下马岭组油页岩热模拟实验抽提物中三芴系列化合物演化特征

doi:10.11764/j.issn.1672-1926.2019.03.004

天然气地球科学

下马岭组油页岩热模拟实验抽提物中三芴系列化合物演化特征

杨娟，王作栋，薄海波，张婷，吉生军，王静莹

1.青海师范大学化学化工学院，青海西宁 810008；
2.中国科学院油气资源研究重点实验室，甘肃兰州 730000；
3.中国科学院大学，北京 100049

收稿日期:2018-12-03 修回日期:2019-03-10 出版日期:2019-07-10
作者简介:杨娟(1993-)，女，四川南充人，在读硕士，主要从事地球化学研究.E-mail：805677835@qq.com.
基金资助:
国家自然科学基金项目 “地质条件下温度对甾烷的形成和分布的影响研究”（编号：41772133)；中国科学院仪器设备功能开发技术创新项目“GCMA快速热分离进样装置的研发”（编号：2019g106)；中国科学院地质与地球物理研究所兰州油气资源研究中心“十三五”创新基金课题（编号：135CCJJ20160523)联合资助.

Evolution characteristics of trifluorene compounds in the extracts of oil shale of Xiamaling Formation by thermal simulation test

Yang Juan，Wang Zuo-dong，Bo Hai-bo，Zhang Ting，Ji Sheng-jun，Wang Jing-ying

1.Department of Chemistry，Qinghai Normal University，Xining 810008，China；
2.Key Laboratory of Petroleum Resources，Chinese Academy of Sciences，Lanzhou 730000，China；3.University of Chinese Academy of Sciences，Beijing 100049，China

Received:2018-12-03 Revised:2019-03-10 Online:2019-07-10
About author:Yang Juan(1993-), Female, Master degree candidate, Mainly engaged in geochemistry research. E-mail：805677835@qq.com.
Supported by:
Supported by the National Natural Science Foundation of China “Study on the effect of temperature on the formation and distribution of sterane under geological conditions” (Grant No. 41772133); the Chinese Academy of Sciences Instrument and Equipment Function Development Technology Innovation Project “Development of GCMA rapid thermal separation sampler” (Grant No. 2019g106); the 13th Five-Year Innovation Fund Project of Lanzhou Oil and Gas Resources Research Center, Institute of Geology and Geophysics, Chinese Academy of Sciences (Grant No. 135CCJJ20160523)

摘要/Abstract

摘要： 对华北张家口中元古界下马岭组低熟海相页岩进行温压模拟实验，并对原始样品和模拟后的残渣抽提物做了GC/MS分析，讨论了2种温压模式下三芴系列化合物（以下简称“三芴”)的演化规律。结果表明，三芴的相对含量受温度影响，且压力在不同温度条件下对三芴含量也有较大影响。主要表现在以下方面：①随着温度升高、压力增大，呈现出F的相对含量增大、OF含量减小、SF含量无明显变化的规律，三芴相对丰度表现出F>OF>SF特征；②温度低于390℃时，温压共同作用比单一温度作用更易使有机质进入成熟阶段；③温度低于337℃时，加压抑制了共轭烯键的芳构化；温度高于337℃时，加压促进了共轭烯键芳构化；在327～450℃温度范围内，硫芴表现出较好的热稳定性；④随着温度的升高，模拟实验样品的成熟度从未成熟演化到成熟晚期，三芴含量的原始比例构成发生了较大变化，故利用三芴相对含量判断有机质沉积环境时，要考虑温度对三芴相对含量变化的影响。

关键词: 三芴, 下马岭组, 温压模拟实验, 低熟海相页岩

Abstract: Temperature-pressure simulating experiment was conducted for the low mature marine shale samples from the Cambrian Xiamaling Formation in the middle Proterozoic in Zhangjiakou of North China，then GC/MS was applied to analyze the original samples and the residue collected from the simulating test in the experiments.The results show that the relative content of trifluorene is affected by temperature，and the pressure has great effect on the content of trifluorene under different temperature conditions.It is reflected in the following aspects：(1)With the increase of temperature and pressure，the relative content of F increases，the content of OF decreases，and the SF content has no obvious changes.The relative abundance of trifluorene showed the characteristic of F>OF>SF；(2)When the temperature is lower than 390℃，the interaction of temperature and pressure can make organic matter into mature stage more easily than that of single temperature；(3)When the temperature is lower than 337℃，the aromatization of conjugated olefinic bond is inhibited by pressure；when the temperature is higher than 337℃，it is the opposite，in 327-450℃ temperature range，dibenzothiophene show good thermal stability；(4)With the increase of temperature，the maturity of the simulated sample never evolved to the lately mature，and the original proportion of trifluorene content changed greatly.Therefore，when the relative content of trifluorene was used to judge the organic matter sedimentary environment，the effect of temperature on the relative content of trifluorene should be considered.

