泥质烃源岩中不同赋存状态有机质定量表征——以东营凹陷沙河街组为例
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摘要
泥质烃源岩中的滞留有机质存在多种赋存状态,包括游离态有机质和矿物结合态有机质。不同赋存状态有机质的性质存在较大差别,故而在烃源岩精细评价中的意义不同,但尚无完善的对其定量表征的方法。采用东营凹陷沙三段中亚段、沙三段下亚段和沙四段上亚段泥质烃源岩黏粒级样品,通过分析溶剂抽提和连续化学处理过程中(碱解-HCl酸解-HF/HCl酸解处理)样品热解参数的变化,包括游离烃、裂解烃和总有机碳含量等参数的变化规律,以及定量测定不同赋存状态有机质的产率,建立了不同赋存状态滞留有机质的定量表征方法。研究结果表明,矿物结合态可溶有机质在烃源岩滞留有机质中的数量十分可观,传统地化分析中的Rock-Eval热解评价方法和氯仿沥青A评价方法评价烃源岩生烃潜力存在较大局限性。深入研究矿物结合态有机质的地化特征,将会拓宽对油气生成理论及滞留油气赋存状态的认知。
The organic matters retained in argillaceous source rocks are of various occurrences, including free state and mineral-bindingstate organic matters which have quite different geochemical natures and different significance in detailed source rock evaluation. However,a comprehensive quantitative characterization technique for both occurrences has not been established yet. With the argillaceous sourcerocks sampled from the middle Es3, the lower Es3 and the upper Es4 of the Shahejie formation, Dongying sag, and based on the analysis onthe changes of pyrolysis parameters during the processes of solvent extraction and sequential chemical treatment including the variations offree hydrocarbon, cracked hydrocarbon and TOC, the paper measures the abundance of the organic matters with different occurrences quan-titatively and establishes a quantitative characterization method of retained organic matters with different occurrences. The results showthat the quantity of soluble organic matters of mineral-binding state is quite large in the organic matters retained in source rocks. Tradition-al evaluation methods such as Rock-Eval pyrolysis method and chloroform bitumen A method have some limitations. Profound study on thegeochemical characteristics of the organic matters of mineral-binding state will widen the knowledge of hydrocarbon generation theory andretained hydrocarbon occurrences.
The organic matters retained in argillaceous source rocks are of various occurrences, including free state and mineral-bindingstate organic matters which have quite different geochemical natures and different significance in detailed source rock evaluation. However,a comprehensive quantitative characterization technique for both occurrences has not been established yet. With the argillaceous sourcerocks sampled from the middle Es3, the lower Es3 and the upper Es4 of the Shahejie formation, Dongying sag, and based on the analysis onthe changes of pyrolysis parameters during the processes of solvent extraction and sequential chemical treatment including the variations offree hydrocarbon, cracked hydrocarbon and TOC, the paper measures the abundance of the organic matters with different occurrences quan-titatively and establishes a quantitative characterization method of retained organic matters with different occurrences. The results showthat the quantity of soluble organic matters of mineral-binding state is quite large in the organic matters retained in source rocks. Tradition-al evaluation methods such as Rock-Eval pyrolysis method and chloroform bitumen A method have some limitations. Profound study on thegeochemical characteristics of the organic matters of mineral-binding state will widen the knowledge of hydrocarbon generation theory andretained hydrocarbon occurrences.
引文
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[15]刘全有,刘文汇,王晓锋,等.不同烃源岩实验评价方法的对比[J].石油实验地质,2007,29(1):88-94.LIU Quanyou,LIU Wenhui,WANG Xiaofeng,et al.Comparisons of geochemical methods for assessment of hydrocarbon generating potential[J].Petroleum Geology&Experiment,2007,29(1):88-94.
[16]曾花森,霍秋立,张晓畅,等.应用岩石热解数据S2-TOC相关图进行烃源岩评价[J].地球化学,2010,39(6):574-579.ZENG Huasen,HUO Qiuli,ZHANG Xiaochang,et al.Source rock evaluation using the S2-TOC plot from Rock-Eval pyrolysis[J].Geochimica,2010,39(6):574-579.
