液态CO₂注入煤层驱替置换CH₄是近年来强化瓦斯抽采及碳封存的重要手段之一。液态CO₂注入煤层后，经“液相渗流-相变增压-气液传质”等过程，与煤体发生物理和化学作用，煤的微观特征如孔隙分布、表面化学性质和吸附特征发生变化。煤孔隙中充填的矿物质及有机质极大堵塞了其连通性，是造成渗透性偏低的主要原因。液态CO₂属于非极性流体，煤层注入CO₂流体会引起煤体中的无机矿物质、有机质进一步与酸性流体之间发生强烈的水岩相互作用，煤中的矿物质发生不同程度的溶蚀、转化和沉淀，有机物质发生溶出及萃取作用，导致煤岩物理结构、化学结构等储层物化性质进一步改变。因此，研究液态CO₂注入煤层后在不同阶段对煤中无机矿物质、有机物质的作用及其对煤体孔隙结构的改造机制具有重要工程应用价值。

选取三种不同变质程度的煤样为研究对象，采用理论分析、数值模拟和实验测试等相结合的研究方法，开展液态CO₂萃取与溶蚀对煤体改性相关研究。分别开展不同变质程度、压力和时间等条件下液态CO₂萃取和溶蚀煤体实验，对原煤和残煤进行微观结构、组分含量和气体吸附特征测试，掌握液态CO₂对煤体理化作用前后物性参数演化规律，取得的主要研究成果如下：

（1）基于萃取物料颗粒的质量守恒和溶蚀过程矿物颗粒分形特征，建立液态CO₂萃取及溶蚀煤体数学模型，结合数值模拟分析有机质萃取和矿物溶蚀过程组分演化特征。随萃取压力增大，有机小分子在煤体内扩散速率增大，有利于小分子有机质溶出；在较大孔隙中，液态CO₂与孔隙表面接触面积增大，小分子有机质易于析出；矿物在煤体孔裂隙中主要以充填或薄膜状附着两种状态赋存，溶蚀速率与矿物溶蚀相对反应时间呈明显非线性关系，溶蚀前一半矿物颗粒所需时间相对较短，随着CO₂压力升高，方解石溶解度迅速增加，其它矿物溶解度增大的速率较为缓慢。

（2）开展了不同变质程度、压力和时间等条件下液态CO₂萃取煤样单因素实验，对比分析了不同参数对液态CO₂萃取煤中有机质含量的影响规律和动力学特征。三种煤样原煤与萃取后残煤红外光谱基本一致，吸收峰强度有明显差异，液态CO₂萃取作用未显著破坏煤的大分子结构；三种煤样经液态CO₂萃取后，脂肪烃和芳香烃相对含量与压力呈正相关趋势，酮类、醇类、醚类和酯类化合物的溶出具有阶段性、时序性和爆发性等特点；萃取初始阶段，溶出物多为“游离”于大分子网络结构中、分子间引力较小的小分子化合物，随着萃取压力和时间的增大，呈“嵌入”态、分子作用力较强的烃类、非烃类小分子化合物被溶出。

（3）模拟地层温度和压力进行CO₂与含水煤样溶蚀单因素实验，并对原煤样及反应后煤样进行矿物成分和元素相对含量测试分析。元素或元素组合的迁移与矿物赋存特征紧密相关，与碳酸盐矿物有关的Ca、Mn、Cu、Zn和Sr等元素，在反应初期具有较大的迁移率；与硫化物和硫酸盐矿物有关的Fe和S元素，在反应中期迁移率较大；在硅酸盐矿物中赋存的V、Ti、Al和Si等元素在反应后期表现出较大的迁移；三种煤样中高岭石、伊利石、石英和钾长石等矿物在不同溶蚀压力下，在反应过程中发生矿物相互转化作用，在反应中期，含量有明显变化；碳酸盐矿物在反应初期快速溶蚀，CO₂压力对反应影响较大，对煤体孔裂隙结构重构起主导作用；黄铁矿在溶蚀反应中期发生微弱氧化还原反应，含量降低。

