二甲基二苯并噻吩生成实验及地球化学意义
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摘要
二苯并噻吩类化合物(DBTs)是当前油气地球化学研究中常用的一类分子标志化合物,但因其地质成因机理尚存争论,导致与之相关的地化参数大多源自经验,缺乏理论基础。在10 MPa和200～500℃下,对3,3′-二甲基联苯和单质硫混合物进行封闭体系热模拟实验。结果表明,在无催化条件下由联苯类化合物生成DBTs具有特定的空间选择性。在地质条件下该反应所需的温度可低于200℃,因为体系压力的增加可降低反应门限温度。与实际地质样品相似,随着温度的升高,产物中不同甲基取代位的DBTs相对含量会发生变化,进而导致热成熟度参数MDR(4-/1-MDBT)先升高后降低。因此,MDR作为成熟度参数时需要结合实际地质条件,在合适的成熟度范围内使用。
Dibenzothiophene(DBT) and its homologues are important molecular markers in petroleum geochemistry. However, DBT-related geochemical indicators were derived mainly based on empirical observations due to insufficient understanding of the mechanisms through which these organosulfur compounds were generated in sedimentary environments. Thermal simulation experiments with 3,3'-dimethylbiphenyl and sulfur in closed gold tubes at 200-500 ℃ and 10 MPa afforded three main dimethyldibenzothiophene isomers(DMDBTs). Importantly, DBTs could be generated at a temperature as moderate as 200 ℃ under geological conditions, because the temperature threshold of the reaction could be reduced by increasing the system pressure. Further investigations revealed that the regioselectivity of the thiophene formation reaction was strongly influenced by temperature. This is similar to the process that occurs in natural geological systems. It should also be noted that the maturity index 4-/1-MDBT(MDR) reaches a maximum around 1.5%(Easy%R_o). It indicates that MDR index should be used in a suitable maturity regions combined with the given geological setting.
Dibenzothiophene(DBT) and its homologues are important molecular markers in petroleum geochemistry. However, DBT-related geochemical indicators were derived mainly based on empirical observations due to insufficient understanding of the mechanisms through which these organosulfur compounds were generated in sedimentary environments. Thermal simulation experiments with 3,3'-dimethylbiphenyl and sulfur in closed gold tubes at 200-500 ℃ and 10 MPa afforded three main dimethyldibenzothiophene isomers(DMDBTs). Importantly, DBTs could be generated at a temperature as moderate as 200 ℃ under geological conditions, because the temperature threshold of the reaction could be reduced by increasing the system pressure. Further investigations revealed that the regioselectivity of the thiophene formation reaction was strongly influenced by temperature. This is similar to the process that occurs in natural geological systems. It should also be noted that the maturity index 4-/1-MDBT(MDR) reaches a maximum around 1.5%(Easy%R_o). It indicates that MDR index should be used in a suitable maturity regions combined with the given geological setting.
引文
[1] CHAKHMAKHCHEV A,SUZUKI M,TAKAYAMA K.Distribution of alkylated dibenzothiophenes in petroleum as a tool for maturity assessments[J].Organic Geochemistry,1997,26(7/8):483-489.
[2] HUGHES W B,HOLBA A G,DZOU L I P.The ratios of dibenzothiophene to phenanthrene 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.
[3] CONNAN J,BOUROULLEC J,DESSORT D,et al.The microbial input in carbonate-anhydrite facies of a sabkha palaeoenvironment from Guatemala:a molecular approach[J].Organic Geochemistry,1986,10(1/3):29-50.
[4] LI Meijun,WANG T G,SIMONEIT B R T,et al.Qualitative and quantitative analysis of dibenzothiophene,its methylated homologues,and benzonaphthothiophenes in crude oils,coal,and sedi-ment extracts[J].Journal of Chromatography A,2012,1233:126-136.
[5] 包建平,王铁冠,陈发景.烃源岩中烷基二苯并噻吩组成及其地球化学意义[J].石油大学学报(自然科学版),1996,20(1):19-23. BAO Jianping,WANG Tieguan,CHEN Fajing.Relative abundance of alkyl dibenzothiophene in the source rocks and their geochemical significances[J].Journal of the University of Petroleum,China,1996,20(1):19-23.
[6] HUGHES W B.Use of thiophenic organosulfur compounds in characterizing crude oils derived from carbonate versus siliciclastic sources[M]//PALACAS J G.Petroleum Geochemistry and Source Rock Potential of Carbonate Rocks.Tulsa,Oklahoma:AAPG,1984:181-196.
