烃源岩与&lt;2μm黏粒级组分的热解—色谱特征对比及其意义

郭敏, 蔡进功, 蒋启贵, 丁飞

doi:10.11764/j.issn.1672-1926.2016.04.0688

天然气地球科学 >

2016 , Vol. 27 >Issue 4: 688 - 698

DOI: https://doi.org/10.11764/j.issn.1672-1926.2016.04.0688

天然气地球化学

烃源岩与<2μm黏粒级组分的热解—色谱特征对比及其意义

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1.同济大学海洋地质国家重点实验室，上海 200092；
2.中国石油辽河油田分公司勘探开发研究院，辽宁盘锦 124010；
3.中国石化石油勘探开发研究院无锡石油地质研究所，江苏无锡 214151

郭敏(1988-)，女，湖北天门人，硕士研究生，主要从事油气地球化学研究. E-mail:guominxy@163.com.

收稿日期: 2015-08-20

修回日期: 2015-10-27

网络出版日期: 2019-09-20

基金资助

国家自然科学基金(编号：41372130;41072089)；国家科技重大专项(编号：2016ZX05006-001)联合资助.

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Comparison and its significance of pyrolysis-gas chromatography characteristics in source rock and clay fraction with diameter <2μm

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1.State Key Laboratory of Marine Geology,Tongji University,Shanghai 200092,China;2.Exploration & Development
Research Institute,PetroChina Liaohe Oilfield Company,Panjin 124010,China;3.Wuxi Research Institute of
Petroleum Geology,Petroleum Exploration and Production Research Institute,SINOPEC,Wuxi 214151,China

Received date: 2015-08-20

Revised date: 2015-10-27

Online published: 2019-09-20

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摘要

选取济阳坳陷东营凹陷古近系不同埋深的11块烃源岩样品，粉碎后提取粒径小于2μm黏粒级组分，分3个温度段(＜300℃、300～500℃、500～650℃)进行全岩和黏粒级组分样品的热解—色谱检测，探讨不同温度段释放烃的特征和意义，以及黏粒级组分对于烃源岩生烃的贡献。结果表明：在不同温度段，不管是烃源岩全岩还是黏粒级组分，轻质油(C₅—C₁₄)组分在所有组分中含量高，在300℃以前和300～500℃段轻质油组分含量超过50%，而在500～650℃段气态烃(C₁—C₄)(特别是甲烷)含量明显增加，而轻质油含量有所下降。在300～500℃段，不论是烃源岩全岩，还是黏粒级组分，生烃产率和产烃量的值都是最高的，其次是500～650℃段，最低的是300℃以前。通过不同温度段特征的比较，发现全岩和黏粒级组分的热解特征有相似之处，轻质油组分是烃源岩热解生烃的主要组分，且300～500℃是烃源岩生烃高峰温度段。对300～500℃段热解—色谱特征进一步研究发现，黏粒级组分的轻烃(C₁—C₁₄)百分含量高于全岩，重烃组分(C₁₅⁺)则相反，而且黏粒级组分总烃产量占全岩的平均值高达72.57%，这些特征表明黏粒级组分是烃源岩生烃的主要贡献者，且黏土吸附的有机质在有机质生烃过程中对轻烃组分(C₁—C₁₄)的贡献显著。对烃源岩和黏粒级组分开展热解—色谱特征研究，可获取不同温度段释放烃或烃赋存等特征，这对开展有机质生烃和资源评价以及非常规油气赋存特征的研究都具有重要意义。

关键词： 热解—色谱; 烃类; 黏粒级组分; 产烃量

本文引用格式

郭敏, 蔡进功, 蒋启贵, 丁飞 . 烃源岩与<2μm黏粒级组分的热解—色谱特征对比及其意义[J]. 天然气地球科学, 2016 , 27(4) : 688 -698 . DOI: 10.11764/j.issn.1672-1926.2016.04.0688

