煤样中单体显微组分的激光微裂解分析
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摘要
镜质体和树脂体是煤中重要的有机显微组成,认识其化学组成及结构,对生烃潜力的评价具有重要意义。通过结合光学显微镜和优化的激光微裂解-色谱-质谱技术,分析了云南红河古近系煤样中单个镜质体和树脂体的激光微裂解产物。结果表明,单芳烃、双芳烃、二萜类化合物和正构烯烃/烷烃对等在两显微组分中均有检出,且芳烃化合物和二萜类化合物分布非常相似;丰富的降海松烷和扁枝烷指示了裸子植物,尤其是针叶树脂的贡献;脂肪烃以及藿类化合物的组成及分布不同,表明激光微裂解-色谱-质谱技术能够区分同一样品中不同显微组分的成烃差异,从而对有效生烃组分的判识提供重要的分子证据。除此之外,还探讨了与传统地球化学分析技术相比激光微裂解-色谱-质谱分析技术所具有的优势。
Vitrinite and resinite are important macerals within the coal.To understand their chemical compositions and structures is of great significance for the evaluation of hydrocarbon potential.The combination of optical microscope and modified laser micropyrolysis GC-MS technique was employed to analyze the vitrinite and resinite within a Paleogene coal of Honghe region of Yunnan Province.The pyrolyzates have shown to have the ubiquitous mono and diaromatic hydrocarbons,diterpenoids as well as n-alkene/ane doublets for both of vitrinite and resinite,among which,the similar distribution of aromatic hydrocarbons and diterpenoids were obvious,and abundant norpimarane and phyllocladane were derived from gymnospermae,especially contributed by conifer resins.However,the distributions of aliphatic hydrocarbons and hopanoids in the pyrolyzates were distinct.The successful application of laser micropyrolysis indicates it is a micrometer scale method to recognize hydrocarbon generation characteristics of various macerals within a single sam-ple,and thus make it possible to identify effective hydrocarbon-generation macerals.In addition,compared with conventional geochemical techniques,the superiority of laser micropyrolysis GC-MS technique was discussed as well.
Vitrinite and resinite are important macerals within the coal.To understand their chemical compositions and structures is of great significance for the evaluation of hydrocarbon potential.The combination of optical microscope and modified laser micropyrolysis GC-MS technique was employed to analyze the vitrinite and resinite within a Paleogene coal of Honghe region of Yunnan Province.The pyrolyzates have shown to have the ubiquitous mono and diaromatic hydrocarbons,diterpenoids as well as n-alkene/ane doublets for both of vitrinite and resinite,among which,the similar distribution of aromatic hydrocarbons and diterpenoids were obvious,and abundant norpimarane and phyllocladane were derived from gymnospermae,especially contributed by conifer resins.However,the distributions of aliphatic hydrocarbons and hopanoids in the pyrolyzates were distinct.The successful application of laser micropyrolysis indicates it is a micrometer scale method to recognize hydrocarbon generation characteristics of various macerals within a single sam-ple,and thus make it possible to identify effective hydrocarbon-generation macerals.In addition,compared with conventional geochemical techniques,the superiority of laser micropyrolysis GC-MS technique was discussed as well.
引文
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[14]陈建平,邓春萍,王汇彤,等.中国西北侏罗纪煤系显微组分热解油生物标志物特征及其意义[J].地球化学,2006,35(2):141-150.CHEN Jianping,DENG Chuanping,WANG Huitong,et al.Biomarker and its implication of pyrolysis oils of macerals from Jurassic coal measures,Northwest China[J]. Geochimica,2006,35(2):141-150.
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[18] RATHBONE R F,DAVIS A.The effects of depositional environment on vitrinite fluorescence intensity[J].Organic Geochemistry,1993,20(2):177-186.
[19]文志刚,张爱云,王正允,等.基质镜质体成烃的新认识[J].石油与天然气地质,2001,22(2):102-104.WEN Zhigang,ZHANG Aiyun,WANG Zhengyun,et al.New recognition on hydrocarbon generation of desmocollinite[J]. Oil&Gas Geology,2001,22(2):102-104.
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[21] ZHANG Z,GREENWOOD P,ZHANG Q,et al.Laser ablation GCMS analysis of oil-bearing fluid inclusions in petroleum reservoir rocks[J].Organic Geochemistry,2012,43:20-25.
[22] ZHANG Z,HU W,SONG X,et al. A comparison of results from two different flash pyrolysis methods on a solid bitumen sample[J].Organic Geochemistry,2014,69(2):36-41.
[23] GOOSSENS H,DE LEEUW J W,SCHENCK P A,et al.Tocopherols as likely precursors of pristane in ancient sediments and crude oils[J].Nature,1984,312:440-442.
[24] BROWN M R,MULAR M,MILLER I,et al. The vitamin content of microalgae used in aquaculture[J].Journal of Applied Phycology,1999,11:247-255.
[25] NASSIRY M,AUBERT C,MOUZDAHIR A,et al.Generation of isoprenoid compounds,notably prist-1-ene,via photo and autoxidative degradation of vitamin E[J].Organic Geochemistry,2009,40:38-50.
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