员,主要从事热模拟实验和天然气地质与地球化学方面的研究。地址:北京市海淀区北四环中路267号奥运大厦803室,中国石化石油勘探开发研究院,邮政编码:100083。E-mail:pengwl26@yeah.net

收稿日期: 2019-12-01

  修回日期: 2020-09-03

  网络出版日期: 2020-09-22

基金资助

国家自然科学基金(41902160,41625009);国家重大科技专项(2016ZX05007-001);国家重点研发计划(2017YFC0603102);中国博士后科学基金项目(2019M650967,2020T130721);中国科学院A类战略先导科技专项(XDA14010404)

收起

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

  • PENG Weilong ,
  • LIU Quanyou ,
  • HU Guoyi ,
  • LYU Yue ,
  • ZHU Dongya ,
  • MENG Qingqiang ,
  • GUO Fengtao ,
  • WANG Ruoli
Expand
  • 1. State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Sinopec, Beijing 100083, China;
    2. Petroleum Exploration and Production Research Institute, Sinopec, Beijing 100083, China;
    3. PetroChina Research Institute of Petroleum Exploration & Development, Beijing 100083, China;
    4. The Eleventh Oil Extraction Plant, PetroChina Changqing Oilfield Company, Qingyang 745000, China

Received date: 2019-12-01

  Revised date: 2020-09-03

  Online published: 2020-09-22

Fold

摘要

选取鄂尔多斯盆地低成熟煤样品开展封闭体系黄金管热模拟实验,分析产物特征,从实验角度探讨天然气碳同位素分馏机理,分析天然气碳同位素组成地球化学“异常”特征。鄂尔多斯盆地低成熟煤2 ℃/h(慢速)和20 ℃/h(快速)升温的烷烃气最大产率分别为302.74 mL/g和230.16 mL/g;低成熟煤快速升温和慢速升温的δ13C1值分别为-34.8‰~-23.6‰和-35.5‰~-24.0‰,δ13C2值分别为-28.0‰~-9.0‰和-28.9‰~-8.3‰,δ13C3值分别为-25.8‰~-14.7‰和-26.4‰~-13.2‰。实验产物中烷烃气在快速升温550 ℃出现了明显的碳同位素组成系列部分倒转,其他温度都表现为正碳同位素组成系列。升温系列中δ13C1表现为先变轻后变重的演化规律,δ13C1值的非单调性变化是由于早期CH4来源并非单一所致,可能是有机质的非均质性或者早期富集12CH4和富集13CH4活化能差值的变化形成的同位素分馏效应所致。重烃气碳同位素值的反转既可以发生在高过成熟的页岩气(油型气)中,也可以发生在煤成气中。结合甲苯热模拟实验,明确烷烃气在高过成熟阶段重烃气碳同位素值可发生反转和倒转现象。芳香烃脱甲基以及甲基链接所产生的同位素分馏效应可能是高过成熟烷烃气碳同位素组成反转、倒转的重要原因。图6表3参56

关键词： 热模拟实验; 天然气; 碳同位素组成; 分馏机理; 低熟煤; 芳香烃裂解

本文引用格式

彭威龙 , 刘全有 , 胡国艺 , 吕玥 , 朱东亚 , 孟庆强 , 郭丰涛 , 王若丽 . 天然气形成过程中碳同位素分馏机理——来自热模拟实验的地球化学证据[J]. 石油勘探与开发, 2020 , 47(5) : 972 -983 . DOI: 10.11698/PED.2020.05.11

Abstract

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 (fast), 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, the δ13C1 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‰; and δ13C3 ranges of -25.8‰ to -14.7‰ and -26.4‰ to -13.2‰, respectively. Alkane gas in the thermal simulation products of fast temperature rise process showed obvious partial reversal of carbon isotope series at 550°C, and at other temperatures showed positive carbon isotope series. In the two heating processes, the δ13C1 turned lighter first and then heavier, and the non-monotonic variation of the δ13C1 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.