Abstract

Argillaceous source rock samples of Oligocene with varial depth were selected from the Dongying Sag in Jiyang Depression,and clay fractions (<2μm) were separated from the argillaceous source rocks.Pyrolysis-gas chromatography detection was made on the whole rock and the clay fraction in three temperature intervals (< 300℃,300-500℃,500-650℃) to discuss the characteristic and significance of the released hydrocarbon in different temperature intervals,as well as to examine the contribution of clay fractions to the source rocks hydrocarbon generation.The results show that whether the whole rock or the clay fraction in different temperature intervals,light oil C₅—C₁₄) accounts for the large proportion in all of the pyrolysis products,which is more than 50% at T<300℃ or of 300-500℃;and at 500-650℃,the content of gaseous hydrocarbon (C₁—C₄) (particularly the CH₄) increases apparently with the decrease of light oil.For the hydrocarbon productivity and yield both in the whole rock and clay fraction,300-500℃ is the highest than other temperature intervals,the lower is 500-650℃ and the lowest is <300℃.Via comparison of pyrolysis-gas chromatography characteristics in different temperature intervals,it can be found that there exists the same characteristics between whole rock and clay fraction that the light oil is the main constituent of pyrolysis hydrocarbon products,and 300-500℃ is the temperature interval of hydrocarbon generation peak.Further analysis of pyrolysis-gas chromatography characteristics in 300-500℃ shows,the percent of light hydrocarbon (C₁—C₁₄) in clay fractions are higher than that in whole rocks,but the heavy hydrocarbon(C₁₅⁺)are on the contrary.Total hydrocarbon yield of the clay fractions accounts for an average of 72.57% in the whole rocks.These findings indicate that the clay fractions (<2μm) are the main contributor to the hydrocarbon generation of source rock,and the organic matter adsorbed by clay minerals contributes significantly to the light hydrocarbon (C₁—C₁₄) in the hydrocarbon generation process of the organic matter.It is of great significance to study the hydrocarbon generation,resource evaluation and characteristics of unconventional oil and gas occurrence in the coming research.

Key words： Pyrolysis-gas chromatography; Hydrocarbons; Clay fractions; Hydrocarbon yield