[7] 林红梅.渤海湾盆地车镇凹陷下古生界烃源岩生物标志物特征[J].石油实验地质,2017,39(2):230-237. LIN Hongmei.Biomarker characteristics of Lower Paleozoic source rocks in Chezhen Sag,Bohai Bay Basin[J].Petroleum Geology & Experiment,2017,39(2):230-237.
[8] HUANG Haiping,PEARSON M J.Source rock palaeoenvironments and controls on the distribution of dibenzothiophenes in lacustrine crude oils,Bohai Bay Basin,Eastern China[J].Organic Geochemistry,1999,30(11):1455-1470.
[9] 李景贵.海相碳酸盐岩二苯并噻吩类化合物成熟度参数研究进展与展望[J].沉积学报,2000,18(3):480-483. LI Jinggui.Research development and prospect of maturity parameters of methylated dibenzothiophenes in marine carbonate rocks[J].Acta Sedimentologica Sinica,2000,18(3):480-483.
[10] 罗健,程克明,付立新,等.烷基二苯并噻吩:烃源岩热演化新指标[J].石油学报,2001,22(3):27-31. LUO Jian,CHENG Keming,FU Lixin,et al.Alkylated dibenzothiophene index:a new method to assess thermal maturity of source rocks[J].Acta Petrolei Sinica,2001,22(3):27-31.
[11] 魏志彬,张大江,张传禄,等.甲基二苯并噻吩分布指数(MDBI)作为烃源岩成熟度标尺的探讨[J].地球化学,2001,30(3):242-247. WEI Zhibin,ZHANG Dajiang,ZHANG Chuanlu,et al.Methyldibenzothiophenes distribution index as a tool for maturity assessments of source rocks[J].Geochimica,2001,30(3):242-247.
[12] 张敏,张俊.塔里木盆地原油噻吩类化合物的组成特征及地球化学意义[J].沉积学报,1999,17(1):121-126. ZHANG Min,ZHANG Jun.Composition characteristics and geochemical significance of thiophene-type compounds for crude oils in Tarim Basin[J].Acta Sedimentologica Sinica,1999,17(1):121-126.
[13] 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. WANG Tieguang,HE Faqi,LI Meijun,et al.Methyldibenzothiophenes:molecular markers for tracing the pathway of hydrocarbon migration[J].Chinese Science Bulletin,2005,50(2):176-182.
[14] 刘永立,罗明霞,夏永涛,等.塔河油田塔深3井区奥陶系深层油气成藏的地球化学证据[J].石油实验地质,2017,39(3):377-382. LIU Yongli,LUO Mingxia,XIA Yongtao,et al.Geochemical evidence for hydrocarbon accumulation in deep Ordovician in TS3 well block, Tahe oil field[J].Petroleum Geology & Experiment,2017,39(3):377-382.
[15] 葛海霞,张枝焕,闵伟.渤海湾盆地青东凹陷古近系原油地球化学特征及油源分析[J].石油实验地质,2017,39(3):383-389. GE Haixia,ZHANG Zhihuan,MIN Wei.Geochemical characteristics and oil-source correlation of Paleogene oils in Qingdong Sag,Bohai Bay Basin[J].Petroleum Geology & Experiment,2017,39(3):383-389.
[16] 李宁,覃军,江瀚,等.西湖凹陷T气田油气分布特征与主控因素[J].断块油气田,2017,24(3):329-332. LI Ning,QIN Jun,JIANG Han,et al.Hydrocarbon distribution features and its main controlling factors of T gas field,Xihu Sag, East China Sea Shelf Basin[J].Fault-Block Oil and Gas Field,2017,24(3):329-332.
[17] 李美俊,师生宝,王铁冠,等.应用石油中“三芴”系列判识沉积环境的几个问题[J].地球科学前沿,2013,3:22-28. LI Meijun,SHI Shengbao,WANG Tieguan,et al.Several problems on the use of relative abundances of fluorenes,dibenzofurans and dibenzothiophenes in the study of depositional environment[J].Advances in Geosciences,2013,3:22-28.
[18] 李水福,何生.原油芳烃中三芴系列化合物的环境指示作用[J].地球化学,2008,37(1):45-50. LI Shuifu,HE Sheng.Geochemical characteristics of dibenzothiophene,dibenzofuran and fluorene and their homologues and their environmental indication[J].Geochimica,2008,37(1):45-50.