Key words： thermal simulation experiment; natural gas; carbon isotope composition; fractionation mechanism; low maturity coal; aromatic hydrocarbon pyrolysis

参考文献

[1] 戴金星. 油气地质学的若干问题[J]. 地球科学进展, 2001, 16(5): 710-718.
DAI Jinxing.Some problems in the study of petroleum geology[J]. Advance in Earth Sciences, 2001, 16(5): 710-718.
[2] 张水昌, 胡国艺, 米敬奎, 等. 三种成因天然气生成时限与生成量及其对深部油气资源预测的影响[J]. 石油学报, 2013, 34(S1): 41-50.
ZHANG Shuichang, HU Guoyi, MI Jingkui, et al.Time-limit and yield of natural gas generation from different origins and their effects on forecast of deep oil and gas resource[J]. Acta Petrolei Sinica, 2013, 34(S1): 41-50.
[3] 黄第藩, 秦匡宗, 王铁冠, 等. 煤成油的形成和成烃机理[M]. 北京: 石油工业出版社, 1995.
HUANG Difan, QIN Kuangzong, WANG Tieguan, et al. Formation and hydrocarbon generation mechanism of coal-derived oil[M]. Beijing: Petroleum Industry Press, 1995.
[4] 陈建平, 赵文智, 王招明, 等. 海相干酪根天然气生成成熟度上限与生气潜力极限探讨: 以塔里木盆地研究为例[J]. 科学通报, 2007, 52(SI): 95-100.
CHEN Jianping, ZHAO Wenzhi, WANG Zhaoming, et al.Discussion on the upper maturity limit and gas potential limit of marine kerogen: A case study of the Tarim Basin[J]. Chinese Science Bulletin, 2007, 52(SI): 95-100.
[5] 戴金星, 裴锡古, 戚厚发. 中国天然气地质学(卷一)[M]. 北京: 石油工业出版社, 1992: 116-129.
DAI Jinxing, PEI Xigu, QI Houfa. Natural gas geology in China(Vol.1)[M]. Beijing: Petroleum Industry Press, 1992: 116-129.
[6] 赵靖舟. 天然气地质学[M]. 北京: 石油工业出版社, 2013.
ZHAO Jingzhou. Natural gas geology[M]. Beijing: Petroleum Industry Press, 2013.
[7] SCHOELL M.The hydrogen and carbon isotopic composition of methane from natural gases of various origins[J]. Geochimica et Cosmochimica Acta, 1980, 44(5): 649-661.
[8] THOMPSON K F M. Classification and thermal history of petroleum based on light hydrocarbons[J]. Geochimica et Cosmochimica Acta, 1983, 47(2): 303-316.
[9] SCHOELL M.Genetic characterization of natural gas[J]. AAPG Bulletin, 1983, 67: 2225-2238.
[10] JENDEN P D, KAPLAN I R, POREDA R, et al.Origin of nitrogen-rich natural gases in the California Great Valley: Evidence from helium, carbon and nitrogen isotope ratios[J]. Geochimica et Cosmochimica Acta, 1988, 52(4): 851-861.
[11] 刘文汇, 王晓锋, 腾格尔, 等. 中国近十年来天然气示踪地球化学研究进展[J]. 矿物岩石地球化学通报, 2013, 32(3): 279-289.
LIU Wenhui, WANG Xiaofeng, TENGER, et al. Research progress of gas geochemistry during the past decade in China[J]. Bulletin of Mineralogy, Petrology and Geochemistry, 2013, 32(3): 279-289.
[12] LIU Quanyou, WU Xiaoqi, WANG Xiaofeng, et al.Carbon and hydrogen isotopes of methane, ethane, and propane: A review of genetic identification of natural gas[J]. Earth-Science Reviews, 2019, 190: 247-272.
[13] TILLEY B, MCLELLAN S, HIEBERT S, et al.Gas isotope reversals in fractured gas reservoirs of the western Canadian Foothills: Mature shale gases in disguise[J]. AAPG Bulletin, 2011, 95(8): 1399-1422.
[14] ZUMBERGE J, FERWORN K, BROWN S.Isotopic reversal (‘rollover’) in shale gases produced from the Mississippian Barnett and Fayetteville formations[J]. Marine and Petroleum Geology, 2012, 31(1): 43-52.