参考文献

［1］Fan Fu,Cai Jingong,Song Mingshui,et al.An exploratory study [JP]on density fractionation and organic matter preservation of muddy source rock[J].Journal of Tongji University:Natural Science,2011,39(9):1359-1364.[樊馥,蔡进功,宋明水,等.泥质烃源岩密度分组及有机质赋存类型初探[J].同济大学学报：自然科学版,2011,39(9):1359-1364.]
[2]Cai Jingong,Bao Yujin,Yang Shouye,et al.Research on preservation and enrichment mechanisms of organic matter in muddy sediment and mudstone[J].Science in China:Series D，2007,37 (2):234-243.[蔡进功,包于进,杨守业,等.泥质沉积物和泥岩中有机质的赋存形式与富集机制[J].中国科学：D辑,2007,37(2):234-243.]
[3]Lu Longfei,Cai Jingong,Liu Wenhui,et al.Water bridges mechanism of organo-smectite interaction in argillaceous hydrocarbon source rocks:Evidences from in situ DRIFT spectroscopic study[J].Oil & Gas Geology,2011,32(1):47-55.[卢龙飞,蔡进功,刘文汇,等.泥质烃源岩中蒙皂石与有机质的水桥结合作用——来自原位漫反射红外光谱的证据[J].石油与天然气地质,2011,32(1):47-55.]
[4]Fan Fu,Cai Jingong,Xu Jinli,et al.Original preservation of different organic micro-components in muddy source rock[J].Journal of Tongji University:Natural Science,2011,39(3):47-55.[樊馥,蔡进功,徐金鲤,等.泥质烃源岩不同有机显微组分的原始赋存态[J].同济大学学报:自然科学版,2011,39(3):47-55.]
[5]Arnarson T S,Keil R G.Mechanisms of pore water organic matter adsorption to montmorillonite[J].Marine Chemistry,2000,71:309-320.
[6]Kaiser K,Guggenberger G.The role of DOM sorption to mineral surfaces in the preservation of organic matter in soils[J].Organic Geochemistry,2000,31:711-725.
[7]Guggenberger G,Kaiser K.Dissolved organic matter in soil:Challenging the paradigm of sorptive preservation[J].Geoderma,2003,113:293-310.
[8]Chenu C,Plante A F.Clay-sized organo-mineral complexes in a cultivation chronosequence:Revising the concept of the ‘primary organo-mineral complex’[J].European Journal of Soil Science,2006,57:596-607.
[9]Fan Fu,Ye Wenqing,Cai Jingong,et al.Advances on organic matter preservation by clay in source rock[J].Xinjiang Petroleum Geology,2009,30(3):390-392.[樊馥,叶文青,蔡进功,等.烃源岩中粘土对有机质保存的研究进展[J].新疆石油地质,2009,30(3):390-392.]
[10]Kennedy M J,Pevear D R,Hill R H.Mineral surface control of organic carbon in black shale[J].Science,2002,295:657-660.
[11]Salmon V,Derenne S,Lallie-verges E,et al.Protection of organic matter by mineral matrix in a Cenomanian black shale[J].Organic Geochemistry,2000,31:463-474.
[12]Williama L B,Canfield B,Voglesonger K M,et al.Organic molecules formed in a ‘primordial womb’[J].Geology,2005,33:913-916.
[13]Mayer L M.Extent of coverage of mineral surfaces by organic matter in sediments[J].Geochimica et Cosmichimica Acta,1999,63:207-215.
[14]Cai Jingong.Organo-clayComplexes in Muddy Rocks and Sediments[M].Beijing:Science Press,2004:95-107.[蔡进功.泥质沉积物和泥岩中有机粘土复合体[M].北京：科学出版社,2004:95-107.]
[15]Guan Ping,Xu Yongchang,Liu Wenhui.Occurrence of organic matter in hydrocarbon source rocks and quantity estimation[J].Chinese Science Bulletin,1998,43(14):1556-1559.[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):1556-1559.]
[16]Salmon V,Derenne S,Largeau C,et al.Kerogen chemical structure and source organisms in a Cenomanian organic-rich black shale (Central Italy)-Indications for an important role of the “sorptive protection” pathway[J].Organic Geochemistry,1997,27(7/8):423-438.
[17]Zhang Yonggang,Cai Jingong,Xu Weiping.Research on Enrichment Mechanisms of Organic Matter in Muddy Source Rock[M].Beijing:Petroleum Industry Press,2007:133-144.[张永刚,蔡进功,许卫平.泥质烃源岩中有机质富集机制[M].北京:石油工业出版社,2007:133-144.]
[18]Cai Jingong,Lu Longfei,Song Mingshui,et al.Characteristics of extraction of organo-clay complexes and their significance to petroleum geology[J].Oil & Gas Geology,2010,31(3):300-308.[蔡进功,卢龙飞,宋明水,等.有机粘土复合体抽提特征及其石油地质意义[J].石油与天然气地质,2010,31(3):300-308.]
[19]Wang Xiao’e,Li Qingchun,Tian Fenglan.Application of pyrolysis chromatographic technique in Dongpu Sag hydrocarbon reservoir evaluation[J].Mud Logging Engineering,2005,16(4):27-31.[王晓鄂,李庆春,田凤兰.热解色谱分析技术在东濮凹陷油气层评价中的应用[J].录井工程,2006,16(4):27-31.]
[20]Gao Gang.Method of petroleum-generating simulation and its petroleum geological significance[J].Natural Gas Geoscience,2000,11(2):25-29.[高岗.油气生成模拟方法及其石油地质意义[J].天然气地球科学,2000,11(2):25-29.]