[17]CHEN Z,LIU X,GUO Q,et al.Inversion of source rock hydrocarbon generation kinetics from Rock-Eval data[J].Fuel,2017,194:91-101.
[18]LIAO L,WANG Y,CHEN C,et al.Kinetic study of marine and lacustrine shale grains using Rock-Eval pyrolysis:implications to hydrocarbon generation,retention and expulsion[J].Marine and Petroleum Geology,2018,89:164-173.
[19]MAYER L M,SCHICK L L,HARDY K R,et al.Organic matter in small mesopores in sediments and soils[J].Geochimica et Cosmochimica Acta,2004,68:3 863-3 872.
[20]ZHU X,CAI J,LIU W,et al.Occurrence of stable and mobile organic matter in the clay-sized fraction of shale:significance for petroleum geology and carbon cycle[J].International Journal of Coal Geology,2016,160-161:1-10.
[21]LI Y,CAI J,WANG X,et al.Smectite-illitization difference of source rocks developed in saline and fresh water environments and its influence on hydrocarbon generation:a study from the Shahejie formation,Dongying depression,China[J].Marine and Petroleum Geology,2017,80:349-357.
[22]夏燕青,张更新.未成熟油可能主要来自原生可溶有机质——I.饱和烃提供的直接证据[J].石油实验地质,2001,23(4):438-443.XIA Yanqing,ZHANG Gengxin.Immature crude oils possibly mainly originating from primary soluble organic matter-I.direct evidences from saturated hydrocarbons[J].Petroleum Geology&Experiment,2001,23(4):438-443.
[23]RAHMAN H M,KENNEDY M,LOHR S,et al.Clay-organic association as a control on hydrocarbon generation in shale[J].Organic Geochemistry,2017,105:42-55.
[24]WU L M,ZHOU C H,KEELING J,et al.Towards an understanding of the role of clay minerals in crude oil formation,migration and accumulation[J].Earth-Science Reviews,2012,115:373-386.
[25]宋一涛,廖永胜,张守春.半咸-咸水湖相烃源岩中两种赋存状态可溶有机质的测定及其意义[J].科学通报,2005,50(14):1 531-1 534.SONG Yitao,LIAO Yongsheng,ZHANG Shouchun.Quantitative characterization of organic matters of two different occurrences in brackish-saline lacustrine source rocks and its significance[J].Chinese Science Bulletin,2005,50(14):1 531-1 534.
[26]BU H,YUAN P,LIU H,et al.Effects of complexion between organic matter(OM)and clay mineral on OM pyrolysis[J].Geochimica et Cosmochimica Acta,2017,212:1-15.
[27]蔡郁文,张水昌,何坤,等.烃源岩中无机矿物对有机质生烃的影响[J].石油实验地质,2017,39(2):253-260.CAI Yuwen,ZHANG Shuichang,HE Kun,et al.Effects of inorganic minerals in source rocks on hydrocarbon generation from organic matter[J].Petroleum Geology&Experiment,2017,39(2):253-260.
[28]王行信,蔡进功,包于进.粘土矿物对有机质生烃的催化作用[J].海相油气地质,2006,11(3):27-38.WANG Xingxin,CAI Jingong,BAO Yujin.Catalysis of clay mineral to organic matter in hydrocarbon genesis[J].Marine Petroleum Geology,2006,11(3):27-38.
[29]杨燕,雷天柱,邢蓝田,等.不同类型有机黏土中化学结合态有机质生油能力差异性研究[J].石油实验地质,2015,37(4):487-493.YANG Yan,LEI Tianzhu,XING Lantian,et al.Oil generation abilities of chemically bound organic matter in different types of organic clay complexes[J].Petroleum Geology&Experiment,2015,37(4):487-493.
[2]丁飞,蔡进功,宋明水,等.泥质烃源岩中<2μm黏粒级组分的有机质与比表面关系[J].中国科学:地球科学,2013,43(4):634-641.DING Fei,CAI Jingong,SONG Mingshui,et al.The relationship between organic matter and specific surface area in<2μm clay size fraction of muddy source rock[J].Science China:Earth Sciences,2013,43(4):634-641.
[3]KENNEDY M J,PEVEAR D R,HILL R J.Mineral surface control of organic carbon in black shale[J].Science,2002,295:657-660.