Key words: Trifluorene, Xiamaling Formation, Temperature-pressure simulating experiment, Low-maturity marine shale

中图分类号:

TE122.1⁺13

杨娟, 王作栋, 薄海波, 张婷, 吉生军, 王静莹. 下马岭组油页岩热模拟实验抽提物中三芴系列化合物演化特征[J]. 天然气地球科学, 2019, 30(7): 1063–1071.

Yang Juan, Wang Zuo-dong, Bo Hai-bo, Zhang Ting, Ji Sheng-jun, Wang Jing-ying. Evolution characteristics of trifluorene compounds in the extracts of oil shale of Xiamaling Formation by thermal simulation test[J]. Natural Gas Geoscience, 2019, 30(7): 1063–1071.

参考文献

［1］Zhang M，Philp P.Geochemical characterization of aromatic hydrocarbons in crude oils from the Tarim，Qaidam and Turpan Basins，NW China[J].Petroleum Science，2010，7(4)：448-457.
[2]Chakhmakhchev A，Suzuki M，Takayama K.Distribution of alkylated dibenzothiophenes in petroleum as a tool for maturity assessments[J].Organic Geochemistry，1997，26(7)：483-489.
[3]Luo Binjie，Li Xinyu.Characteristics of aromatic hydrocarbons in crude oils[J].Geochimica，1993，(2)：127-135.
罗斌杰，李新宇.原油中芳烃化合物特征[J].地球化学，1993，(2)：127-135.
[4]Hughes W B，Holba A G，Dzou L I P．The ratios of dibenzothiophene to phennanthrene and pristane to phytane as indicators of depositional environment and lithology of petroleum source rocks[J].Geochimica et Cosmochimica Acta，1995，59(17)：3581-3598．
[5]Radke M，Vriend S P，Ramamampisoa L R．Alkyl dibenzofurans in terrestrial rocks：Influnence of organic facies and maturation[J].Geochimica et Cosmochimica Acta，2000，64(2)：275-286．
[6]Lin Renzi，Wang Peirong，Dai Yunjian，et al.Petroleum Geochemical Significance of Polycyclic Aromatic Hydrocarbons in Fossil Fuels[C].Collection of papers on Organic Geochemistry，Beijing：Geological Publishing House，1987：129-140．
林壬子，王培荣，戴允健，等.矿物燃料中多环芳烃的石油地球化学意义[C].有机地球化学论文集，北京：地质出版社，1987：129-140．
[7]Xia Yanqing，Wang Chunjiang，Meng Qianxiang，et al.Genetic simulation of thiofluorene and oxyfluorene[J].Chinese Science Bulletin，1998，43(15)：1661-1663.
夏燕青，王春江，孟仟祥，等.硫芴和氧芴成因模拟[J].科学通报，1998，43(15)：1661-1663.
[8]Wang Tieguan，He Faqi，Li Meijun，et al.Alkyl dibenzothiophene：A molecular marker of the filling pathway in a tracer reservoir[J].Chinese Scientific Bulletin，2005，50(2)：176-182.
王铁冠，何发岐，李美俊，等.烷基二苯并噻吩类：示踪油藏充注途径的分子标志物[J].科学通报，2005，50(2)：176-182.
[9]Ma Jun，Li Shuifu，Hu Shouzhi，et al.The composition of aromatic hydrocarbon and its application in petroleum geochemistry[J].Geological Science and Technology Information，2010，29(6)：73-79.
马军，李水福，胡守志，等.芳烃化合物组成及其在油气地球化学中的应用[J].地质科技情报，2010，29(6)：73-79．
[10]Wang Chuanyuan，Du Jianguo，Duan Yi，et al.Geochemical characteristics and significance of aromatic hydrocarbons in oil and gas[J].Xinjiang Petroleum Geology，2007，28(1)：29-32.
王传远，杜建国，段毅，等.芳烃地球化学特征及地质意义[J].新疆石油地质，2007，28(1)：29-32．
[11]Zhang Ting，Wang Zuodong，Qian Yu，et al.Evolution characteristics of the phenanthrene and anthracene series in the liquid products from the temperature-pressure experiments[J].Petroleum Geology and Oilfield Development in Daqing，2018，37(2)：48-55.