[21]Jiang Qigui,Ma Yuanyuan,Li Xin.Application of single cold trap pyrolysis chromatography in source rock evaluation[J].Petroleum Geology & Experiment,2011,33(5):546-558.[蒋启贵,马媛媛,李欣.单冷阱热解色谱仪在烃源岩评价中的应用[J].石油实验地质，2011,33(5):546-558.]
[22]Cai Jingong,Song Mingshui,Lu Longfei,et al.Organo-clay complexes in source rocks:A natural material for hydrocarbon generation[J].Marine Geology & Quaternary Geology,2013,33(3):123-131.[蔡进功,宋明水,卢龙飞,等.烃源岩中有机黏粒复合体——天然的生烃母质[J].海洋地质与第四纪地质,2013,33(3):123-131.]
[23]Zhao Xingyuan,Zhang Youyu.Clay Mineral and Clay Mineral Analysis[M].Beijing:China Ocean Press,1990:73-83.[赵杏媛,张有瑜.粘土矿物与粘土矿物分析[M].北京:海洋出版社,1990:73-83.]
[24]Song Yitao,Liao Yongsheng,Zhang Shouchun.Two occurrences of soluble organic matter determine in salty lacustrine source rocks and significance[J].Chinese Science Bulletin,2005,50(14):1531-1534.[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):1531-1534.]
[25]Sanei H,Stasiuk L D,Goodarzi F.Petrological changes occuring in organic matter from recent lacustrine sediments during thermal alteration by Rock-Eval pyrolysis[J].Organic Geochemistry,2005,36:1190-1203.
[26]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.[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.]
[27]Ye Wenqing,Cai Jingong,Fan Fu,et al.Argillaceous hydrocarbon source rock density separation and dstribution of oganic carbon[J].Geological Journal of China Universities,2009,15(4):547-556.[叶文青,蔡进功,樊馥,等.泥质烃源岩密度分级分离与有机碳分配[J].高校地质学报,2009,15(4):547-556.][JP]
[28]Lu Longfei,Cai Jingong,Liu Wenhui,et al.Occurrence and thermostability of absorbed organic matter on clay minerals in mudstones and muddy sediments[J].Oil & Gas Geology,2013,34(1):16-26.[卢龙飞,蔡进功,刘文汇,等.泥岩与沉积物中粘土矿物吸附有机质的三种赋存状态及其热稳定性[J].石油与天然气地质,2013,34(1):16-26.]
[29]Lu Longfei,Cai Jingong,Liu Wenhui,et al.Infra-red emission spectroscopy study of thermal evolution of organic matter bound by clay minerals in muddy hydrocarbon source rocks[J].Petroleum Geology & Experiment,2012,34(2):215-222.[卢龙飞,蔡进功,刘文汇,等.泥质烃源岩中粘土矿物结合有机质热演化的红外发射光谱研究[J].石油实验地质,2012,34(2):215-222.][JP]
[30]Theng B K.Formation and Properties of Clay-polymer Complexes[M].Amsterdam:Elsevier:1979,1-154.
[31]Cai Jingong,Lu Longfei,Bao Yujin,et al.The significance and variation characteristics of interlay water in smectite of hydrocarbon source rocks[J].Science China:Earth Science,2012,42(4):438-491.[蔡进功,卢龙飞,包于进,等.烃源岩中蒙皂石结合有机质后层间水的变化特征及其意义[J].中国科学：地球科学,2012,42(4):438-491.]
[32]Zhang Jingqiao,Cai Jingong,Wang Xujun,et al.Palynofacies of lacustrine source rocks in Dongying Depression and its significance[J].Journal of Central South University:Science and Technology,2013,44(8):3446-3452.[张晶巧,蔡进功,王学军,等.东营凹陷湖相烃源岩孢粉相特征及其意义[J].中南大学学报:自然科学版,2013,44(8):3446-3452.]
[33]Li Guangzhi,Hu Bin,Deng Tianlong,et al.Analytic techniques and petroleum geological significance of different existing states of light hydrocarbons[J].Natural Gas Geoscience,2007,18(1):111-116.[李广之,胡斌,邓天龙,等.不同赋存状态轻烃的分析技术及石油地质意义[J].天然气地球科学,2007,18(1):111-116.]
[34]Guggenberger G,Christensen B T,Zech W.Land-use effects on the composition of organic matter in particle-size separates of soil:I.Lignin and carbohydrate signature[J].European Journal Soil Science,1994,45:449-458.
[35]Jandl G,Leinweber P,Schulten H R,et al.The concentrations of fatty acids in organo-mineral particle-size fractions of a Chernozem[J].European Journal Soil Science,2004,55:459-470.
[36]Lu Longfei,Cai Jingong,Bao Yu jin,et al.Summary of processes and significance of clay minerals in marine sedimentary organic matter preservation and in global carbon cycle[J].Advances in Earth Science,2006,21(9):932-937.[卢龙飞,蔡进功,包于进,等.黏土矿物保存海洋沉积有机质研究进展及其碳循环意义[J].地球科学进展,2006,21(9):932-937.]
[37]Fang Xuan,Lei Huaiyan.Research of clay minerals pyrolysis effects on biological-thermal catalytic transitional zone with organic matter[J].Natural Gas Geoscience,1993,6:80-85.[房玄,雷怀彦.黏土矿物对生物—热催化过渡带有机质热解影响的研究[J].天然气地球科学,1993,6:80-85.]

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