（4）基于液态CO₂萃取及溶蚀煤体的物化反应实验，借助扫描电镜、CT扫描、低温N₂吸附等孔裂隙测试手段，分别对液态CO₂与煤物化反应前后表面和内部孔隙结构分布及连通性进行测试和对比分析。煤样经液态CO₂萃取后，萃取残煤的颗粒大小分布比较均匀，表面形态明显变得平整光滑，矿物的部分溶蚀使孔裂隙和微裂隙进一步扩展和小范围连通，部分矿物反应后表面产生了大量的溶蚀孔；无烟煤、烟煤和褐煤经液态CO₂萃取后，微孔数量减少，过渡孔和中孔含量增加，液态CO₂萃取对微孔具有扩孔作用；三种煤样在CO₂-H₂O的溶蚀作用下，微孔、过渡孔和中孔数量均有明显增加，平均孔径增大；三种煤样经液态CO₂萃取后，BET比表面积随萃取压力增大逐渐减小，微孔比表面积变化在整个孔隙比表面积中起主导作用，过渡孔和中孔比表面积在萃取前后无显著变化，煤中有机质萃取后，微孔被扩大、连通形成较大的孔，在扩孔的作用下导致煤样的总比表面积变小。

（5）基于液态CO₂萃取与溶蚀前后煤体微观孔隙结构测试结果，分析了煤体孔隙结构对气体吸附特征的影响规律。各煤样对CO₂气体分子表面吸附属于多层吸附；三种煤样经液态CO₂萃取后，孔隙比表面积呈减小趋势，CO₂吸附量随萃取压力增大而减小，无烟煤吸附量减小量大于烟煤和褐煤；经不同CO₂压力溶蚀后，吸附量随溶蚀压力升高逐渐增大，烟煤吸附量增幅大于无烟煤和褐煤，经溶蚀后，烟煤适合CO₂地质封存。

Liquid CO₂ injection into coal seam to displace methane is one of the important means to strengthen gas drainage and carbon sequestration in recent years. After the liquid CO₂ is injected into the coal seam, through the process of "liquid seepage-phase change pressurization-gas-liquid mass transfer", it has physical and chemical interaction with coal, and the microscopic characteristics of coal, such as pore distribution, surface chemical properties and adsorption characteristics, change. The minerals and organic matter filled in the pores of coal greatly block its connectivity, which is the main reason for the low permeability. Liquid CO₂ is a non-polar fluid. The injection of CO₂ fluid into coal seam will cause a strong water-rock interaction between inorganic minerals and organic matter in coal and acidic fluid. Minerals in coal will be corroded, transformed and precipitated in different degrees, and organic matter will be dissolved and extracted, which will further change the physical and chemical properties of coal and rock. Therefore, it is of great engineering application value to study the effect of liquid CO₂ fluid on inorganic minerals and organic substances in coal at different stages after liquid CO₂ is injected into coal seam, and the mechanism of reforming coal pore structure.

Coal samples with different metamorphic degrees from three regions were selected as the research objects, and the related research on coal modification by liquid CO₂ extraction and dissolution was carried out by using theoretical analysis, numerical simulation, experimental test and other research methods. Experiments on extraction and dissolution of coal by liquid CO₂ under different metamorphic degrees, pressures, time and other conditions were carried out. The microstructure, component content and gas adsorption characteristics of raw coal and residual coal were tested to master the evolution law of coal physical properties before and after the physical and chemical effects of liquid CO₂ on coal. The main research results are as follows:

(1) Based on the mass conservation of extracted material particles and fractal characteristics of mineral particles in the dissolution process, a model of liquid CO₂ extraction and dissolution of coal was established, and the evolution characteristics of components in the extraction and dissolution process of organic matter and minerals were analyzed by numerical simulation. With the increase of extraction pressure, the diffusion rate of small organic molecules in coal increases, which is beneficial to the dissolution of small organic molecules. In larger pores, the contact area between liquid CO₂ and pore surface increases, and small molecular organic matter is easy to precipitate. In the pores and fissures of mineral coal, it mainly exists in two states: filling or film attachment. The dissolution rate has an obvious nonlinear relationship with the relative reaction time of mineral dissolution. It takes a relatively short time to dissolve the first half of mineral particles. With the increase of CO₂ pressure, the solubility of calcite increases rapidly, while the solubility of other minerals increases slowly.

