碳酸盐岩储层原油裂解过程中的钙、硫分子地球化学研究—同步辐射XANES技术的应用
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中石化石油勘探开发研究院无锡石油地质研究所,中石化石油勘探开发研究院无锡石油地质研究所,中石化石油勘探开发研究院无锡石油地质研究所,中国科学院油气资源研究重点实验室,中国科学院油气资源研究重点实验室,中国科学院油气资源研究重点实验室,中石化石油勘探开发研究院无锡石油地质研究所,中石化石油勘探开发研究院无锡石油地质研究所,中国科学院油气资源研究重点实验室

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国家重点基础研究发展计划(973计划)


Molecular Geochemistry Study of Calcium and Sulfur in the Process of Crude Oil Cracking in Carbonatic Rock Reservoirs: Application of Synchrotron Radiation XANES Technology
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Wuxi Research Institute of Petroleum Geology, SINOPEC,Wuxi Research Institute of Petroleum Geology, SINOPEC,Wuxi Research Institute of Petroleum Geology, SINOPEC,Key Laboratory of Petroleum Resources Research, Chinese Academy of Sciences,Key Laboratory of Petroleum Resources Research, Chinese Academy of Sciences,Key Laboratory of Petroleum Resources Research, Chinese Academy of Sciences,Wuxi Research Institute of Petroleum Geology, SINOPEC,Wuxi Research Institute of Petroleum Geology, SINOPEC,Key Laboratory of Petroleum Resources Research, Chinese Academy of Sciences

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    摘要:

    内容提要:为了研究碳酸盐岩储层原油裂解过程中硫、钙元素赋存状态的变化,采集塔河油田TK772井奥陶系鹰山组产层的原油,通过半开放实验体系“地层孔隙热压生排烃模拟仪”开展仿真地层条件的成气模拟实验,利用同步辐射XANES技术对固体产物中的硫、钙元素的化学赋存状态进行精确检测。结果表明,原油直接裂解(原油 灰岩实验(系列1))固体产物中含硫化合物以噻吩类和硫酸钙为主,是原油裂解过程中部分噻吩类物质被氧化的结果;含钙化合物以碳酸钙为主。有溶解硫酸盐存在的原油裂解(原油 灰岩 硫酸镁实验(系列2))固体产物中含硫化合物以硫酸钙为主,噻吩类为辅,可能是溶解硫酸盐(硫酸镁)的加入、TSR和溶蚀-沉淀作用共同作用的结果。系列2中伴随着温压的升高,H2S的生成和硫酸钙相对百分含量增加,指示原油裂解过程中发生了硫酸盐热化学还原反应(TSR);硫酸钙的生成和富集表明,TSR过程产生的酸性流体可以对碳酸盐岩储层产生明显的溶蚀作用,同时可能会生成次生膏盐。

    Abstract:

    Abstract: In order to study the changes of sulfur and calcium elements when oil cracking in carbonate reservoirs, collecting Ordovician Yingshan formation oil of well TK772 in Tahe Oilfield, through semi-open test system "formation porosity thermocompression simulation experiment instrument" to carry out gas generating simulation experiments in the formation conditions, using synchrotron radiation technology "X-ray absorption near edge structure" to detect the chemical mode of sulfur and calcium elements in solid products. The results showed that sulfur compounds in solid products of crude oil direct lysis (crude oil limestone(Series 1)) are the thiophene and calcium sulfate, is the result of the oxidized of thiophene substances in crude oil; the calcium-containing compound calcium is carbonate-based. The presence of dissolved sulfate crude lysate (crude oil limestone magnesium sulfate(series 2)), sulfur-containing compound is a solid product calcium sulfate-based and supplemented thiophenes, may be result of the dissolved sulfate (magnesium sulphate) , TSR and dissolution - precipitation. Accompanied by elevated temperature and pressure in series 2, H2S generation and calcium sulfate relative percentage increase, indicating the occurrence of thermochemical sulfate reduction (TSR) in crude oil cracking process; calcium sulphate formation and enrichment shows, acidic fluid generated during TSR in carbonate reservoirs can produce significant dissolution, and secondary gypsum may be generated.

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罗厚勇,刘文汇,腾格尔,王万春,梁明亮,苏龙,韩元红,曹涛涛,赵恒.2017.碳酸盐岩储层原油裂解过程中的钙、硫分子地球化学研究—同步辐射XANES技术的应用[J].地质学报,91(3):668-677.
Luo Houyong, Liu Wenhui, teng geer, Wang Wanchun, Liang Mingliang, Sulong, Han Yuanhong, Cao Taotao, Zhao Heng.2017. Molecular Geochemistry Study of Calcium and Sulfur in the Process of Crude Oil Cracking in Carbonatic Rock Reservoirs: Application of Synchrotron Radiation XANES Technology[J]. Acta Geologica Sinica,91(3):668-677.

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  • 收稿日期:2015-12-08
  • 最后修改日期:2016-02-22
  • 录用日期:2016-02-22
  • 在线发布日期: 2017-03-16
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