沉积有机质中苯基菲成熟度参数及其化学机理——基于地球化学数据和量子化学计算  

Maturity Parameter of Phenylphenanthrene in Sedimentary Organic Matter and Its Chemical Mechanism Based on Geochemical Data and Quantum Chemical Calculation

作　　者：朱志立 李美俊 李佳阳[4] 祁灵 刘晓强[6] 韩秋雅 路清华 马媛媛 冷筠滢[1,2,3] ZHU ZhiLi;LI MeiJun;LI JiaYang;QI Ling;LIU XiaoQiang;HAN QiuYa;LU QingHua;MA YuanYuan;LENG JunYing(State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development,Beijing 102206,China;SINOPEC Key Laboratory of Petroleum Accumulation Mechanisms,Wuxi,Jiangsu 214126,China;Wuxi Research Institute of Petroleum Geology,RIPEP,SINOPEC,Wuxi,Jiangsu 214126,China;College of Geosciences,China University of Petroleum(Beijing),Beijing 102249,China;Research Institute of Petroleum Exploration and Development,PetroChina,Beijing 100083,China;College of Chemistry and Environmental Engineering,Sichuan University of Science and Engineering,Zigong,Sichuan 643000,China)

机构地区：[1]页岩油气富集机理与有效开发国家重点实验室,北京102206 [2]中国石化油气成藏重点实验室,江苏无锡214126 [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214126 [4]中国石油大学(北京)地球科学学院,北京102249 [5]中国石油勘探开发研究院,北京100083 [6]四川轻化工大学化学与环境工程学院,四川自贡643000

出　　处：《沉积学报》2023年第2期601-609,共9页Acta Sedimentologica Sinica

基　　金：国家自然科学基金项目(41972148);“页岩油气富集机理与有效开发国家重点实验室”开放基金项目(33550007-21-ZC0613-0016);国家科技重大专项(2016ZX05004-005)。

摘　　要：苯基菲(PhP)广泛分布于沉积有机质和原油中,是重要的苯基多环芳烃化合物。通过标样相对保留时间和标准保留指数对比的方法,对准噶尔盆地和鄂尔多斯盆地26件煤中苯基菲系列进行了系统、准确地鉴定,确定了其在色谱柱(HP-5MS)上的流出顺序:4-、9-、1-、3-、2-苯基菲。采用量子化学计算的方法,精确计算了苯基菲系列的热力学性质,确定了其热稳定性大小顺序为:2->3->9->1->4-PhP。结合不同成熟度煤中该系列的分布特征,提出成熟度参数苯基菲比值(PhPR=(2+3)-PhP/(1+9)-PhP),初步建立了其与镜质组反射率(Ro)的定量关系式:Rc(%)=0.06×PhPR+0.32(Ro>0.4%),并发现沉积环境对苯基菲比值的影响很小,认为该参数是定量评价低熟—高熟原油和烃源岩(Ⅱ~Ⅲ型干酪根)成熟度的良好指标。对比甲基菲(MP)分布特征和热稳定性发现,苯基菲比值的化学机理可能主要与苯基迁移作用有关,即随着成熟度的升高,1-苯基菲可能通过1,2-苯基迁移作用转化为2-和3-苯基菲。相比于对应的甲基菲参数((2+3)-MP/(1+9)-MP),苯基菲比值对成熟度的变化更敏感。Phenylphenanthrenes(PhP)are important phenyl polycyclic aromatic hydrocarbons and are ubiquitous in sedimentary organic matters and crude oils.In this study,PhP were unambiguously identified in 26 coal samples from the Junggar and Ordos Basins by comparing the relative retention times and retention indices.The elution order of PhP in a HP-5MS chromatographic column was 4-,9-,1-,3-,2-PhP.The thermodynamic properties of PhP isomers were accurately calculated by quantum chemical calculation;the thermodynamic stability of PhP isomers is in the se⁃quence 2->3->9->1->4-PhP.Combining the distributions of PhP in coals of different maturity,a maturity parameter PhP ratio PhPR=(2+3)-PhP/(1+9)-PhP is proposed,and its quantitative relationship with vitrinite reflectance(Ro)is preliminarily established as follows:Rc(%)=0.06×PhPR+0.32(Ro>0.4%).In addition,the sedimentary environ⁃ment of organic matter has no significant effect on PhPR.Therefore,PhPR is a useful maturity indicator for quantita⁃tively assessing the thermal maturity of oils and source rocks(Types II⁃III kerogen)with low-high maturation levels.Comparisons of the distribution and thermodynamic stability of PhP and methylphenanthrenes(MP)suggest that the chemical mechanism of the ratio PhPR may be mainly related to a phenyl group shift in which the increase of matura⁃tion 1-PhP may be transformed into 2-and 3-PhP by a 1,2-phenyl shift.For(2+3)-MP/(1+9)-MP,PhPR is more sensitive to maturity change than the corresponding MP.

关 键 词：煤 苯基菲 量子化学计算 热稳定性 成熟度 

分 类 号：P618.13[天文地球—矿床学]