[19] SINNINGHE DAMSTE J S,DE LEEUW J W.Analysis,structure and geochemical significance of organically-bound sulphur in the geosphere:state of the art and future research[J].Organic Geochemistry,1990,16(4/6):1077-1101.
[20] 盛国英,傅家谟,BRASSELL S C,等.膏盐盆地高硫原油中的长链烷基噻吩类化合物[J].地球化学,1986(2):138-146. SHENG Guoying,FU Jiamo,BRASSELL S C,et al.Long chain alkyl-thiophenoid compounds found in sulphur-high crude oil from a hypersaline basin[J].Geochimica,1986(2):138-146.
[21] WHITE C M,LEE M L.Identification and geochemical significance of some aromatic components of coal[J].Geochimica et Cosmochimica Acta,1980,44(11):1825-1832.
[22] 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. XIA Yanqing,WANG Chunjiang,MENG Qianxiang,et al.Gene-ration simulation of dibenzothiophene and dibenzofuran[J].Chinese Science Bulletin,1998,43(15):1661-1663.
[23] ASIF M,ALEXANDER R,FAZEELAT T,et al.Geosynthesis of dibenzothiophene and alkyl dibenzothiophenes in crude oils and sediments by carbon catalysis[J].Organic Geochemistry,2009,40(8):895-901.
[24] LI Meijun,SIMONEIT B R T,ZHONG Ningning,et al.The distribution and origin of dimethyldibenzothiophenes in sediment extracts from the Liaohe Basin,East China[J].Organic Geochemistry,2013,65:63-73.
[25] LEE M L,VASSILAROS D L,WHITE C M,et al.Retention indices for programmed-temperature capillary-column gas chromatography of polycyclic aromatic hydrocarbons[J].Analytical Chemistry,1979,51(6):768-773.
[26] SCHADE T,ANDERSSON J T.Speciation of alkylated dibenzothiophenes through correlation of structure and gas chromatographic retention indexes[J].Journal of Chromatography A,2006,1117(2):206-213.
[27] 师生宝,李美俊,朱雷.石油及沉积有机质中C1-和C2-烷基二苯并噻吩鉴定及分布[J].石油实验地质,2014,36(5):612-617. SHI Shengbao,LI Meijun,ZHU Lei.Identification and distribution of C1- and C2-alkylated dibenzothiophenes in petroleum and sedimentary organic matter[J].Petroleum Geology & Experiment,2014,36(5):612-617.
[28] RADKE M,WILLSCH H.Extractable alkyldibenzothiophenes in Posidonia shale (Toarcian) source rocks:relationship of yields to petroleum formation and expulsion[J].Geochimica et Cosmochimica Acta,1994,58(23):5223-5244.
[29] SCHOU L,MYHR M B.Sulfur aromatic compounds as maturity parameters[J].Organic Geochemistry,1988,13(1/3):61-66.
[30] LI Meijun,ZHONG Ningning,SHI Shengbao,et al.The origin of trimethyldibenzothiophenes and their application as maturity indicators in sediments from the Liaohe Basin,East China[J].Fuel,2013,103:299-307.
[31] SWEENEY J J,BURNHAM A K.Evaluation of a simple model of vitrinite reflectance based on chemical kinetics[J].AAPG Bulletin,1990,74(10):1559-1570.
[32] JOHNS W D.Clay mineral catalysis and petroleum generation[J].Annual Review of Earth & Planetary Sciences,1979,7(1):183-198.
[33] 李术元,郭绍辉,郑红霞.褐煤催化降解生烃过程的动力学研究[J].石油勘探与开发,1997,24(3):21-23. LI Shuyuan,GUO Shaohui,ZHENG Hongxia.A study of catalytic degradation kinetics of fanshi lignite[J].Petrolum Exploration and Development,1997,24(3):21-23.
[34] 潘长春,耿安松,钟宁宁,等.矿物和水对干酪根热解生烃作用的影响:甾、藿烷(烯)的形成与热演化[J].地质学报,2006,80(3):446-453. PAN Changchun,GENG Ansong,ZHONG Ningning,et al.The effects of minerals and water on hydrocarbon generation from kerogen:Ⅲ.steranes and triterpane generation and maturation[J].Acta Geologica Sinica,2006,80(3):446-453.