[4]关平,徐永昌,刘文汇.烃源岩有机质的不同赋存状态及定量估算[J].科学通报,1998,43(14):1 556-1 559.GUAN Ping,XU Yongchang,LIU Wenhui.Preservation occurrence of organic matters in source rocks and its quantitative characterization[J].Chinese Science Bulletin,1998,43(14):1 556-1 559.
[5]王兆云,程克明.碳酸盐岩中不同赋存状态有机质地球化学特征对比及对成烃的贡献[J].沉积学报,2000,18(4):600-605.WANG Zhaoyun,CHENG Keming.The organic geochemical characteristics comparison and contributors of different existing state organic matter in carbonate rocks[J].Acta Sedimentologica Sinica,2000,18(4):600-605.
[6]解启来,周中毅,陆明勇.碳酸盐矿物结合有机质一种重要的成烃物质[J].矿物学报,2000,20(1):59-62.XIE Qilai,ZHOU Zhongyi,LU Mingyong.Organic matter enclosed in carbonate mineralsa kind of important hydrocarbon-producing matter[J].Acta Mineralogica Sinica,2000,20(1):59-62.
[7]FARRIMOND P,LOVE G D,BISHOP A N,et al.Evidence for the rapid incorporation of hopanoids into kerogen[J].Geochimicaet Cosmochimica Acta,2003,67:1 383-1 394.
[8]BISHOP A N,LOVE G D,MCAULAY A D,et al.Release of kerogen-bound hopanoids by hydropyrolysis[J].Organic Geochemistry,1998,29:989-1 001.
[9]孙永革,MEREDITH W,SNAPE C E,等.加氢催化裂解技术用于高演化源岩有机质表征研究[J].石油与天然气地质,2008,29(2):276-282.SUN Yongge,MEREDITH W,SNAPE C E,et al.Study on the application of hydropyrolysis technique to the description of organic matter in highly mature source rocks[J].Oil&Gas Geology,2008,29(2):276-282.
[10]蒋启贵,黎茂稳,钱门辉,等.不同赋存状态页岩油定量表征技术与应用研究[J].石油实验地质,2016,38(6):842-849.JIANG Qigui,LI Maowen,QIAN Menhui,et al.Quantitative characterization of shale oil in different occurrence states and its application[J].Petroleum Geology&Experiment,2016,38(6):842-849.
[11]郑伦举,马中良,何生.海相烃源岩二次生烃潜力定量评价新方法[J].沉积学报,2012,30(3):594-602.ZHENG Lunju,MA Zhongliang,HE Sheng.The new methods for quantitative evaluation secondary hydrocarbon generation potential of marine source rocks[J].Acta Sedimentologica Sinica,2012,30(3):594-602.
[12]卢双舫,钟宁宁,薛海涛,等.碳酸盐岩有机质二次生烃的化学动力学研究及其意义[J].中国科学D辑:地球科学,2007,37(2):178-184.LU Shuangfang,ZHONG Ningning,XUE Haitao,et al.Kinetic research of secondary hydrocarbon generation of organic matters in carbonate source rocks and its significance[J].Science in China Series D:Earth Sciences,2007,37(2):178-184.
[13]宋国奇,张林晔,卢双舫,等.页岩油资源评价技术方法及其应用[J].地学前缘,2013,20(4):221-228.SONG Guoqi,ZHANG Linye,LU Shuangfang,et al.Resource evaluation method for shale oil and its application[J].Earth Science Frontiers,2013,20(4):221-228.
[14]张金川,林腊梅,李玉喜,等.页岩油分类与评价[J].地学前缘,2012,19(5):322-331.ZHANG Jinchuan,LIN Lamei,LI Yuxi,et al.Classification and evaluation of shale oil[J].Earth Science Frontiers,2012,19(5):322-331.
[15]刘全有,刘文汇,王晓锋,等.不同烃源岩实验评价方法的对比[J].石油实验地质,2007,29(1):88-94.LIU Quanyou,LIU Wenhui,WANG Xiaofeng,et al.Comparisons of geochemical methods for assessment of hydrocarbon generating potential[J].Petroleum Geology&Experiment,2007,29(1):88-94.