张婷，王作栋，钱宇，等.温压实验液态产物中菲和蒽系列的演化特征[J].大庆石油地质与开发，2018，37(2)：48-55.
[12]Wang Zuodong，Liang Mingliang，Zheng Jianjing，et al.Molecular fingerprint of source rocks of Xiamaling Formation of Meso-Neoproterozoic in North China[J].Natural Gas Geoscience，2013，24(3)：599-603.
王作栋，梁明亮，郑建京，等.华北中—上元古界下马岭组烃源岩分子指纹特征[J].天然气地球科学，2013，24(3)：599-603.
[13]Gough M A，Rhead M M，Rowland S J.Biodegradation studies of unresolved complex mixtures of hydrocarbons，model UCM hydrocarbons and the aliphatic UCM[J].Organic Geochemistry，1992，18(1)：17-22.
[14]Warton B，Alexander B，Kagi R.Characterization of ruthenium tetroxide oxidation products from the aromatic unresolved complex mixture of a biodegraded crude oil[J].Organic Geochemistry，1999，30(10)：1255-1272.
[15]Cao Zhenghua，Hu Chaoyong，Huang Xianyu，et al.Cobalt-rich crust molecular fossils indicate microbial mineralization[J].Marine Geology & Quaternary Geology，2008，(3)：84-92，114.
曹振华，胡超涌，黄咸雨，等.富钴结壳分子化石指示的微生物成矿作用[J].海洋地质与第四纪地质，2008，(3)：84-92，114.
[16]Wenger L M，Isaksen G H.Control of hydrocarbon seepage intensity on level of biodegradation in sea bottom sediments[J].Organic Geochemistry，2002，33(12)：1277-1292.
[17]Hoering T C，Navale V.A search for molecular fossils in the kerogen of Precambrian sedimentary rocks[J].Precabrian Research，1987，34(3/4)：247-267.
[18]Corbett R E，Smith R A.Lichens and fungi.PartⅥ：Dehydration rearrangements of 15-hydroxyhopanes[J].Journal of the Chemical Society C，1969，(1)：44-47.
[19]Ourisson G，Rohmer M，Poralla K.Prokaryotic hopanoids and other polyterpenoid sterol surrogates[J].Annual Review of Microbiology，1987，41(1)：301-333
[20]Ding Anna，Hui Rongyao，Zhang Zhongning.Aromatic geochemical of crude oils and source rocks in Baijiahai Convexity in Junggar Basin[J].Petroleum Exploration and Development，1997，24(3)：15-20.
丁安娜，惠荣耀，张中宁.准葛尔盆地白家海凸起湖相原油与烃源岩芳烃地球化学特征[J].石油勘探与发，1997，24(3)：15-20.
[21]Meng Jianghui，Liu Luofu，Zhang Min，et al.Indicative function of aromatic hydrocarbon in crude oil depositional environmental[J].Journal of China University of Mining & Technology，2011，40(6)：901-907.
孟江辉，刘洛夫，张敏，等.原油芳烃的沉积环境指示作用[J].中国矿业学学报，2011，40(6)：901-907.
[22]Luo Changrong，Zhao Zhenyi，Liu Hangang，et al.Effect of pyrolytic temperature β-carotene on the pyrolytic products[J].Journal of Wuxi University of Light Industry，2003，22(3)：67-75.
罗昌荣，赵震毅，刘涵刚，等.β-胡萝卜素裂解温度对其裂解产物的影响[J].无锡轻工业学学报，2003，22(3)：67-75.
[23]Xia Yanqing，Meng Jianxiang，Wang Hongyong，et al.The mechanism on formation of fluorene series compounds[J].Acta Sedimentologica Sinica，1999，17(4)：158-161.
夏燕青，孟仟祥，王红勇，等.芴系列化合物的成因[J].沉积学报，1999，17(4)：158-161.
[24]Xia Yanqing，Wang Chunjiang，Meng Qianxiang，et al.The simulation on the mechanism of formation of thiophene series compounds[J].Geochemistry，1999，28(4)：393-396.
夏燕青，王春江，孟仟祥，等.噻吩系列化合物的形成机理模拟[J].地球化学，1999，28(4)：393-396.