[35] 李术元,林世静,郭绍辉,等.矿物质对干酪根热解生烃过程的影响[J].石油大学学报(自然科学版),2002,26(1):69-71. LI Shuyuan,LIN Shijing,GUO Shaohui,et al.Catlaytic effects of minerals on hydrocarbon generation in kerogen degradation[J].Journal of the University of Petroleum,China,2002,26(1):69-71.
[36] 妥进才,王随继.油气形成过程中的催化反应[J].天然气地球科学,1995,6(2):37-40. TUO Jincai,WANG Suiji.Catalytical reaction during the petro-leum generation[J].Natural Gas Geoscience,1995,6(2):37-40.
[37] YANG Sibo,LI Meijun,LIU Xiaoqiang,et al.Thermodynamic stability of methyldibenzothiophenes in sedimentary rock extracts:based on molecular simulation and geochemical data[J].Organic Geochemistry,2019,129:24-41.
[38] RADKE M.Application of aromatic compounds as maturity indicators in source rocks and crude oils[J].Marine and Petroleum Geology,1988,5(3):224-236.
[39] RADKE M,VRIEND S P,RAMANAMPISOA L R.Alkyldibenzofurans in terrestrial rocks:influence of organic facies and maturation[J].Geochimica et Cosmochimica Acta,2000,64(2):275-286.
[40] LI Meijun,WANG T G,SHI Shengbao,et al.Oil maturity assessment using maturity indicators based on methylated dibenzothiophenes[J].Petroleum Science,2014,11(2):234-246.
[2] HUGHES W B,HOLBA A G,DZOU L I P.The ratios of dibenzothiophene to phenanthrene 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.
[3] CONNAN J,BOUROULLEC J,DESSORT D,et al.The microbial input in carbonate-anhydrite facies of a sabkha palaeoenvironment from Guatemala:a molecular approach[J].Organic Geochemistry,1986,10(1/3):29-50.
[4] LI Meijun,WANG T G,SIMONEIT B R T,et al.Qualitative and quantitative analysis of dibenzothiophene,its methylated homologues,and benzonaphthothiophenes in crude oils,coal,and sedi-ment extracts[J].Journal of Chromatography A,2012,1233:126-136.
[5] 包建平,王铁冠,陈发景.烃源岩中烷基二苯并噻吩组成及其地球化学意义[J].石油大学学报(自然科学版),1996,20(1):19-23. BAO Jianping,WANG Tieguan,CHEN Fajing.Relative abundance of alkyl dibenzothiophene in the source rocks and their geochemical significances[J].Journal of the University of Petroleum,China,1996,20(1):19-23.
[6] HUGHES W B.Use of thiophenic organosulfur compounds in characterizing crude oils derived from carbonate versus siliciclastic sources[M]//PALACAS J G.Petroleum Geochemistry and Source Rock Potential of Carbonate Rocks.Tulsa,Oklahoma:AAPG,1984:181-196.
[7] 林红梅.渤海湾盆地车镇凹陷下古生界烃源岩生物标志物特征[J].石油实验地质,2017,39(2):230-237. LIN Hongmei.Biomarker characteristics of Lower Paleozoic source rocks in Chezhen Sag,Bohai Bay Basin[J].Petroleum Geology & Experiment,2017,39(2):230-237.
[8] HUANG Haiping,PEARSON M J.Source rock palaeoenvironments and controls on the distribution of dibenzothiophenes in lacustrine crude oils,Bohai Bay Basin,Eastern China[J].Organic Geochemistry,1999,30(11):1455-1470.
[9] 李景贵.海相碳酸盐岩二苯并噻吩类化合物成熟度参数研究进展与展望[J].沉积学报,2000,18(3):480-483. LI Jinggui.Research development and prospect of maturity parameters of methylated dibenzothiophenes in marine carbonate rocks[J].Acta Sedimentologica Sinica,2000,18(3):480-483.
[10] 罗健,程克明,付立新,等.烷基二苯并噻吩:烃源岩热演化新指标[J].石油学报,2001,22(3):27-31. LUO Jian,CHENG Keming,FU Lixin,et al.Alkylated dibenzothiophene index:a new method to assess thermal maturity of source rocks[J].Acta Petrolei Sinica,2001,22(3):27-31.