(2) Single-factor experiments of extracting coal samples with liquid CO₂ under different metamorphic degrees, pressures, time and other conditions were carried out, and the effects of different parameters on the organic matter content in coal extracted with liquid CO₂ and its dynamic characteristics were compared and analyzed. The infrared spectra of raw coal and residual coal after extraction of three coal samples are basically the same, and the absorption peak intensity is obviously different. The macromolecular structure of coal is not obviously damaged by the extraction of liquid CO₂. After the three coal samples were extracted by liquid CO₂, the relative content of aliphatic hydrocarbon and aromatic hydrocarbon showed a positive correlation trend with the pressure, and the dissolution of ketones, alcohols, ethers and esters was characterized by stages, time series and explosiveness. At the initial stage of extraction, the dissolved substances are mostly small molecular compounds which are "free" in the macromolecular network structure and have low intermolecular attraction. With the increase of extraction pressure and time, hydrocarbon and non-hydrocarbon small molecular compounds which are "embedded" and have strong molecular force are dissolved out.

(3) Simulate the formation temperature and pressure, carry out the single factor experiment of CO₂ and water-bearing coal samples, and test and analyze the mineral composition and relative content of elements of raw coal samples and coal samples after reaction. The migration of elements or combination of elements is closely related to the occurrence of minerals, and the elements related to carbonate minerals, such as Ca, Mn, Cu, Zn and Sr, have great mobility at the initial stage of the reaction. Fe and S elements related to sulfide and sulfate minerals have higher mobility in the middle of the reaction. Elements such as V, Ti, Al and Si existing in silicate minerals show great migration in the later stage of the reaction; Minerals such as kaolinite, illite, Shi Ying and potash feldspar in three coal samples undergo mineral transformation in the reaction process under different corrosion pressures, and their contents change obviously in the middle of the reaction. Carbonate minerals are rapidly dissolved in the initial stage of the reaction, and CO₂ pressure has a great influence on the reaction, which plays a leading role in the reconstruction of coal pore and fissure structure. In the middle stage of pyrite dissolution reaction, a weak oxidation-reduction reaction occurred, and the content of pyrite decreased.

(4) Based on the experiment of extraction of liquid CO₂ and physical and chemical reaction of dissolved coal, with the help of scanning electron microscope, CT scanning and low-temperature N₂ adsorption, the surface cracks, internal pore structure distribution and connectivity before and after the physical and chemical reaction of liquid CO₂ with coal were tested and compared. After the coal sample is extracted by liquid CO₂, the coal particle size distribution of the extracted residual coal is relatively uniform, and the surface morphology becomes smooth obviously. Partial dissolution of minerals makes the pores and micro-cracks further expand and connect in a small range, and a large number of dissolved pores are formed on the surface of some minerals after reaction. After anthracite, bituminous coal and lignite are extracted by liquid CO₂, the number of micropores decreases and the content of transition pores and mesopores increases. Liquid CO₂ extraction can enlarge micropores. Under the corrosion of CO₂-H₂O, the number of micropores, transition pores and mesopores of the three coal samples increased obviously, and the average pore diameter increased. After the three kinds of coal samples were extracted by liquid CO₂, the BET specific surface area gradually decreased with the increase of extraction pressure, and the change of micropore specific surface area played a leading role in the whole pore specific surface area. The specific surface areas of transition pore and mesopore had no significant change before and after extraction. After the organic matter in coal was extracted, micropores were enlarged and connected to form larger pores, which led to the decrease of total specific surface area of coal samples under the effect of reaming.

(5) The gas adsorption characteristics of coal samples before and after the action of liquid CO₂ are compared and analyzed. Based on the test results of coal micro-pore structure before and after the extraction and dissolution of liquid CO₂, the influence of coal pore structure reconstruction on gas adsorption characteristics is analyzed. The adsorption of CO₂ gas molecules by coal samples on coal surface belongs to multi-layer adsorption; After three kinds of coal samples were extracted by liquid CO₂, the pore specific surface area decreased, the adsorption capacity decreased with the increase of extraction pressure, and the adsorption capacity of anthracite coal decreased more than that of bituminous coal and lignite. After CO₂ corrosion at different pressures, the adsorption capacity gradually increases with the corrosion pressure, and the adsorption capacity of bituminous coal increases more than that of anthracite and lignite. After corrosion, bituminous coal is suitable for CO₂ geological storage.

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