煤系地层中不同类型镜质体可能的化学结构与生物母质

doi:10.11743/ogg20040404

摘要/Abstract

摘要：

通过固体¹³C核磁共振(NMR)及瞬时热解-色谱/质谱(Py-GC/MS)实验,研究了中国准噶尔盆地东部侏罗系、吐哈盆地侏罗系、鄂尔多斯盆地石炭-二叠系煤系镜质体的结构特征。侏罗系富氢基质镜质体脂碳部分具有较高比例的亚甲基碳(-CH₂-),热解产物中脂肪烃所占比例较高。侏罗系均质镜质体虽然也是富氢镜质体,但同基质镜质体相比,脂肪碳中含有更高比例的甲基(-CH₃)、次甲基(-CH-)、季碳(-C-)等;热解产物以酚类及烷基苯为主,且支链取代基较多,链长较短。鄂尔多斯盆地石炭-二叠系镜质体虽然多以基质镜质体为主,但脂肪碳所占比例相对较低,且以气潜力碳为主;热解产物以酚类及芳烃为主,为典型气源岩。在成熟度相似的情况下,不同沉积环境与生物母质决定了镜质体的结构特征。准噶尔盆地东部、吐哈盆地富氢基质镜质体较高的长链脂肪烃结构是由于超微类脂体的贡献。通过与藻质体、角质体、孢子体、木栓质体的裂解产物对比,结合其他证据大致认为高等植物壳质组更有可能是超微类脂体的主要成分。

关键词: 镜质体, 固体¹³C核磁共振, 热解, 化学结构, 生烃母质

Abstract:

Chemical constitutions of vitrinites in Jurassic coal measures in eastern Junggar basin and Turpan-Hami basin,and Permo-Carboniferous coal measures in Ordos basin,are studied through solid-state ¹³C NMR and transient pyrolysis-GC/MS. The aliphatic carbons in Jurassic hydrogen-rich desmocollinites have relatively high proportion of methylene carbon(-CH₂-),and the proportion of aliphatic hydrocarbons in pyrolysis products are relatively high. Being compared with desmocollinites, although the Jurassic telocollinites are also hydrogen-rich, their aliphatic carbons have even higher proportion of methyl(-CH₃),methine(-CH-) and quaternary carbon, and their pyrolysis products are mainly phenols and alkylbenzenes, with more branched substitiuents but shorter chain length. Though the Permo-Carboniferous vitrinites in Ordos basin are mostly composed of desmocollinites, they contain a relatively small proportion of aliphatic carbons, and most of which are gas-prone carbons. The pyrolysis products are mainly phenols and aromatic hydrocarbons, thus they are typical gas source rocks. With similar maturities, the structures of vitrinites are determined by sedimentary environments and original bilological materials. Ultramicroliptinites might have contributed to the relatively high constitutions of long chain aliphatic hydrocarbons in hydrogen-rich vitrinites in eastern Junggar and Turpan-Hami basins. Based on comparison with pyrolysis products of phycoplast,cutinites, sporinites and suberinite, and in combination with other evidences, it is believed that exinites of higher plants are more likely to be the main components of Ultramicroliptinites.

Key words: vitrinite, solid ¹³C NMR, pyrolysis, chemical structure, parent material of hydrocarbons

中图分类号:

TE112.113

刘大永,彭平安. 煤系地层中不同类型镜质体可能的化学结构与生物母质[J]. 石油与天然气地质, 2004, 25(4): 377-384. doi: 10.11743/ogg20040404 Liu Dayong,Peng Ping'an. Possible chemical constitutions and original biological materials of various vitrinites in coal measure strata[J]. Oil & Gas Geology, 2004, 25(4): 377-384. doi: 10.11743/ogg20040404

