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超临界CO2−水−岩作用下黔北牛蹄塘组页岩表面能演化机制

Evolution mechanism of surface energy of Niutitang Formation shale in Northern Guizhou under supercritical CO2-water-rock interactions

  • 摘要: 表面能是影响页岩储层气液流体存储状态的关键因素。为研究储层温压条件下超临界CO2与水−岩体系相互作用对页岩表面能的影响,以黔北牛蹄塘组页岩为研究对象,采用接触角测试法和van Oss-Chaudhury-Good(vOCG)理论,结合X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜及能量色散光谱(SEM/EDS)等测试技术,系统研究了超临界CO2−水−岩作用下页岩表面能演化规律及其影响机制。结果表明:页岩与非极性测试液(二碘甲烷)的接触角明显小于与极性测试液(丙三醇和蒸馏水)的接触角,说明该测试页岩样品具有较强的非极性特征。超临界CO2−水−岩作用后,页岩表面能出现了明显增大趋势,且表面能极性分量的增大幅度高于非极性分量;页岩表面能非极性分量的变化主要源于钠长石和石英等非极性矿物质量分数的增大,而其极性分量的变化则受控于官能团变化引起的表面电子供给能力改变。超临界CO2−水−岩作用后,页岩表面能增大会促使其对CO2、CH4和H2O分子的吸附能力增大,这会导致CO2和CH4在页岩储层中更容易以吸附态形式存在,且页岩微纳米孔隙中残余水分子产生的水锁效应也会增强,这对CO2长期稳定封存是有利的,但对页岩气采收则会产生不利影响。研究成果可为贵州页岩气高效开采和CO2地质封存提供支撑。

     

    Abstract: Surface energy is a key factor governing the storage states of gaseous and liquid fluids in shale reservoirs. To investigate the effects of supercritical CO2-water-rock interactions on shale surface energy under reservoir temperature and pressure conditions, this study takes shale collected from the Niutitang Formation in northern Guizhou as the research subject. Utilizing the contact angle measurement method and the van Oss-Chaudhury-Good (vOCG) theory, combined with analytical techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy and energy-dispersive spectroscopy (SEM/EDS), the evolutionary patterns and influencing mechanisms of shale surface energy under supercritical CO2-water-rock interaction were systematically studied. The results indicate that the contact angles between shale and the non-polar test liquid (diiodomethane) are significantly smaller than those with polar test liquids (glycerol and distilled water), demonstrating that the tested shale samples possess strong non-polar characteristics. After supercritical CO2-water-rock interaction, the shale surface energy showed a significant increasing trend, with the polar component increasing more markedly than the non-polar component. The change in the non-polar component of the shale surface energy mainly stems from the increased percentage of non-polar minerals such as albite and quartz in the shale, while the change in the polar component is controlled by alterations in the surface electron-donating capacity resulting from changes in functional groups. The increase in shale surface energy after supercritical CO2-water-rock interaction enhances its adsorption capacity for CO2, CH4, and H2O molecules, which would lead to CO2 and CH4 being more likely to exist in adsorbed states within the shale reservoir, and the water-blocking effect caused by residual water molecules in the micro-nano pores of shale would also be intensified. This is beneficial for the long-term stable sequestration of CO2, but may adversely affect shale gas recovery. The research findings provide support for the efficient extraction of shale gas and CO2 geological storage in Guizhou.

     

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