超临界CO₂（ScCO₂）注入深部煤层可增强煤层气开采（CO₂-ECBM）、实现碳封存，成为目前国内外众多学者的研究热点。但微观角度研究不同变质程度煤与ScCO₂作用演变规律、探讨煤分子结构变化对吸附作用机制较少。本文选取不同变质程度的煤——来自新疆（XY）的褐煤、淮北（HY）的烟煤、赵庄（ZY）的无烟煤，采用实验模拟相结合的方法开展研究，旨在揭示ScCO₂作用下煤分子结构的演变规律和气体吸附特征，研究结果如下：

运用系列表征方法，分析不同变质程度煤的表面结构、微观结构和芳香条纹的变化，构建了不同变质程度煤的大分子结构模型。新疆原煤（XY）的结构模型分子式为C₁₂₁H₁₀₇NO₃₉，淮北原煤（HY）的结构模型分子式为C₁₁₁H₇₈N₂O₂₂S，赵庄原煤（ZY）的结构模型分子式为C₁₁₆H₆₆N₂O₁₄。

ScCO₂、水与煤发生物理化学反应，其表面和微观结构发生一系列的变化。其中低阶煤（XY）芳碳率增加，微晶尺寸增大，桥碳周碳比增大；中高阶煤（HY和ZY）芳碳率降低，微晶尺寸减小，桥碳周碳比减小。但中低阶煤（XY和HY）晶片堆砌层数增多，芳香条纹的有序性增强；高阶煤（ZY）堆砌层数减少，芳香条纹有序性变差。萃取的物质以环烷烃和正构烷烃的比例最大。而高阶煤（ZY）的溶胀作用破坏芳香层片的交联键，减弱层面间的作用力，达到降低芳香性的效果，萃取物中出现萘系化合物。依据煤的演化规律，构建并优化了ScCO₂作用后的煤大分子结构模型。ScCO₂作用后新疆煤（XC）的结构模型分子式为C₁₀₃H₉₃NO₃₂，淮北煤（HC）的结构模型分子式为C₁₆₀H₁₁₀N₂O₃₄S，赵庄煤（ZC）的结构模型分子式为C₁₃₀H₆₆N₂O₁₆。

不同变质程度煤吸附曲线均为Ⅱ型曲线，且均为H3型滞后环，孔形状为狭缝型孔。XY的滞后环明显大于HY，则说明其存在的开放性孔的数量更多。ScCO₂作用后XC存在拐点，说明其存在一定数量的墨水瓶形孔。XY和HY的微孔体积变小，ZY微孔体积增大。

不同变质程度煤ScCO₂作用后对温度的敏感程度不同，低阶煤对温度的敏感性更强。三种煤样在ScCO₂作用前后CH₄吸附量均降低，而HC的降低幅度最大。ScCO₂作用后，XY和XC吸附CH₄和CO₂呈现相反的变化，XY和HY的吸附热随着吸附量的增加而增加，ZY则随着吸附量的增加而减少，与ScCO₂反应后，XC、HC和ZC吸附热均随着吸附量的增加而降低。建立不同变质程度煤吸附气体模型。煤吸附CH₄的模型为微孔的Dubinin-Astahov-1（D-A-1）和中大孔Langmuir-Freundlich（L-F）模型的结合；而煤吸附CO₂的吸附模型为微孔的D-A-2或者D-A-3模型，而介大孔的拟合模型则为3参数BET（T-BET）-2或T-BET-3模型。

构建煤孔结构的分子模型，分析了ScCO₂作用对煤孔结构中孤立孔和连通孔的影响。ScCO₂作用后一部分孤立孔变为连通孔，结合球棍模型揭示了煤中孤立孔和连通孔的配位数的变化。研究孤立孔和连通孔中不同压强、气体类型和含水量对气体吸附性能的影响，采用分子动力学方法分析气体微观自扩散系数（D^s）、校正扩散系数（D^c）和宏观传输扩散系数（D^t）之间的关系，即：D^sct，同时结合径向分布函数（RDF），查明了煤与气体的吸附主要与煤大分子骨架中碳原子和气体分子之间作用强度相关。

