在“双碳”目标和我国“相对富煤、缺油、少气”的背景下，将CO₂注入到一定深度的煤层，一方面可实现CO₂地质封存的目的，另一方面可驱替煤层CH₄，提高煤层气产收率，具有重要的现实意义。前人对CO₂驱替煤层CH₄做了大量研究，但对超临界CO₂（ScCO₂）对不同埋深煤的孔隙和分子结构及气体吸附能力作用机制方面研究较少。基于此，本文以鄂尔多斯盆地东缘保德区块（8+9#煤层和4+5#煤层）和临汾区块（5#煤层和8#煤层）为研究对象，以四种不同埋深（800m、1000m、1500m、2000m）煤层的实际储层温压为实验条件，在高温高压反应釜中模拟ScCO₂与煤样的作用过程，采用低温氮气吸附、低场核磁共振、CH₄等温吸附和CO₂等温吸附等测试手段，探讨ScCO₂对煤体孔隙结构和吸附性能的作用特征，采用傅里叶红外光谱、碳谱核磁共振、索氏抽提和气相色谱-质谱联用等测试手段，从分子角度揭示ScCO₂对煤的作用机制。取得的主要结论和认识如下：

第一，查明了ScCO₂对不同埋深煤孔隙结构的作用特征。ScCO₂作用促使煤的微孔向过渡孔转变，孔体积增加，比表面积降低，增加孔隙连通性，表现出扩孔、增透作用，有利于CH₄的解吸、扩散和渗流。ScCO₂作用后煤样的孔隙类型不会有明显的改变，其作用主要是改变孔隙的大小。

第二，阐明了ScCO₂对不同埋深煤吸附性能的作用特征。原煤对CO₂的吸附量远远大于对CH₄的吸附量，说明CO₂相对于CH₄更有利于被煤层吸附。800米埋深和1000米埋深原煤对CH₄的吸附量低于1500米埋深和2000米埋深原煤。经过ScCO₂作用后， CH₄的吸附量减少，这与ScCO₂的扩孔作用导致煤孔隙比表面积减小有关，CO₂吸附量明显增加，说明ScCO₂作用既可以进行CO₂地质封存又能达到驱替CH₄增加煤层气产量的效果。

第三，揭示了ScCO₂对不同埋深煤分子结构的作用特征及其机制。ScCO₂作用后煤中多种官能团占比降低，ScCO₂会将煤中的小分子化合物萃取出来，并且破坏芳香层面之间连接的化学键，降低了芳香层面之间的作用力，增加了芳香层面网间距，破坏芳香环增加烷基侧链，造成分子结构变得松散，使其缩合程度降低。同时ScCO₂会破坏煤样的脂肪侧支链，降低脂肪结构丰度。

第四，厘清了ScCO₂对不同埋深煤小分子化合物的作用特征及其机制。ScCO₂作用过程中会将煤中的小分子化合物萃取出来，同时改造煤体储层结构。800米埋深和1000米埋深煤样中的正构烷烃、三环萜烷和藿烷等饱和烃以及菲类化合物等芳香烃的含量降低，萘类化合物含量升高；1500米埋深和2000米埋深煤样中的正构烷烃、三环萜烷和藿烷等饱和烃以及萘类化合物和菲类化合物等芳香烃含量升高。

Under the background of "dual carbon" goal and China's "relatively rich coal, lack of oil and less gas", CO₂ injection into a certain depth of coal seam can achieve the purpose of CO₂ geological storage on the one hand, on the other hand, it can displace coal seam CH₄ and improve the yield of coalbed gas, which has important practical significance. A lot of studies have been done on CO₂ displacement of coal seam CH₄, but few studies have been done on the mechanism of supercritical CO₂ (ScCO₂) on pore and molecular structure and gas adsorption capacity of coal at different buried depths. Based on this, this paper takes Bade Block (8+9# coal seam and 4+5# coal seam) and Linfen Block (5# coal seam and 8# coal seam) in the eastern margin of Ordos Basin as the research object, and takes the actual reservoir temperature and pressure of four coal seams with different burial depths (800m, 1000m, 1500m, 2000m) as the experimental conditions. The interaction between ScCO₂ and coal samples was simulated in a high-temperature and high-pressure reactor, and the effects of ScCO₂ on pore structure and adsorption properties of coal were investigated by means of low-temperature nitrogen adsorption, low-field nuclear magnetic resonance, CH₄ isothermal adsorption and CO₂ isothermal adsorption. Fourier infrared spectroscopy, carbon NMR, Soxhlet extraction and gas chromatography-mass spectrometry were used to reveal the molecular mechanism of ScCO₂ on coal. The main conclusions and understandings are as follows:

First, the effects of ScCO₂ on pore structure of coal at different buried depths were identified. ScCO₂ can promote the transformation of coal micropores into transition pores, increase pore volume, decrease specific surface area, increase pore connectivity, and show the effects of pore expansion and anti-reflection, which is conducive to the desorption, diffusion and seepage of CH₄. The pore type of coal sample does not change significantly after ScCO₂, and its effect is mainly to change the pore size.

Second, the effect of ScCO₂ on the adsorption properties of coal at different buried depths is illustrated. The adsorption amount of CO₂ in raw coal is much greater than that of CH₄, indicating that CO₂ is more favorable to be adsorbed by coal seam than CH₄. The adsorption capacity of CH₄ in raw coal buried at 800 meters and 1000 meters is lower than that in raw coal buried at 1500 meters and 2000 meters. After ScCO₂ action, the adsorption amount of CH₄ decreases, which is related to the reduction of specific surface area of coal pores caused by ScCO₂ reaming action. The adsorption amount of CO₂ increases significantly, indicating that ScCO₂ action can not only carry out CO₂ geological storage but also achieve the effect of displacing CH₄ to increase coalbed methane production.

Thirdly, the effect of ScCO₂ on the molecular structure of coal at different buried depths and its mechanism were revealed. After the action of ScCO₂, a variety of functional groups in coal will change, ScCO₂ will extract small molecular compounds in coal, and destroy the chemical bond between the aromatic layers, reduce the force between the aromatic layers, increase the spacing of the aromatic layers, destroy the aromatic ring and increase the alkyl side chain, resulting in the molecular structure becoming loose and reducing the degree of condensation. At the same time, ScCO₂ can destroy the fatty collateral chain of coal sample and reduce the fat structure abundance.

Fourthly, the effects and mechanisms of ScCO₂ on small molecule compounds in coal at different burial depths were clarified. In the process of ScCO₂, small molecular compounds in coal are extracted and the structure of coal reservoir is reformed. The content of saturated hydrocarbons such as n-alkanes, tricyclic terpenes and hopanes and aromatic hydrocarbons such as phenanthrene compounds decreased in the coal samples buried at 800 m and 1000 m, while the content of nano compounds increased. The content of saturated hydrocarbons such as n-alkanes, tricyclic terpenes and hopanes, and aromatic hydrocarbons such as nano and phenanthrene compounds increased in the coal samples buried at 1500 m and 2000 m.

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