[25]Xia Yanqing，Wang Chunjiang，Meng Qianxiang，et al.Formation mechanism of biphenyl series compounds and benzonaphthylthiophene series compounds[J].Scientia Sinica：Terrae，1999，29(3)：257-262.
夏燕青，王春江，孟仟祥，等.联苯系列化合物与苯并萘噻吩系列化合物的形成机制[J].中国科学：D辑，1999，29(3)：257-262.
[26]Milner C W D，Rogers M A，Evans C R.Petroleum transformations in reservoirs[J].Journal of Geochemical Exploration，1977，7(2)：101-153.
[27]Lin R Z，Wang P R.PAH in fossils and their geochemical significance[J].Journal of Southeast Asian Earth Sciences，1991，5(1-4)：257-262.
[28]Li Sumei，Wang Tieguan，Zhang Aiyun，et al.Geochemical characteristics and significance of the pyrrolic compounds in petroleum[J].Acta Sedimentologica Sinica，1999，17(2)：147-152.
李素梅，王铁冠，张爱云，等.原油中吡咯类化合物的地球化学特征及其意义[J].沉积学报，1999，17(2)：147-152.
[29]Chen Zhilin，Li Sujuan，Wang Zhong.A study on maturity indicatorssome of some aromatics in low-midmature thermal evolution zones[J].Acta Sedimentologica Sinica，1997，15(2)：192-197.
陈致林，李素娟，王忠.低—中成熟演化阶段芳烃成熟度指标的研究[J].沉积学报，1997，15(2)：192-197.
[30]Zhang Gangqing，Li Shuifu，He Sheng，et al.Composition characteristics and geochemical significance of aromatics hydrocarbons of crude oil from the Banqiao Depression[J].Acta Sedimentologica Sinica，2009，27(2)：367-371.
张刚庆，李水福，何生，等.板桥凹陷原油芳烃组成特征及地球化学意义[J].沉积学报，2009，27(2)：367-371.
[31]Gao Yang.Characteristics and distribution of salt lake source rocks from lower submemeber of 4th member of Shahejie formation，north Dongying Depression[J].Petroleum Geology and Recovery Efficiency，2014，21(1)：10-15.
高阳.东营凹陷北部沙四段下亚段盐湖相烃源岩特征及展布[J].油气地质与采收率，2014，21(1)：10-15.
[32]Chen Yan，Bao Jianping，Liu Zhaoxi，et al.Relationship between methylphenanthrene index，methylphenanthrene ratio and organic thermal evolution：Take the northern margin of Qaidam Basin as an example[J].Petroleum Exploration and Development，2010，37(4)：508-512.
陈琰，包建平，刘昭茜，等.甲基菲指数及甲基菲比值与有机质热演化关系——以柴达木盆地北缘地区为例[J].石油勘探与开发，2010，37(4)：508-512.
[33]Tang Qi，Li Meijun.Relationship between methylphenanthrene index and maturity of organic matter in marine shale[J].Petroleum Geology and Recovery Efficiency，2015，22(3)：62-66.
唐琪，李美俊.海相页岩有机质甲基菲指数与成熟度关系[J].油气地质与采收率，2015，22(3)：62-66.
[34]Li Ying，Zhu Yangming，Hao Fang，et al.Thermal evolution and application of aromatics in high mature coal measures source rocks of Upper Triassic Xujiahe formation in northern Sichuan Basin[J].Scientia Sinica：Terrae，2015，45(7)：953-962.
李颖，朱扬明，郝芳，等.四川盆地北部上三叠统须家河组高成熟煤系烃源岩芳烃热演化与应用[J].中国科学：地球科学，2015，45(7)：953-962.
[35]Zhou Wen，Wu Qingyu，Wang Ruiyong，et al.Distribution of aromatic hydrocarbon biomarkers in heat simulated products of Coccolithopsis[J].Chinese Science Bulletin，2000，45(22)：2438-2446.
周文，吴庆余，王睿勇，等.颗石藻热模拟产物中芳烃生物标志物分布[J].科学通报，2000，45(22)：2438-2446.

Metrics

Viewed

Full text

Abstract

Cited

Shared

Discussed

[1]	王作栋，梁明亮，郑建京，李晓斌，李中平，钱宇. 华北中—上元古界下马岭组烃源岩分子指纹特征[J]. 天然气地球科学, 2013, 24(3): 599-603.
[2]	陈践发,孙省利 . 华北新元古界下马岭组富有机质层段的地球化学特征及成因初探[J]. 天然气地球科学, 2004, 15(2): 110-114.