[16]曾花森,霍秋立,张晓畅,等.应用岩石热解数据S2-TOC相关图进行烃源岩评价[J].地球化学,2010,39(6):574-579.ZENG Huasen,HUO Qiuli,ZHANG Xiaochang,et al.Source rock evaluation using the S2-TOC plot from Rock-Eval pyrolysis[J].Geochimica,2010,39(6):574-579.
[17]CHEN Z,LIU X,GUO Q,et al.Inversion of source rock hydrocarbon generation kinetics from Rock-Eval data[J].Fuel,2017,194:91-101.
[18]LIAO L,WANG Y,CHEN C,et al.Kinetic study of marine and lacustrine shale grains using Rock-Eval pyrolysis:implications to hydrocarbon generation,retention and expulsion[J].Marine and Petroleum Geology,2018,89:164-173.
[19]MAYER L M,SCHICK L L,HARDY K R,et al.Organic matter in small mesopores in sediments and soils[J].Geochimica et Cosmochimica Acta,2004,68:3 863-3 872.
[20]ZHU X,CAI J,LIU W,et al.Occurrence of stable and mobile organic matter in the clay-sized fraction of shale:significance for petroleum geology and carbon cycle[J].International Journal of Coal Geology,2016,160-161:1-10.
[21]LI Y,CAI J,WANG X,et al.Smectite-illitization difference of source rocks developed in saline and fresh water environments and its influence on hydrocarbon generation:a study from the Shahejie formation,Dongying depression,China[J].Marine and Petroleum Geology,2017,80:349-357.
[22]夏燕青,张更新.未成熟油可能主要来自原生可溶有机质——I.饱和烃提供的直接证据[J].石油实验地质,2001,23(4):438-443.XIA Yanqing,ZHANG Gengxin.Immature crude oils possibly mainly originating from primary soluble organic matter-I.direct evidences from saturated hydrocarbons[J].Petroleum Geology&Experiment,2001,23(4):438-443.
[23]RAHMAN H M,KENNEDY M,LOHR S,et al.Clay-organic association as a control on hydrocarbon generation in shale[J].Organic Geochemistry,2017,105:42-55.
[24]WU L M,ZHOU C H,KEELING J,et al.Towards an understanding of the role of clay minerals in crude oil formation,migration and accumulation[J].Earth-Science Reviews,2012,115:373-386.
[25]宋一涛,廖永胜,张守春.半咸-咸水湖相烃源岩中两种赋存状态可溶有机质的测定及其意义[J].科学通报,2005,50(14):1 531-1 534.SONG Yitao,LIAO Yongsheng,ZHANG Shouchun.Quantitative characterization of organic matters of two different occurrences in brackish-saline lacustrine source rocks and its significance[J].Chinese Science Bulletin,2005,50(14):1 531-1 534.
[26]BU H,YUAN P,LIU H,et al.Effects of complexion between organic matter(OM)and clay mineral on OM pyrolysis[J].Geochimica et Cosmochimica Acta,2017,212:1-15.
[27]蔡郁文,张水昌,何坤,等.烃源岩中无机矿物对有机质生烃的影响[J].石油实验地质,2017,39(2):253-260.CAI Yuwen,ZHANG Shuichang,HE Kun,et al.Effects of inorganic minerals in source rocks on hydrocarbon generation from organic matter[J].Petroleum Geology&Experiment,2017,39(2):253-260.
[28]王行信,蔡进功,包于进.粘土矿物对有机质生烃的催化作用[J].海相油气地质,2006,11(3):27-38.WANG Xingxin,CAI Jingong,BAO Yujin.Catalysis of clay mineral to organic matter in hydrocarbon genesis[J].Marine Petroleum Geology,2006,11(3):27-38.
[29]杨燕,雷天柱,邢蓝田,等.不同类型有机黏土中化学结合态有机质生油能力差异性研究[J].石油实验地质,2015,37(4):487-493.YANG Yan,LEI Tianzhu,XING Lantian,et al.Oil generation abilities of chemically bound organic matter in different types of organic clay complexes[J].Petroleum Geology&Experiment,2015,37(4):487-493.