[11] 魏志彬,张大江,张传禄,等.甲基二苯并噻吩分布指数(MDBI)作为烃源岩成熟度标尺的探讨[J].地球化学,2001,30(3):242-247. WEI Zhibin,ZHANG Dajiang,ZHANG Chuanlu,et al.Methyldibenzothiophenes distribution index as a tool for maturity assessments of source rocks[J].Geochimica,2001,30(3):242-247.
[12] 张敏,张俊.塔里木盆地原油噻吩类化合物的组成特征及地球化学意义[J].沉积学报,1999,17(1):121-126. ZHANG Min,ZHANG Jun.Composition characteristics and geochemical significance of thiophene-type compounds for crude oils in Tarim Basin[J].Acta Sedimentologica Sinica,1999,17(1):121-126.
[13] 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. WANG Tieguang,HE Faqi,LI Meijun,et al.Methyldibenzothiophenes:molecular markers for tracing the pathway of hydrocarbon migration[J].Chinese Science Bulletin,2005,50(2):176-182.
[14] 刘永立,罗明霞,夏永涛,等.塔河油田塔深3井区奥陶系深层油气成藏的地球化学证据[J].石油实验地质,2017,39(3):377-382. LIU Yongli,LUO Mingxia,XIA Yongtao,et al.Geochemical evidence for hydrocarbon accumulation in deep Ordovician in TS3 well block, Tahe oil field[J].Petroleum Geology & Experiment,2017,39(3):377-382.
[15] 葛海霞,张枝焕,闵伟.渤海湾盆地青东凹陷古近系原油地球化学特征及油源分析[J].石油实验地质,2017,39(3):383-389. GE Haixia,ZHANG Zhihuan,MIN Wei.Geochemical characteristics and oil-source correlation of Paleogene oils in Qingdong Sag,Bohai Bay Basin[J].Petroleum Geology & Experiment,2017,39(3):383-389.
[16] 李宁,覃军,江瀚,等.西湖凹陷T气田油气分布特征与主控因素[J].断块油气田,2017,24(3):329-332. LI Ning,QIN Jun,JIANG Han,et al.Hydrocarbon distribution features and its main controlling factors of T gas field,Xihu Sag, East China Sea Shelf Basin[J].Fault-Block Oil and Gas Field,2017,24(3):329-332.
[17] 李美俊,师生宝,王铁冠,等.应用石油中“三芴”系列判识沉积环境的几个问题[J].地球科学前沿,2013,3:22-28. LI Meijun,SHI Shengbao,WANG Tieguan,et al.Several problems on the use of relative abundances of fluorenes,dibenzofurans and dibenzothiophenes in the study of depositional environment[J].Advances in Geosciences,2013,3:22-28.
[18] 李水福,何生.原油芳烃中三芴系列化合物的环境指示作用[J].地球化学,2008,37(1):45-50. LI Shuifu,HE Sheng.Geochemical characteristics of dibenzothiophene,dibenzofuran and fluorene and their homologues and their environmental indication[J].Geochimica,2008,37(1):45-50.
[19] SINNINGHE DAMSTE J S,DE LEEUW J W.Analysis,structure and geochemical significance of organically-bound sulphur in the geosphere:state of the art and future research[J].Organic Geochemistry,1990,16(4/6):1077-1101.
[20] 盛国英,傅家谟,BRASSELL S C,等.膏盐盆地高硫原油中的长链烷基噻吩类化合物[J].地球化学,1986(2):138-146. SHENG Guoying,FU Jiamo,BRASSELL S C,et al.Long chain alkyl-thiophenoid compounds found in sulphur-high crude oil from a hypersaline basin[J].Geochimica,1986(2):138-146.
[21] WHITE C M,LEE M L.Identification and geochemical significance of some aromatic components of coal[J].Geochimica et Cosmochimica Acta,1980,44(11):1825-1832.
[22] 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. XIA Yanqing,WANG Chunjiang,MENG Qianxiang,et al.Gene-ration simulation of dibenzothiophene and dibenzofuran[J].Chinese Science Bulletin,1998,43(15):1661-1663.
[23] ASIF M,ALEXANDER R,FAZEELAT T,et al.Geosynthesis of dibenzothiophene and alkyl dibenzothiophenes in crude oils and sediments by carbon catalysis[J].Organic Geochemistry,2009,40(8):895-901.
