华南龙马溪组海相页岩溶剂抽提物的GC-MS分析  

GC-MS analysis of solvent extracts from marine shale of Longmaxi Formation in South China

作　　者：陈凤杰 张小东[1,3] 杨燕青 刘晓 李贵中[5] 张硕[1] CHEN Fengjie;ZHANG Xiaodong;YANG Yanqing;LIU Xiao;LI Guizhong;ZHANG Shuo(School of Energy Science and Engineering,Henan Polytechnic University,Jiaozuo 454000,China;Department of Geological and Surveying Engineering,Shanxi Institute of Energy,Jinzhong 030600,China;Collaborative Innovation Center of Coalbed Methane(Shale Gas)in Central Plains Economic Zone,Jiaozuo 454000,China;Shanxi Lanyan Coalbed Methane Group Co.,Ltd.,Jincheng 048200,China;Research Institute of Petroleum Exploration&Development,Beijing 100083,China)

机构地区：[1]河南理工大学能源科学与工程学院,河南焦作454000 [2]山西能源学院地质与测绘工程系,山西晋中030600 [3]中原经济区煤层气(页岩气)协同创新中心,河南焦作454000 [4]山西蓝焰煤层气集团有限责任公司,山西晋城048200 [5]中国石油勘探开发研究院,北京100083

出　　处：《煤炭学报》2021年第8期2637-2649,共13页Journal of China Coal Society

基　　金：国家自然科学基金联合基金资助项目(U1904126);山西省高等学校科技创新资助项目(2020L0727)。

摘　　要：华南志留系龙马溪组海相页岩是我国页岩气勘探的重要目标层位,为了解华南地区龙马溪组海相页岩中可溶有机质的化学组成特征,采用正己烷、氯仿、丙酮、甲醇4种不同极性溶剂对来自重庆涪陵、云南昭通、湖北宜昌地区的龙马溪组页岩样品进行了索氏抽提,通过气相色谱/质谱联用仪(GC/MS)对抽提物的化合物组成进行了测定。研究发现,华南龙马溪组海相页岩的溶剂抽提率普遍较低(0.02%~0.73%)。相比而言,云南昭通龙马溪组下段页岩的溶剂抽提率最高,其次为重庆涪陵和湖北宜昌的龙马溪组下段页岩,重庆涪陵龙马溪组中段页岩抽提率明显低于下段;不同溶剂抽提率对比,氯仿抽提率最高,其次为甲醇和丙酮,正己烷的抽提率最低;华南龙马溪组页岩中的可溶有机小分子化合物由微量的芳香烃、少量的脂肪烃和大量的含杂原子化合物组成,脂肪烃主要为烷烃及脂环烃,杂原子化合物中酯类较多,其次为卤代烃,醇类和酮类较少,其中邻苯二甲酸酯类和1-碘-2-甲基十一烷占有重要地位;不同地区页岩可溶有机质组成相比略有差异,表现为重庆涪陵龙马溪组中段页岩中脂肪烃相对较少,重庆涪陵龙马溪组下段页岩中脂肪烃和卤代烃相对较多,云南昭通龙马溪组下段页岩中醇类少、酮类稍多;正己烷、甲醇、丙酮溶剂对页岩中含氧小分子化合物有较好的溶出能力,氯仿溶剂对脂肪烃、卤代烃和含氧小分子化合物均有较好的溶出能力;正己烷和甲醇抽提物主要组分为酯类,氯仿抽提物主要组分为酯类、卤代烃和脂肪烃,丙酮抽提物主要组分为酯类、酰胺类、酮类和醇类。研究认为,华南龙马溪组海相页岩的溶剂抽提率、可溶有机质中脂肪烃和卤代烃含量受到沉积环境和沉积物组成的影响,可作为潜在的指相参数。The marine shale of Longmaxi formation of Silurian in South China is the main exploration target for shale gas in China.In order to study the chemical nature of soluble organic matter in marine shale of Longmaxi formation in South China,Soxhlet extractions of shale samples from Longmaxi formation of Silurian in Fuling of Chongqing,Zhaotong of Yunnan Province and Yichang of Hubei Province were carried out with four polar solvents,including n-hexane,chloroform,acetone and methanol.It was found that the extraction rate of marine shale of Longmaxi Formation in South China is generally low,ranging from 0.02%to 0.73%.In comparison,the shale in the lower part of Longmaxi Formation in Zhaotong area of Yunnan Province exhibits the highest extraction rate,followed by the lower shale of Longmaxi Formation in Fuling of Chongqing and Yichang of Hubei Province,and the shale in the middle part of Longmaxi Formation in Fuling area of Chongqing shows the lowest extraction rate.By comparing the efficiency of different extraction solvents,the extraction rate of chloroform is the highest,followed by methanol and acetone,and n-hexane extraction rate is the lowest.The soluble organic small molecular compounds of Longmaxi shale in South China are composed of trace aromatic hydrocarbons,a small amount of aliphatic hydrocarbons and a large number of heteroatom compounds.The aliphatic hydrocarbons are mainly alkanes and alicyclic hydrocarbons with more esters of hetero-atomic compounds,followed by halogenated hydrocarbons and fewer alcohols and ketones,among which phthalates and 1-iodo-2-methylundecanone play an important role.There is a slight difference in the composition of soluble organic matter in shale in different areas,which is manifested as that there are relatively few aliphacic hydrocarbons in the middle shale of the Fuling Longmaxi formation in Chongqing,more aliphatics and halogenated hydrocarbons in the lower shale of the Fuling Longmaxi formation in Chongqing,and less alcohols and slightly more ketones in the lower shale of

关 键 词：龙马溪组 页岩 溶剂抽提 可溶有机质 气相色谱/质谱联用仪 

分 类 号：P618.13[天文地球—矿床学]