富有机质粘土岩中膨胀性粘土矿物对乙二醇乙醚（EGME）法测定粘土岩全比表面积的影响和机理

The specific surface area of organic-rich clay rocks is of great significance for understanding the surface-interface reactivity of clay rocks. Ethylene glycol monoethyl ether (EGME) adsorption method is the most commonly used method to evaluate the total specific surface area (TSSA) of clay rocks. Montmorillonite (Mt) is a kind of important swelling clay mineral components in organic-rich clay rocks. It was proposed in the research topic that the combination types between Mt and organic matter (OM) might affect the EGME adsorption mechanism of clay rocks, thus influencing the accurate analysis of TSSA. For this purpose, the present proposal starts with the Mt, Mt-OM complexes, and the EGME adsorption behavior of Mt, interlayer Mt-OM complexes and external Mt-OM complexes are investigated. The planning work includes the investigation on the changes of the microstructure and surface properties of Mt and Mt-OM complexes before and after EGME adsorption, and the effects and related mechanisms of OM with contents, the types of functional groups, and the associations between Mt and OM on the EGME adsorption of Mt-OM complexes will be found out. After based a combined analysis of the EGME adsorption characteristics of clay mineral-OM complexes in the organic-rich clay rocks, the key mineralogical influence factors and related mechanisms of EGME adsorption in the measurement of specific surface area can be revealed. The research results of the project are expected to obtain an in-depth understanding of EGME adsorption mechanism for clay mineral-OM complexes and even organic-rich clay rocks. In addition, based on these mentioned results, it will provide theoretical and experimental evidence for the accurate measurement of TSSA for clay rocks as well as applicable assessment of EGME adsorption method.

富有机质粘土岩比表面积对深入认识粘土岩表-界面反应性具有重要意义，乙二醇乙醚（EGME）吸附法是目前实现全表面积测定较常用的方法。本课题经分析提出，蒙脱石是富有机质粘土岩中重要的膨胀性粘土矿物，其与有机质间的复合方式可能影响粘土岩对EGME的吸附机制，从而影响全比表面积的准确分析。为此，拟由蒙脱石及蒙脱石-有机质复合体入手，考察蒙脱石-有机质层间和层外复合体的EGME吸附行为，探索蒙脱石及复合体微结构和表面性质在吸附前后的变化和机理，探明有机质含量、官能团类型及赋存形式对复合体EGME吸附的影响机制；并结合富有机质粘土岩中粘土矿物-有机质复合体的EGME吸附特征，揭示EGME吸附法在比表面积测量时的关键矿物学影响因素和相关机理。研究结果可望为深入理解粘土矿物-有机质复合体乃至富有机质粘土岩对EGME的吸附机制奠定基础，为准确评估粘土岩全比表面积和EGME法的适用性和条件提供理论和实验依据。

富有机质粘土岩比表面积对深入认识粘土岩表-界面反应性具有重要意义，乙二醇乙醚（E.GME）吸附法是目前实现全表面积测定较常用的方法。蒙脱石-有机质复合体是富有机质粘土岩中重要的组成部分，其对EGME的吸附机制对评估富有机质黏土岩的全比表面积具有重要的影响。为此，本研究通过开展蒙脱石及其有机质复合体的EGME吸附研究，并在上述样品表面性质、孔隙结构等分析的基础上，探讨有机质赋存对黏土岩EGME吸附的影响，进而分析影响黏土岩EGME比表面积测定的准确性因素。结论如下：（1）蒙脱石与有机质的复合方式对EGME的吸附具有显著影响，从而影响EGME比表面积（全比表面积）大小。层间复合体的EGME吸附作用取决于层间有机质的排布以及有机质分子类型，层外复合体的EGME吸附作用与有机质性质以及粘土矿物本身孔结构特征有关；（2）EGME吸附法可对纯相的黏土矿物进行全比表面积的表征，还能够作为一种验证XRD定量全岩矿物的手段；（3）有机质赋存强烈制约EGME吸附法测定富有机质黏土岩全比表面积，层间有机质的存在更是为EGME吸附法的使用提供了难点与不确定性，这与其与黏土矿物的界面作用及富有机制黏土岩中复杂的孔隙网络结构有关。本研究工作为揭示富有机质粘土岩对EGME的吸附机制奠定基础，为准确评估粘土岩全比表面积和EGME法的适用性和条件提供理论和实验依据。