本文的研究对CO₂-ECBM技术和煤层CO₂长期安全封存提供基础理论数据。

The introduction of supercritical CO₂ (ScCO₂) into deep coal seams can enhance coalbed methane recovery (CO₂-ECBM) and achieve carbon sequestration, garnering significant attention from researchers globally. However, limited studies have been conducted on the interaction evolution between coal with varying metamorphic degrees and ScCO₂, as well as the coal molecular structure's changes during adsorption from a microscopic perspective. In this study, the lignite coal from Xinjiang (XY), bituminous coal in Huaibei (HY), and anthracite coal in Zhaozhuang (ZY) with different metamorphic degrees were investigated using experimental and simulation approaches. The aim is to reveal the evolution of coal molecular structure and gas adsorption characteristics under the action of ScCO₂. The findings are as follows:

(1) A range of characterization methods was employed to analyze the alterations in surface structure, microstructure, and aromatic fringes of coals with differing metamorphic levels. Macromolecular structure models is constructed, and the structural model of molecular formula from Xinjiang coal (XY) is C₁₂₁H₁₀₇NO₃₉, Huaibei coal (HY) is C₁₁₁H₇₈N₂O₂₂S, and Zhaozhuang coal (ZY) is C₁₁₆H₆₆N₂O₁₄.

(2) The interaction between ScCO₂, water, and coal involved numerous physical and chemical reactions, particularly in surface and microstructure. For low-rank coal (XY), the aromatic carbon ratio, microcrystalline size, and bridge carbon ratio increase, while these parameters decrease for medium and high-rank coals (HY and ZY). The stacking layer number for medium and low-rank coals (XY and HY) increases, as do the orderliness of aromatic stripes. Conversely, the stacking layer number for high-rank coal (ZY) reduces, and the order of aromatic stripes deteriorates. Among the extracted substances, cycloalkanes and n-alkanes constitute the largest proportions. The swelling of high-rank coal (ZY) disrupts the cross-linking bond of aromatic layers, weakens interlayer forces, and diminishes aromaticity effects. Naphthalene compounds are present in ZY extractions. Based on the evolution law, macromolecular structure models of coal are constructed and optimized after reacting with ScCO₂. The structural model of molecular formulas for Xinjiang supercritical coal (XC), Huaibei supercritical coal (HC), and Zhaozhuang supercritical coal (ZC) are determined as C₁₀₃H₉₃NO₃₂, C₁₆₀H₁₁₀N₂O₃₄S, and C₁₃₀H₆₆N₂O₁₆, respectively.

(3) The adsorption curves for the three coal samples are classified as type II curves, with all exhibiting H3 hysteresis loops and slit pore shapes. The hysteresis loop of XY is significantly larger than that of HY, indicating the presence of more open pores. An inflection point is observed in XC, suggesting a specific number of ink bottle pores. The micropore volume of XY and HY decrease, while the micropore volume of ZY increases.

(4) After reacting with ScCO₂, the temperature sensitivity of coal with different metamorphic degrees varies, with low-rank coal exhibiting greater sensitivity. The CH₄ adsorption capacity of the three coal samples decrease before and after reacting with ScCO₂, with HC experiencing the largest decrease. Upon reacting with ScCO₂, the adsorption of CH₄ and CO₂ by XY and XC demonstrate inverse changes. The adsorption heat of XY and HY increase alongside the growth of adsorption capacity, whereas ZY decreases with the rising adsorption capacity. After reacting with ScCO₂, the adsorption heat of XC, HC, and ZC diminish as adsorption capacity increases. The model for CH₄ adsorption on coal with varying metamorphic degrees is a combination of the Dubinin-Astahov-1 (D-A-1) and Langmuir-Freundlich (L-F) models. The CO₂ adsorption model is the D-A-2 or D-A-3 model for micropore fitting, while the fitting model for medium and large pores is the 3-parameter BET (T-BET)-2 or T-BET-3 model.

(5) A molecular model of coal pore structure was constructed, and the effects of coal's reaction with ScCO₂ on isolated and connected pores within the coal pore structure were analyzed. After reacting with ScCO₂, some isolated pores became connected pores. The changes in the coordination number of isolated and connected pores in coal were analyzed using the ball-stick model. The impact of varying pressure, gas type, and water content on adsorption in isolated and connected pores was investigated. Microscopic pore structure alterations are integrated with macroscopic ones. The relationship between gas microscopic self-diffusion coefficient (D^s), correction diffusion coefficient (D^c), and macroscopic transport diffusion coefficient (D^t) was analyzed, with D^s < D^c < D^t. In conjunction with the radial distribution function (RDF), coal and gas adsorption primarily depends on the interaction between carbon and gas.

In this study, it can provide basic theoretical data for CO₂-ECBM technology and long-term safe storage of CO₂ in coal seams.

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