钙-XANES技术在固体沥青温压模拟实验研究中的应用

Application of calcium-XANES technique in solid bitumen simulation experiments under temperature and pressure

魏志红 罗厚勇 刘文汇 腾格尔 王万春 梁明亮 苏龙 赵屹东

Wei Zhihong Luo Houyong Liu Wenhui Tenger Wang Wangchun Liang Mingliang Su Long Zhao Yidong

中国石化 勘探分公司, 成都 610041 2. 中国科学院 油气资源研究重点实验室, 兰州 730000 3. 中国石油化工集团公司 油气成藏重点实验室, 江苏 无锡 214151 4. 中国科学院 高能物理研究所, 北京 100049

Branch of Exploration Company, SINOPEC, Chengdu, Sichuan 610041, China 2. Key Laboratory of Petroleum Resources Research, Chinese Academy of Sciences, Lanzhou Gansu 730000, China 3. SINOPEC Key Laboratory of Petroleum Accumulation Mechanisms, Wuxi, Jiangsu 214151, China 4. Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

为了研究固体沥青热解和TSR过程中钙元素赋存状态的演化,采集川西北矿山梁地区的下寒武统含硫低熟固体沥青,通过半开放实验体系"高温高压模拟仪"开展仿真地层条件的模拟实验,并利用钙的K边XANES分析技术对固体产物中的钙元素的化学赋存状态进行精确检测。结果表明,沥青热解模拟实验固体产物中含钙化合物以碳酸钙为主;沥青TSR模拟实验过程中,伴生着温压的升高,硫化氢产率和硫酸钙相对百分含量的增加,指示实验过程中既发生了还原态硫化物的氧化反应,也发生了氧化态的硫酸盐的还原反应;硫酸钙矿物的生成和富集表明,TSR过程伴生的酸性流体可以对白云岩储层产生明显的溶蚀作用。

The Lower Cambrian solid bitumen, with high organic content, high hydrogen index and low asphaltene maturity, was collected from the Kuangshanliang area in the northwestern Sichuan Basin to study the evolution of calcium speciation during TSR and pyrolysis of solid bitumen.. The generation and expulsion simulation experiments were carried out in a high temperature and pressure simulator, and the calcium speciation was determined using a direct, non-destructive synchrotron-based calcium K-edge X-ray Absorption Near Edge Structure (XANES). Calcium carbonate was the major calcium compound in the asphalt pyrolysis simulation experiments (series 1). However, in the asphalt TSR simulation experiment (series 2), with the increases of temperature and pressure, the yield of H2S and sulfate increased, indicating that both oxidation and reduction reactions occurred. The generation and enrichment of calcium sulfate in the simulation experiments of series 2 indicated that the acidic fluid from the TSR process could produce significant dissolution in dolomite reservoirs.

国家重点基础研究发展计划(973计划)项目(2012CB214801)资助。

https://doi.org/10.11781/sysydz201504512