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天然气地球科学

• 天然气地球化学 • 上一篇    下一篇

四川盆地志留系龙马溪组页岩气气体地球化学特征及意义

曹春辉，张铭杰，汤庆艳，吕宗刚，汪扬，杜丽，李中平   

  1. 1.兰州大学地质科学与矿产资源学院，甘肃省西部矿产资源重点实验室，甘肃 兰州 730000；
    2.甘肃省油气资源研究重点实验室/中国科学院油气资源研究重点实验室，甘肃 兰州 730000；
    3.中国石油西南油气分公司蜀南气矿,四川 泸州 646000
  • 收稿日期:2015-04-11 修回日期:2015-05-22 出版日期:2015-08-10 发布日期:2015-08-10
  • 通讯作者: 张铭杰(1965-)，男，甘肃漳县人，教授，博士生导师，主要从事岩石圈流体与成矿成藏地球化学研究. E-mail：mjzhang@lzu.edu.cn.
  • 作者简介:曹春辉(1983-)，男，河北石家庄人，工程师，博士在读，主要从事石油天然气地球化学研究. E-mail：caochunhui@lzb.ac.cn.
  • 基金资助:

    国家自然科学基金项目(编号：41502143；41472070;41372095);国家重点基础研究发展计划(编号：2012CB214701)；教育部科学技术研究重大项目(编号：311010)联合资助.

Geochemical Characteristics and Implications of Shale Gas in Longmaxi Formation,Sichuan Basin,China

CAO Chun-hui，ZHANG Ming-jie，TANG Qing-yan，Lv Zong-gang，WANG Yang，DU Li，LI Zhong-ping   

  1. 1.School of Earth Sciences & Key Lab of Mineral Resources in Western China,Gansu Province,Lanzhou University,
    Lanzhou 730000,China;2.Key Laboratory of Petroleum Resources,Gansu Province/Key Laboratory of Petroleum
    Resources Research,Institute of Geology and Geophysics,Chinese Academy of Sciences,Lanzhou 730000,China;
    3.Shu'nan Gas-mine Field,PetroChina Southwest Oil & Gas Field Branch Company,Luzhou 646000,China
  • Received:2015-04-11 Revised:2015-05-22 Online:2015-08-10 Published:2015-08-10

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摘要：

四川盆地威远地区和川南长宁地区志留系龙马溪组页岩气化学组成以及碳、氢和氦同位素组成分析表明，该区页岩气CH4含量占绝对优势(94.0%～98.5%)、湿度低(0.3%～0.6%)、非烃气体含量较低(以CO2和N2为主、含微量的He、未检测出H2S)。烷烃气体碳同位素值随碳数增加出现局部反序分布特征：δ13C1>δ13C2；δ13CCO2=-2.4‰~-6.0‰，3He/4He =0.01~0.03Ra。威远和长宁2个地区页岩气碳同位素组成有所差异，威远地区页岩气的碳同位素值比长宁地区的偏低，δ13C1值偏低约8‰，δ13C2值偏低6‰；重复性实验结果表明2个地区页岩气碳同位素的差异可能源于其地质演化条件。川南长宁龙马溪页岩处于高—过成熟阶段，封闭性好，页岩气主要为干酪根初次裂解气和液态烃二次裂解气不同比例的混合，非烃气体中除有机质热裂解成因外含少量碳酸盐矿物分解产生的CO2。液态烃二次裂解可能是碳同位素值随碳数分布发生反序分布的原因。威远地区页岩中沥青含量较长宁地区多，同时后期的构造作用和抬升可能导致威远地区页岩气的烷烃气体的碳同位素值偏低。

关键词: 稳定同位素, 化学组成, 页岩气, 龙马溪组, 四川盆地

Abstract:

Gas geochemical analysis has been conducted for the shale gas from Longmaxi Formation in Weiyuan-Changning areas,Sichuan Basin,China.Chemical composition,carbon,hydrogen and helium isotopic compositions were measured using an integrated method of gas chromatography combined with mass spectrometry.The results show that Longmaxi shale gases after are dominated by methane (94.0%-98.6%) with low wetness (0.3%-0.6%),minor non-hydrocarbon gases,which are mainly CO2 and N2,and trace amount of He.δ13CCO2=-2.5‰--6.0‰,3He/4He=0.01-0.03Ra.The shale gases in Weiyuan and Changning areas have reversed carbon isotope between methane and ethane (δ13C1>δ13C2) and distinct carbon isotopic compositions.Shale gas from the Weiyuan pilot has heavier carbon isotopic compositions for methane (δ13C1:-34.5‰--36.8‰),ethane (δ13C2:-37.6‰--41.9‰) and CO2 (δ13CCO2:-4.5‰--6.0‰) than those in Changning pilot (δ13C1:-27.2‰--27.3‰,δ13C2:-33.7‰--34.1‰,δ13CCO2:-2.5‰--4.6‰).The Longmaxi shale was at thermally high or over mature stage of organic matter with good sealing condition.The shale gas after hydraulic fracturing could be originated from the thermal decomposition of kerogen and the secondary cracking of liquid hydrocarbons which caused the reversal pattern of carbon isotopes.Some CO2 could be derived from decomposition of carbonate.The differences in carbon isotopes of gases between Weiyuan and Changning areas could be derived from different mixing proportion of gas from the secondary cracking of liquid hydrocarbons caused by the specific geological and geochemical conditions.

Key words: Stable isotope, Chemical composition, Shale gas, Longmaxi Formation, Sichuan Basin

中图分类号: 