[15] XIA X, CHEN J, BRAUN R, et al.Isotopic reversals with respect to maturity trends due to mixing of primary and secondary products in source rocks[J]. Chemical Geology, 2013, 339(2): 205-212.
[16] TILLEY B, MUEHLENBACHS K.Isotope reversals and universal stages and trends of gas maturation in sealed, self-contained petroleum systems[J]. Chemical Geology, 2013, 339: 194-204.
[17] DAI J, NI Y, HUANG S, et al.Secondary origin of negative carbon isotopic series in natural gas[J]. Journal of Natural Gas Geoscience, 2016, 1(1): 1-7.
[18] MI J, WANG H, HE K, et al.Demethylation as a mechanism for isotopic reversals of shale gas generated at over maturity[J]. Journal of Analytical and Applied Pyrolysis, 2018, 135: 361-368.
[19] BURRUSS R C, LAUGHREY C D.Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons[J]. Organic Geochemistry, 2010, 41(12): 1285-1296.
[20] CRAMER B, FABER E, GERLING D, et al.Reaction kinetics of stable carbon isotope in natural gas-insights from dry, open system pyrolysis experiments[J]. Energy and Fuels, 2001, 15(3): 517-532.
[21] DU J, JIN Z, XIE H, et al, Stable carbon isotope compositions of gaseous hydrocarbons produced from high pressure and high temperature pyrolysis of lignite[J]. Organic Geochemistry, 2003, 34: 97-104.
[22] 毛榕, 米敬奎, 张水昌, 等. 不同煤系源岩生烃特征的黄金管热模拟实验对比研究[J]. 天然气地球科学, 2012, 23(6): 1127-1134.
MAO Rong, MI Jingkui, ZHANG Shuichang, et al.Study on the hydrocarbon generation characteristics of different coaly source rocks by gold-tube pyrolysis experiments[J]. Natural Gas Geoscience, 2012, 23(6): 1127-1134.
[23] ZHANG S, MI J, HE K, et al. Synthesis of hydrocarbon gases from four different carbon sources and hydrogen gas using a gold-tube system by Fischer-Tropsch method[J]. Chemical Geology, 2013, 349/350: 27-35.
[24] MI J, ZHANG S, HE K.Experimental investigations about the effect of pressure on gas generation from coal[J]. Organic Geochemistry, 2014, 74: 116-122.
[25] MI J, ZHANG S, SU J, et al.The upper thermal maturity limit of primary gas generated from marine organic matters[J]. Marine and Petroleum Geology, 2018, 89: 120-129.
[26] HE K, ZHANG S, MI J, et al.Pyrolysis involving n-hexadecane, water and minerals: Insight into the mechanisms and isotope fractionation for water-hydrocarbon reaction[J]. Journal of Analytical and Applied Pyrolysis, 2018, 130: 198-208.
[27] GAO J, LIU J, NI Y.Gas generation and its isotope composition during coal pyrolysis: The catalytic effect of nickel and magnetite[J]. Fuel, 2018, 222: 74-82.
[28] PENG W L, HU G Y, LIU Q Y, et al.Research status on thermal simulation experiment and several issues of concern[J]. Journal of Natural Gas Geoscience, 2018, 3(5): 283-293.
[29] HE K, ZHANG S, MI J, et al.The evolution of chemical groups and isotopic fractionation at different maturation stages during lignite pyrolysis[J]. Fuel, 2018, 211: 492-506.