[24] LI Meijun,SIMONEIT B R T,ZHONG Ningning,et al.The distribution and origin of dimethyldibenzothiophenes in sediment extracts from the Liaohe Basin,East China[J].Organic Geochemistry,2013,65:63-73.
[25] LEE M L,VASSILAROS D L,WHITE C M,et al.Retention indices for programmed-temperature capillary-column gas chromatography of polycyclic aromatic hydrocarbons[J].Analytical Chemistry,1979,51(6):768-773.
[26] SCHADE T,ANDERSSON J T.Speciation of alkylated dibenzothiophenes through correlation of structure and gas chromatographic retention indexes[J].Journal of Chromatography A,2006,1117(2):206-213.
[27] 师生宝,李美俊,朱雷.石油及沉积有机质中C1-和C2-烷基二苯并噻吩鉴定及分布[J].石油实验地质,2014,36(5):612-617. SHI Shengbao,LI Meijun,ZHU Lei.Identification and distribution of C1- and C2-alkylated dibenzothiophenes in petroleum and sedimentary organic matter[J].Petroleum Geology & Experiment,2014,36(5):612-617.
[28] RADKE M,WILLSCH H.Extractable alkyldibenzothiophenes in Posidonia shale (Toarcian) source rocks:relationship of yields to petroleum formation and expulsion[J].Geochimica et Cosmochimica Acta,1994,58(23):5223-5244.
[29] SCHOU L,MYHR M B.Sulfur aromatic compounds as maturity parameters[J].Organic Geochemistry,1988,13(1/3):61-66.
[30] LI Meijun,ZHONG Ningning,SHI Shengbao,et al.The origin of trimethyldibenzothiophenes and their application as maturity indicators in sediments from the Liaohe Basin,East China[J].Fuel,2013,103:299-307.
[31] SWEENEY J J,BURNHAM A K.Evaluation of a simple model of vitrinite reflectance based on chemical kinetics[J].AAPG Bulletin,1990,74(10):1559-1570.
[32] JOHNS W D.Clay mineral catalysis and petroleum generation[J].Annual Review of Earth & Planetary Sciences,1979,7(1):183-198.
[33] 李术元,郭绍辉,郑红霞.褐煤催化降解生烃过程的动力学研究[J].石油勘探与开发,1997,24(3):21-23. LI Shuyuan,GUO Shaohui,ZHENG Hongxia.A study of catalytic degradation kinetics of fanshi lignite[J].Petrolum Exploration and Development,1997,24(3):21-23.
[34] 潘长春,耿安松,钟宁宁,等.矿物和水对干酪根热解生烃作用的影响:甾、藿烷(烯)的形成与热演化[J].地质学报,2006,80(3):446-453. PAN Changchun,GENG Ansong,ZHONG Ningning,et al.The effects of minerals and water on hydrocarbon generation from kerogen:Ⅲ.steranes and triterpane generation and maturation[J].Acta Geologica Sinica,2006,80(3):446-453.
[35] 李术元,林世静,郭绍辉,等.矿物质对干酪根热解生烃过程的影响[J].石油大学学报(自然科学版),2002,26(1):69-71. LI Shuyuan,LIN Shijing,GUO Shaohui,et al.Catlaytic effects of minerals on hydrocarbon generation in kerogen degradation[J].Journal of the University of Petroleum,China,2002,26(1):69-71.
[36] 妥进才,王随继.油气形成过程中的催化反应[J].天然气地球科学,1995,6(2):37-40. TUO Jincai,WANG Suiji.Catalytical reaction during the petro-leum generation[J].Natural Gas Geoscience,1995,6(2):37-40.
[37] YANG Sibo,LI Meijun,LIU Xiaoqiang,et al.Thermodynamic stability of methyldibenzothiophenes in sedimentary rock extracts:based on molecular simulation and geochemical data[J].Organic Geochemistry,2019,129:24-41.
[38] RADKE M.Application of aromatic compounds as maturity indicators in source rocks and crude oils[J].Marine and Petroleum Geology,1988,5(3):224-236.
[39] RADKE M,VRIEND S P,RAMANAMPISOA L R.Alkyldibenzofurans in terrestrial rocks:influence of organic facies and maturation[J].Geochimica et Cosmochimica Acta,2000,64(2):275-286.
[40] LI Meijun,WANG T G,SHI Shengbao,et al.Oil maturity assessment using maturity indicators based on methylated dibenzothiophenes[J].Petroleum Science,2014,11(2):234-246.