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

发布时间：2018-03-14 19:24

本文选题：X射线吸收近边结物(XANES)　切入点：硫酸盐热化学还原反应　出处：《地质学报》2017年03期 　论文类型：期刊论文

【摘要】：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X射线吸收近边结物(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、硫酸盐热化学还原反应(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]:In order to study the variation of the occurrence of sulfur and calcium during the cracking of carbonate reservoir crude oil was collected from the formation of Ordovician Yingshan formation in TK772 well of Tahe Oilfield. The gas forming simulation experiment of simulating formation conditions was carried out by means of the semi-open experimental system "formation pore thermal compression generating and expelling hydrocarbon simulator". The sulfur in solid products was studied by synchrotron radiation X-ray absorption near edge junction (XANES) technique. The chemical occurrence state of calcium was accurately detected. The results showed that the sulfur compounds in the solid products of direct cracking of crude oil (crude oil limestone experiment (series 1)) were mainly thiophene and calcium sulfate. It is the result of partial oxidation of thiophene in the process of crude oil cracking. Calcium carbonate is the main calcium containing compound. The sulfur compounds in the solid products of crude oil pyrolysis (Limestone magnesium Sulfate experiment (Series 2)) with dissolved sulfate are mainly calcium sulfate, supplemented by thiophene. It is possible that the addition of dissolved sulfate (magnesium sulfate), the reaction of thermochemical reduction of sulfate TSRs and the action of dissolution and precipitation. The formation of H 2S and the increase of the relative percentage of calcium sulfate in series 2 are accompanied by the increase of temperature and pressure. The formation and enrichment of calcium sulfate indicate that the acid fluid produced by TSR process can cause obvious dissolution of carbonate reservoir and may form secondary gypsum salt at the same time.
【作者单位】：南京大学地球科学与工程学院;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;
【基金】：国家“973”计划项目(编号2012CB214801) 国家自然科学青年基金(编号41503033)联合资助成果
【分类号】：P618.13;TE621

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