[30] SHUAI Y H, ZHANG S C, GAO Y, et al.Effect and quantitative evaluation of CO2 derived from organic matter in coal on the formation of tight sandstone reservoirs[J]. SCIENCE CHINA Earth Sciences, 2013, 56(5): 756-762.
[31] 田辉, 肖贤明, 李贤庆, 等. 海相干酪根与原油裂解气甲烷生成及碳同位素分馏的差异研究[J]. 地球化学, 2007, 36(1): 71-77.
TIAN Hui, XIAO Xianming, LI Xianqing, et al.Comparison of gas generation and carbon isotope fraction of methane from marine kerogen and crude oil-cracking gaes[J]. Geochimica, 2007, 36(1): 71-77.
[32] 帅燕华, 邹艳荣, 彭平安. 天然气甲烷碳同位素动力学模型与地质应用新进展[J]. 地球科学进展, 2003, 18(3): 405-411.
SHUAI Yanhua, ZOU Yanrong, PENG Ping’an.Kinetic model for the stable carbon isotope of methane: The state of the art[J]. Advance in Earth Sciences, 2003, 18(3): 405-411.
[33] LORANT F, PRINZHOFER A, BEHAR F, et al.Carbon isotopic and molecular constraints on the formation and the expulsion of thermogenic hydrocarbon gases[J]. Chemical Geology, 1998, 147(3/4): 249-264.
[34] HILL R J, TANG Y, KAPLAN I.Insight into cracking based on laboratory experiments[J]. Organic Geochemistry, 2003, 34(12): 1651-1672.
[35] GALIMOV E M.Isotope organic geochemistry[J]. Organic Geochemistry, 2006, 37(10): 1200-1262.
[36] TANG Y, PERRY J K, JENDEN P D, et al.Mathematical modeling of stable carbon isotope ratios in natural gases[J]. Geochimica et Cosmochimica Acta, 2000, 64(15): 2673-2687.
[37] 张海祖, 熊永强, 刘金钟, 等. 正十八烷的裂解动力学研究(I): 气态烃组分及其碳同位素演化特征[J]. 地质学报, 2005, 79(4): 569-574.
ZHANG Haizu, XIONG Yongqiang, LIU Jinzhong, et al.Pyrolysis kinetics of pure n-C18H38 (I): Gaseous hydrocarbon and carbon isotope evolution[J]. Acta Geologica Sinica, 2005, 79(4): 569-574.
[38] 熊永强, 张祖海, 耿新华, 等. 正十八烷裂解及其地球化学意义[J]. 科学通报, 2004, 49(S1): 72-75.
XIONG Yongqiang, ZHANG Haizhu, GENG Xinhua, et al.N-octadecane pyrolysis and its geochemical significance[J]. Chinese Science Bulletin, 2004, 49(S1): 72-75.
[39] MI J, ZHANG S, CHEN J, et al.Upper thermal maturity limit for gas generation from humic coal[J]. International Journal of Coal Geology, 2015, 152: 123-131.
[40] BERNER U, FABER E.Expirical carbon isotope maturity relationships for gases from algal kerogens and terrigenous organic matter, based on dry, open-system pyrolysis[J]. Organic Geochemistry, 1996, 24: 947-955.
[41] 唐小强, 黄光辉, 张敏, 等. 裂解热模拟实验中碳同位素变化特征及其地球化学意义[J]. 天然气地球科学, 2010, 21(6): 1029-1035.
TANG Xiaoqiang, HUANG Guanghui, ZHANG Min, et al.Stable carbon isotope compositions of gaseous hydrocarbons in pyrolysis experiment and geochemical significance[J]. Natural Gas Geoscience, 2010, 21(6): 1029-1035.
[42] 汤国民, 罗群, 庞雄奇, 等. 柴北缘鄂博梁Ⅲ号构造天然气成因类型及其成藏特征[J]. 新疆石油地质, 2014, 35(2): 17-22.
TANG Guomin, LUO Qun, PANG Xiongqi.Nayural gas genetic type and accumulation characteristics in Erboliang III Structure in north margin of Qaidam Basin[J]. Xinjiang Petroleum Geology, 2014, 35(2): 17-22.
[43] 赵力彬, 黄志龙, 马玉杰, 等. 松辽盆地南部德惠断陷深层天然气地球化学特征及成因[J]. 天然气地球科学, 2006, 17(2): 177-182.
ZHAO Libin, HUANG Zhilong, MA Yujie, et al.A study on geochemical character and origin of natural gas in Dehui Fault Depression of the southern Songliao Basin[J]. Natural Gas Geoscience, 2006, 17(2): 177-182.