参考文献

[1] 程克明.吐哈盆地油气生成[M].北京:石油工业出版社, 1994
[2] 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
[3] 王昌桂,程克明, 徐永昌,等.吐哈盆地侏罗系煤成烃地球化学[M].北京:科学出版社,1996
[4] Bertrand P.Geochemical and petrographic characterization of humic coals considered as possible oil source rocks[J]. Organic Geochemistry, 1984, 6:481～488
[5] 姚素平,毛鹤龄, 金奎励,等.准噶尔盆地侏罗系西山窑组沉积有机相研究及烃源岩评价[J].中国矿业大学学报,1997,26(1):60～64
[6] 赵长毅,何忠华,程克明,等.吐哈盆地煤中基质镜质体生烃潜力与特征[J]. 科学通报,1994,39(21):1979～1981
[7] 孙旭光, 陈建平, 王延斌.吐哈盆地侏罗纪煤中主要组分结构特征与生烃性分析 [J].沉积学报,2002,20(4):721～726
[8] 刘惠永,张爱云,翁成敏.贵州六盘水地区龙潭煤系煤岩富氢显微组分的生烃潜力与生烃贡献[J].石油实验地质,1999,21(1):66～70
[9] Solli H,Leplat P.Pyrolysis-gas chromatography of asphaltenes and kerogens from source rocks and coals:a comparative structural study[J].Organic Geochemistry,1986,10:313～329
[10] Hartgers W A, Damste J S S, de Leeuw J W,et al.Molecular characterization of flash pyrlysates of two carboniferous coals and their constituting maceral frac tions[J]. Energy & Fuels, 1994,8(8):1055～1067
[11] 孙永革, 盛国英, 傅家谟,等.我国主要含煤油气盆地煤系源岩PY-GC热解产物组成及意义 [J].沉积学报,1995,13(2):120～127
[12] 傅家谟, 秦匡宗.干酪根地球化学[M].广州:广东科技出版社,1995.299
[13] 秦匡宗,郭绍辉.NMR在固体化石能源中的应用[J].波谱学杂志,1995,12(5):45 1～458
[14] Dennis L W, Maciel G E, Hatcher P G, et al.¹³C nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by ba saltic intrusions and laboratory simulations[J].Geochimica et Cosmochimica Acta, 1982, 46:901～907
[15] 秦匡宗,郭绍辉, 黄第藩,等.用13C NMR波谱技术研究烃源岩显微组分的化学结构与成烃潜力 [J].石油大学学报,1995,19(4):87～94
[16] 黄第藩.成烃理论的发展--(Ⅱ)煤成油及其初次运移模式[J].地球化学进展,1996,11(7):432～438
[17] Qin K, Chen D, Li Z. A new method to estimate the oil and gas potentials of coals and kerogens by solid state ¹³C NMR spectroscopy[J].Organic Geochemistry, 1991, 17(6):865～872
[18] Larter S R.Application of analytical prolysis techniques to kerogen charact erization and filling fuel exploration[A].In:Voorhees K.Analytical pyrolysis- methods and applications[C].London:Butterworth, 1984.212～272
[19] van Graas G, de Leeuw J W, Schench P A.Kerogen of Toarcian shales of the Paris Basin:a study of its maturation by flash pyrolysis techniques[J]. Geochimica et Cosmochimica Acta, 1981,45,2465～2474
[20] Hartgers W A, Damste J S S.de Leeuw J W, et al.Geochemical significance of alkylbenzene distrubitions in flash pyrolysates of kerogens, coals, and asphalt enes[J].Geochimica et Cosmochimica Acta,1994, 58(7):1759～1775
[21] Senftle J T, Larter S R, Bromley B W,et al.Quantitative chemical character ization of vitrinite concentrates using pyrolysis-gas chromatography:rank vari ation of pyrolysis products[J].Organic Geochemistry,1986,9(6):345～350
[22] del Rio J C,Garcia-Molla J F J, Gonzalez-Vila F J,et al.Flash pyrolysis-gas chromatography of the kerogen and asphaltene fractions isolated from a sequen ce of oil shales[J].Journal of Chromatogrraphy,1993,657:119～122
[23] Iglesias M J,Cuesta M J,Suarez-Ruiz I, et al.Structure of tars derived from low-temperature pyrolysis of pure vitrinites:influence of rank and composit ion of vitrinites[J].Journal of Analytical and Applied Pyrolysis,2001,58～59:255～284
[24] 孙永革, 朱进, 徐华,等.生油煤形成的环境制约[J].地球化学,2002,31(1):9～15
[25] 庄新国,李思田, 王生维.抚顺盆地富氢煤的特征及形成条件[J].石油实验地质, 1999,21(2):150～155
[26] 赵长毅, 赵文智, 程克明,等.吐哈盆地煤油源岩形成条件与生油评价[J].石油学报,1998,19(3):21～26
[27] 姚素平, 张景荣, 金奎励,等.准噶尔盆地侏罗纪含煤地层沉积有机相研究[J].西北地质科学,1996,17(2):75～84
[28] 柳益群,冯乔, 郝建荣.吐-哈盆地侏罗系油藏煤成油问题的讨论[J].石油与天然气地质,2002,23(4):326～331
[29] 李贤庆, 赵师庆.苏鲁一带不同还原型镜质组的显微岩石学特征及其生烃潜力[J ].石油与天然气地质,1995,16(1):24～32
[30] 王飞宇, 傅家谟, 刘德汉.煤和烃源岩镜质体中超微类脂体检出及意义[J].科学通报,1993,38(2):151～154
[31] 刘大锰, 王运泉.鄂尔多斯盆地煤的超微特征[J].煤炭学报,1997,22(5):460 ～465
[32] 王飞宇, 傅家谟, 刘德汉,等.华北东部太原组镜质组中超微类脂体和太原组煤性质异常性的原因[J].地球化学,1995,24(增刊):7～15
[33] 赵长毅, 程克明, 王飞宇.吐哈盆地煤成烃主要贡献组分剖析[J].沉积学报,199 7,15(2):95～99
[34] 陈建平, 黄第藩, 李晋超,等.西北地区侏罗纪煤系有机质成烃模式[J].地球化学,1999,28(4):327～339
[35] 傅家谟, 刘德汉, 盛国英.煤成烃地球化学[M].北京:科学出版社,1992.108
[36] 陈佩元, 孙达三, 丁丕训,等.中国煤岩图鉴[M].北京:煤炭工业出版社,1996.10
[37] 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
[38] Nip M,de Leeuw J W.Chemical structure of bituminous coal and its constitut ing maceral fractions as revealed by flash pyrolysis[J].Energy & Fuels, 1992, 6:125～136
[39] Han Z,Kruge M A.Classification of torbanite and cannel coalⅡ:insights from pyrolysis-GC/MS and multivariate statistical analysis[J].International Journal of Coal Geology, 1999, 38:203～218
[40] Khorasani G K,Michelsen J K.Geological and laboratory evidence for early generation of large amounts of liquid hydrocarbons from suberinite and suberous components[J].Organic Geochemistry,1991,17(6):849～863
[41] 曾凡刚,王铁冠,盛国英,等.广西三种褐煤的生物标志物组合特征[J].石油与天然气地质,1994,15(2):141～150