  • TE122.1+13

[1]Zou Caineng,Dong Dazhong,Wang Shejiao,et al.Geological characteristics,formation mechanism and resource potential of shale gas in China[J].Petroleum Exploration and Development,2010,37(6):641-653.[邹才能,董大忠,王社教,等.中国页岩气形成机理、地质特征及资源潜力[J].石油勘探与开发,2010,37(6):641-653.]
[2]Dai J X,Zou C N,Liao S M,et al.Geochemistry of the extremely high thermal maturity Longmaxi shale gas,southern Sichuan Basin[J].Organic Geochemistry,2014,74:3-12.
[3]Guo T,Zhang H.Formation and enrichment mode of Jiaoshiba Shale Gasfield,Sichuan Basin[J].Petroleum Exploration and  Development,2014,41(1):31-40.
[4]Burruss R C,Laughrey C D.Carbon and hydrogen isotopic reversals in deep basin gas[J].Organic Geochemistry,2010,41(12):1285-1296.
[5]Gao L,Schimmelmann A,Tang Y,et al.Isotope rollover in shale gas observed in laboratory pyrolysis experiments[J].Organic Geochemistry,2014,68:95-106.
[6]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.
[7]Xia X Y,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,2013,339:205-212.
[8]Zumberge J,Ferworn K,Brown S.Isotopic reversal(‘rollover’) in shale gases produced from the Mississippian Barnett and Fayetteville formations[J].Marine Petroleum Geology,2012,31:43-52.
[9]Liu Shugen,Ma Wenxin,Luba Jansa,et al.Characterristics of the shale gas reservoir rock in the Lower Silurian Longmaxi Formation,east Sichuan Basin,China[J].Acta Petroleum Sinica,2011,27(8):2239-2252.[刘树根,马文辛,Luba Jansa,等.四川盆地东部地区下志留统龙马溪组页岩储层特征[J].岩石学报,2011,27(8):2239-2252.]
[10][KG*6/7]Huang Jinliang,Zou Caineng,Li Jianzhong,et al.Shale gas accumulation conditions and favorable zones of Silurian Longmaxi Formation in south Sichuan Basin,China[J].Journal of China Coal Society,2012,37(5):782-787.[黄金亮，邹才能，李建忠，等.川南志留系龙马溪组页岩气形成条件与有利区分析[J].煤炭学报,2012,37(5):782-787.]
[11]Chen S,Zhu Y,Wang H,et al.Shale gas reservoir characterisation:A typical case in the southern Sichuan Basin of China[J].Energy,2011,36(11):6609-6616.
[12]Zou C N,Yang Z,Dai J X,et al.The characteristics and significance of conventional and unconventional Sinian-Silurian gas systems in the Sichuan Basin,central China[J].Marine Petroleum Geology,2015,64:386-402.
[13]Cao Chunhui,Li Liwu,Li Zhongping,et al.Composition of natural gas analysis by gas isotope mass spectrometer and chromatography[J].Chemical Analysis and Meterage,2011,20(3):36-39.[曹春辉,李立武,李中平,等.气体同位素质谱与色谱结合分析天然气组成[J].化学分析计量,2011,20(3):36-39.]
[14]Li Z P,Wang X B,Li L W,et al.Development of new method of δ13C measurement for trace hydrocarbons in natural gas using solid phase micro-extraction coupled to gas chromatography isotope ratio mass spectrometry[J].Journal of chromatography A,2014,1372C:228-235.
[15]Zhang M J,Tang Q Y,Hu P Q,et al.Noble gas isotopic constraints on the origin and evolution of the Jinchuan Ni-Cu-(PGE) sulfide ore-bearing ultramafic intrusion,Western China[J].Chemical Geology,2013,339:301-312.
[16]Cao Chunhui,Li Zhongping,Du Li,et al.Analysis of rare gas isotope in crude oil[J].Analytical Instrumentation,2014,6:12-16.[曹春辉,李中平,杜丽,等.原油溶解气中稀有气体同位素分析[J].分析仪器,2014,6:12-16.]
[17]Kotarba M J,Nagao K.Composition and origin of natural gases accumulated in the Polish and Ukrainian parts of the carpathians,region[J].Chemical Geology,2008,255(3/4):426-438.
[18][KG*6/7]Wang Peng,Shen Zhongmin,Liu Sibing,et al.Geochemical characteristics of non-hydrocarbon in natural gas in west Sichuan Depression and its implications[J].Natural Gas Geoscience,2014,25(3):394-401.[王鹏,沈忠民,刘四兵,等.川西坳陷天然气中非烃气地球化学特征及应用[J].天然气地球科学,2014,25(3):394-401.]
[19]Zhang T W,Zhang M J,Bai B J,et al.Origin and accumulation of carbon dioxide in the Huanghua Depression,Bohai Bay Basin,China[J].AAPG Bulletin,2008,92(3):341-358.
[20]Liu Quanyou,Jin Zhijun,Chen Jianfa,et al.Origin of nitrogen molecules in natural gas and implications for the high risk of N2 exploration in Tarim Basin,NW China[J].Journal of Petroleum Science and Engineering,2012,81:112-121.
[21]Krooss,B M,Littkea R,Müllera B,et al.Generation of nitrogen and methane from sedimentary organic matter[J].Chemical Geology,1995,126,291-318.
[22]Baxby M,Patience R L,Bartle K D,et al.The origin and diagenesis of sedimentary organic nitrogen[J].Journal of Petroleum  Geology,1994,17(2):211-230.