[44] 王杰, 陈践发, 王铁冠, 等. 松辽盆地双城—太平川地区天然气成因类型及气源[J]. 石油学报, 2006, 27(3): 16-21.
ZHANG Jie, CHEN Jianfa, WANG Tieguan, et al.A gas source rocks and gas genetic type in Shuangcheng-Taipingchuan area of Songliao Basin[J]. Acta Petrolei Sinica, 2006, 27(3): 16-21.
[45] 宋振响, 顾忆, 路清华, 等. 松辽盆地梨树断陷天然气成因类型及勘探方向[J]. 石油学报, 2016, 37(5): 22-30.
SONG Zhenxiang, GU Yi, LU Qinghua, et al.Genetic types of natural gas and its exploration direction in Lishu Fault Sag, Songliao Basin[J]. Acta Petrolei Sinica, 2016, 37(5): 22-30.
[46] LI J, LI J, LI Z, et al.The hydrogen isotopic characteristics of the Upper Paleozoic natural gas in Ordos Basin[J]. Organic Geochemistry, 2014, 74: 66-75.
[47] 翟俪娜, 倪云燕, 吴朝东, 等. 川中地区须家河组天然气地球化学特征[J]. 天然气地球科学, 2017, 28(4): 539-549.
ZHAI Li’na, NI Yunyan, WU Chaodong, et al.Geochemical characteristics of the natural gas from Xujiahe Formation in the central Sichuan Basin, China[J]. Natural Gas Geoscience, 2017, 28(4): 539-549.
[48] DAI J, ZOU C, DONG D, et al.Geochemical characteristics of marine and terrestrial shale gas in China[J]. Marine and Petroleum Geology, 2016, 76: 444-463.
[49] DAI J, XIA X, QIN S, et al.Origins of partially reversed alkane δ13C values for biogenic gases in China[J]. Organic Geochemistry, 2004, 35(4): 405-411.
[50] 杨春, 王京红, 米敬奎, 等. 费-托合成实验中烷烃气碳同位素分馏机理[J]. 天然气地球科学, 2011, 22(2): 206-210.
YANG Chun, WANG Jinghong, MI Jingkui, et al.Carbon isotope fractionation mechanism of alkane gases in Fischer-Tropsch synthesis experiments[J]. Natural Gas Geoscience, 2011, 22(2): 206-210.
[51] LANCET M S, ANDERS E.Carbon isotope fractionation in the Fischer-Tropsch synthesis and in meteorites[J]. Science, 1970, 170(3961): 980-982.
[52] 任德贻, 赵峰华, 代世峰, 等. 煤的微量元素地球化学[M]. 北京: 科学出版社, 2006.
REN Deyi, ZHAO Fenghua, DAI Shifeng. Geochemistry of trace elements in coal[M]. Beijing: Sciecne Press, 2006.
[53] 王东良, 张英, 卢双舫, 等. 烃源岩过成熟阶段生气潜力的实验室模拟[J]. 沉积学报, 2012, 30(6): 1172-1179.
WANG Dongliang, ZHANG Ying, LU Shuangfang, et al.The simulation experiment on gas-generating potential of over mature source rocks[J]. Acta Sedimentologica Sinica, 2012, 30(6): 1172-1179.
[54] FUSETTI L, BEHAR F, BOUNACEUR R, et al.New insights into secondary gas generation from the thermal cracking of oil: Methylated monoaromatics. A kinetic approach using 1, 2, 4-trimethylbenzene. Part I: A mechanistic kinetic model[J]. Organic Geochemistry, 2010, 41: 146-167.
[55] FUSETTI L, BEHAR F, LORANT F, et al.New insights into secondary gas generation from the thermal cracking of oil: Methylated monoaromatics. A kinetic approach using 1, 2, 4-trimethylbenzene. Part III: An isotopic fractionation model[J]. Organic Geochemistry, 2010, 41: 431-436.
[56] LI W, LU S, LI J, et al.Carbon isotope fractionation during shale gas transport: mechanism, characterization and significance[J]. SCIENCE CHINA Earth Sciences, 2020, 63: 674-689.
Options
文章导航

/

〈 〉

版权所有：《石油勘探与开发》编辑部；《石油勘探与开发（英文）》编辑部
地址：北京市海淀区学院路20号，中国石油勘探开发研究院数据中心605室　

京ICP备15044687号    技术支持：北京玛格泰克科技发展有限公司