页岩中丙烷的降解特征及对页岩气组成的影响

徐建兵; 梁允干; 邓倩; 程斌; 廖泽文

doi:10.11781/sysydz201803389

页岩中丙烷的降解特征及对页岩气组成的影响

doi: 10.11781/sysydz201803389

徐建兵^1,2,
梁允干^1,2,
邓倩^1,2,
程斌¹,
廖泽文^1, ,

1.
中国科学院广州地球化学研究所, 有机地球化学国家重点实验室, 广州 510640
2. 中国科学院大学, 北京 100049

基金项目: 国家自然科学基金面上项目（41772117）和中科院页岩气先导专项（B类）（XDB10010203）资助。

详细信息

作者简介:
徐建兵(1990-),男,博士研究生,从事油气地球化学研究。E-mail:xujianbing14@mails.ucas.edu.cn。

通讯作者:
廖泽文(1969-),男,博士,研究员,从事有机地球化学、油气地球化学研究。E-mail:liaozw@gig.ac.cn。

中图分类号: TE132.2
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出版历程
- 收稿日期: 2017-09-06
- 修回日期: 2018-04-17
- 刊出日期: 2018-05-28

Degradation characteristics of propane in shale rocks and its implication to shale gas composition

XU Jianbing^1,2,
LIANG Yungan^1,2,
DENG Qian^1,2,
CHENG Bin¹,
LIAO Zewen^{1
, ,}

1.
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, Guangdong 510640, China
2. University of the Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 为探讨高过成熟阶段页岩中小分子烃类的降解对页岩气组成的影响，选取了丙烷和页岩（取自四川盆地龙马溪组同一钻井、不同深度）开展不同系列的模拟实验。对C₃H₈、C₃H₈+页岩、C₃H₈+页岩+水在360℃、50 MPa条件下进行黄金管限定体系恒温热模拟实验，恒温时间包括72，216，360，720 h；同时为探讨更高演化程度条件下页岩中小分子烃类的降解特征，对C₃H₈、C₃H₈+页岩分别在400，450，500，550℃和50 MPa条件下恒温热模拟72 h。结果显示，360℃恒温实验条件下，C₃H₈+页岩体系中CH₄、C₂H₆生成量及CH₄/C₂H₆值比相应的C₃H₈对照实验高，且黏土矿物含量高的S1系列实验生成的CH₄、C₂H₆及CH₄/C₂H₆值基本较S2系列高。提高模拟实验温度后，丙烷的转化率显著提高，C₃H₈+页岩实验中的CH₄、C₂H₆产率均高于对照实验，且CH₄的产率高于C₂H₆。2个系列的模拟实验结果均说明黏土矿物能催化C₃H₈的裂解，且有利于CH₄的产生。含水体系中CH₄、C₂H₆生成量及CH₄/C₂H₆值比无水体系高，说明水能促进页岩中C₃H₈的裂解，且有利于CH₄的富集。页岩中黏土矿物和水对C₃H₈裂解的促进作用导致页岩气向干燥系数高的方向演化，页岩中小分子烃类的降解对高过成熟阶段页岩气的组成具有重要影响，在此过程中水分子起到重要作用，其对高过成熟页岩气资源的评价值得更多关注。
- 丙烷裂解 /
- 矿物催化 /
- 干燥系数 /
- 页岩气
Abstract: Propane and shale samples taken from the same well and different depths in the Longmaxi Formation in the Sichuan Basin were selected to carry out different series of simulation experiments in order to investigate the influence of the degradation of small molecular hydrocarbons on the composition of shale gas in the shale during the over-mature stage. The constant temperature thermal simulation experiments of a gold tube-restricted system were carried out on C₃H₈, C₃H₈ + shale, C₃H₈ + shale + water at 360℃ and 50 MPa for 72, 216, 360, 720 h. Other pyrolysis experiments were performed using C₃H₈ and C₃H₈ + shale samples at 400, 450, 500 and 550℃ with a pressure of 50 MPa for 72 h in order to increase the degradation degree of C₃H₈. The results showed that the CH₄, C₂H₆ yields and the CH₄/C₂H₆ ratio of C₃H₈ + shale at 360℃ are higher than those of C₃H₈ alone. The experiments with S1 shale rock which contains more clay minerals generated more CH₄ and C₂H₆ than those with S2 rock sample, and generally showed higher CH₄/C₂H₆ ratios. After increasing the simulation temperature, the conversion of C₃H₈ was significantly increased. The yields of CH₄ and C₂H₆ in the C₃H₈ + shale experiment were all higher than those in the control experiment, and the yield of CH₄ was higher than that of C₂H₆. These results indicated that clay minerals can catalyze C₃H₈ degradation and produce more CH₄. The yields of CH₄ and C₂H₆, and the CH₄/C₂H₆ ratio from the hydrous experiments were higher than those from anhydrous experiments, which indicated that water can promote the cracking of C₃H₈ to produce more CH₄. The positive effect of clay mineral and water in shale on C₃H₈ cracking increased the dryness index of shale gas. The degradation of small hydrocarbon molecules had an important influence on the composition of shale gas particularly in high-to over-mature shale rocks. It seems that water played a significant role and its effect on the evaluation of shale gas reserve should be thoroughly investigated especially for high-to over-mature shale rocks.
- propane degradation /
- mineral catalysis /
- dryness index /
- shale gas