[23]Tang Q Y,Zhang M J,Cao C H,et al.The molecular and carbon isotopic constrains on origin and storage of Longmaxi Formation shale gas in Changning area,Sichuan Basin,China[J].Interpretation,2015,3(2):35-47.doi.org/10.1190/INT-2014-0158.1.
[24]Yu Cong,Gong Deyu,Huang Shipeng,et al.Geochemical characteristics of carbon and hydrogen isotopes for the Xujiahe Formation natural gas in Sichuan Basin[J].Natural Gas Geoscience,2014,25(1):87-97.[于聪,龚德瑜,黄士鹏,等.四川盆地须家河组天然气碳、氢同位素特征及其指示意义[J].天然气地球科学,2014,25(1):87-97.]
[25]Schoell M.Genetic characterization of natural gases[J].AAPG Bulletin,1983,67:2225-2238.
[26]Gang Wenzhe,Gao Gang,Hao Shisheng,et al.Carbon isotope of ethane applied in the analyses of genetic types of natural gas[J].Petroleum Geology & Experiment,1997,19(2):164-167.[刚文哲，高岗，郝石生，等.论C2H6碳同位素在天然气成因类型研究中的应用[J].石油实验地质，1997,19(2):164-167.]
[27]Ulrich B,Eckhard F,Georg S,et al.Primary cracking of algal and landplant kerogens:Kinetic models of isotope variations in methane,ethane and propane[J].Chemical Geology,1995,126:233-245.
[28]Wang Y P,Zhao C Y,Wang H J,et al.Origins of natural gases from marine strata in northeastern Sichuan Basin(China) from carbon molecular moieties and isotopic data[J].Journal of Asian Earth Science,2013,65(supplement 1):13-20.
[29]Hao F,Zou H Y.Cause of shale gas geochemical anomalies and mechanisms for gas enrichment and depletion in high-maturity shales[J].Marine Petroleum Geology,2013,44:1-12.
[30]Lu J,Larson T E,Smyth R C.Carbon isotope effects of methane transport through Anahuac Shale:A core gas[J].Journal of Geochemical Exploration,2015,148:138-149.
[31]Wang X F,Li X F,Wang X Z,et al.Carbon isotopic fractionation by desorption of shale gases[J].Marine Petroleum Geology,2015,60:79-86.
[32]Warner N R,Kresse T M,Hays P D,et al.Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas[J].Applied Geochemistry,2013,35:207-220.
[33]Zhang Jinchuan,Nie Haikuan,Xu Bo,et al.Geological condition of shale gas accumulation in Sichuan Basin[J].Natural Gas Industry,2008,28(2):151-156.[张金川,聂海宽,徐波,等.四川盆地页岩气成藏地质条件[J].天然气工业,2008,28(2):151-156.]
[34]Zeng Xiangliang,Liu Shugen,Huang Wenming,et al.Comparison of Silurian Longmaxi Formation shale of Sichuan Basin in China and Carboniferous Barnett Formation shale of Fort Worth Basin in United States[J].Geological Bulletin of China,2011,30(2/3):372-384.[曾祥亮,刘树根,黄文明,等.四川盆地志留系龙马溪组页岩与美国Fort Worth盆地石炭系Barnett组页岩地质特征对比[J].地质通报,2011 30(2/3):372-384.]
[35]Zou Q,Xiao X M,Tian H,et al.Modeling free gas content of the Lower Paleozoic shales in the Weiyuan area of the Sichuan Basin,China[J].Marine Petroleum Geology,2014,56:87-96.
[36]Chen S B,Zhu Y M,Qin Y,et al.Reservoir evaluation of the Lower Silurian Longmaxi Formation shale gas in the southern Sichuan Basin of China[J].Marine Petroleum Geology,2014,57:619-630.
[37]Tang Qingyan,Zhang Mingjie,Yu Ming,et al.Pyrolysis constraints on the generationmechanism of shale gas[J].Journal of China Coal Society,2013,38(5):742-747.[汤庆艳,张铭杰,余明,等.页岩气形成机制的生烃热模拟研究[J].煤炭学报,2013,38(5):742-747.]
[38]Firouzi M,Alnoaimi K,Kovscek A,et al.Klinkenberg effect on predicting and measuring helium permeability in gas shales[J].International Journal of Coal Geology,2014,123(supplement):62-68.
[39]Chen Shangbin,Zhu Yanming,Wang Hongyan,et al.Structure characteristics and accumulation significance of nanopores in Longmaxi shale gas reservoir in the southern Sichuan Basin[J].Journal of China Coal Society,2012,37(3):438-444.[陈尚斌，朱炎铭，王红岩，等.川南龙马溪组页岩气储层纳米孔隙结构特征及其成藏意义[J].煤炭学报,2012,37(3):438-444.]
[40]Chen Wenling,Zhou Wen,Luo Ping,et al.Analysis of the shale gas reservoir in the Lower Silurian Longmaxi Formation,Changxin 1 well,southeast Sichuan Basin,China[J].Acta Petroleum Sinica,2013,29(3):1073-1086.[陈文玲，周文，罗平，等.四川盆地长芯1井下志留系龙马溪组页岩气储层特征研究[J].岩石学报,2013,29(3):1073-1086.]
[41]Tang Y C,Huang Y,Ellis G S,et al.A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil[J].Geochimica et Cosmochimica Acta,2005,69(18):4505-4520.
[42]Ni Y Y,Ma Q S,Ellis G S,et al.Fundamental studies on kinetic isotope effect(KIE) of hydrogen isotope fractionation in natural gas systems[J].Geochimica et Cosmochimica Acta,2011,75(10):2696-2707.
[43]Zhang T W,Yang R S,Kitty L,et al.Chemical and isotopic composition of gases released by crush methods from organic rich mudrocks[J].Organic Geochemistry,2014,73:16-28.
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