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参考文献(21)

[1]	邹才能,陶士振,侯连华,等.非常规油气地质[M].2版.北京:地质出版社,2013:142-143. ZOU Caineng,TAO Shizhen,HOU Lianhua,et al.Unconventional petroleum geology[M].2nd ed.Beijing:Geological Publishing House,2013:142-143.
[2]	ROSS D J K,BUSTIN R M.The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs[J].Marine and Petroleum Geology,2009,26(6):916-927.
[3]	CUI X A,BUSTIN R M,BREZOVSKI R,et al.A new method to simultaneously measure in-situ permeability and porosity under reservoir conditions:Implications for characterization of unconventional gas reservoirs[C]//Canadian Unconventional Resources and International Petroleum Conference.Calgary,Alberta,Canada:Society of Petroleum Engineers,2010.
[4]	DING Wenlong,LI Chao,LI Chunyan,et al.Fracture development in shale and its relationship to gas accumulation[J].Geoscience Frontiers,2012,3(1):97-105.
[5]	陈吉,肖贤明.南方古生界3套富有机质页岩矿物组成与脆性分析[J].煤炭学报,2013,38(5):822-826. CHEN Ji,XIAO Xianming.Mineral composition and brittleness of three sets of Paleozoic organic-rich shales in China South area[J].Journal of China Coal Society,2013,38(5):822-826.
[6]	聂海宽,张金川.页岩气聚集条件及含气量计算:以四川盆地及其周缘下古生界为例[J].地质学报,2012,86(2):349-361. NIE Haikuan,ZHANG Jinchuan.Shale gas accumulation conditions and gas content calculation:A case study of Sichuan Basin and its periphery in the Lower Paleozoic[J].Acta Geologica Sinica,2012,86(2):349-361.
[7]	ZHANG Tongwei,ELLIS G S,RUPPEL S C,et al.Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems[J].Organic Geochemistry,2012,47:120-131.
[8]	LEWAN M D.Experiments on the role of water in petroleum formation[J].Geochimica et Cosmochimica Acta,1997,61(17):3691-3723.
[9]	PRICE L C,SCHOELL M.Constraints on the origins of hydrocarbon gas from compositions of gases at their site of origin[J].Nature,1995,378(6555):368-371.
[10]	EVANS C R,ROGERS M A,BAILEY N J L.Evolution and alteration of petroleum in western Canada[J].Chemical Geo-logy,1971,8(3):147-170.
[11]	DAI Jinxing,ZOU Caineng,DONG Dazhong,et al.Geochemical characteristics of marine and terrestrial shale gas in China[J].Marine and Petroleum Geology,2016,76:444-463.
[12]	李忠.试论油气形成过程中粘土矿物的催化作用[J].石油实验地质,1992,14(1):59-63. LI Zhong.On the catalysis of clay minerals in the process of oil and gas generation[J].Experimental Petroleum Geology,1992,14(1):59-63.
[13]	MACKENZIE A S,LEWIS C A,MAXWELL J R.Molecular parameters of maturation in the Toarcian shales,Paris Basin,France-IV.Laboratory thermal alteration studies[J].Geochimica et Cosmochimica Acta,1981,45(12):2369-2376.
[14]	高先志,张万选,张厚福.矿物质对热解影响的研究[J].石油实验地质,1990,12(2):201-205. GAO Xianzhi,ZHANG Wanxuan,ZHANG Houfu.Study of the influence of minerals on pyrolysis[J].Experimental Petroleum Geology,1990,12(2):201-205.
[15]	姜兰兰,潘长春,刘金钟.矿物对原油裂解影响的实验研究[J].地球化学,2009,38(2):165-173. JIANG Lanlan,PAN Changchun,LIU Jinzhong.Experimental study on effects of minerals on oil cracking[J].Geochimica,2009,38(2):165-173.
[16]	WU Linmei,ZHOU Chunhui,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(4):373-386.
[17]	LI Shuyuan,GUO Shaohui,TAN Xuefei.Characteristics and kinetics of catalytic degradation of immature kerogen in the presence of mineral and salt[J].Organic geochemistry,1998,29(5/7):1431-1439.
[18]	HUIZINGA B J,TANNENBAUM E,KAPLAN I R.The role of minerals in the thermal alteration of organic matter-Ⅲ.Generation of bitumen in laboratory experiments[J].Organic Geoche-mistry,1987,11(6):591-604.
[19]	JOHNS W D.Clay mineral catalysis and petroleum generation[J].Annual Review of Earth and Planetary Sciences,1979,7:183-198.
[20]	马向贤,郑建京,王晓锋,等.黏土矿物对油气生成的催化作用:研究进展与方向[J].岩性油气藏,2015,27(2):55-61. MA Xiangxian,ZHENG Jianjing,WANG Xiaofeng,et al.Research progress and new direction:Catalysis of clay minerals on oil and gas generation[J].Lithologic Reservoirs,2015,27(2):55-61.
[21]	SEEWALD J.S.Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures:Constraints from mineral buffered laboratory experiments[J].Geochimica et Cosmochimica Acta,2001,65(10):1641-1664.