我国是世界煤炭第一生产大国，众多未经开发的地下采空区域资源存在利用效率偏低的现象。特别是在当前我国积极响应“双碳”政策的形势下，对于CO₂地质储存技术的发展尤为迫切。煤矿废弃采空区所蕴藏的巨大潜力，使其成为非常规CO₂储存地质体的有力候选，其CO₂储存容量的精准评估意义重大。然而，在CO₂注入所导致的溶解、矿化等固碳作用机理及多重因素影响下煤岩体孔隙结构的变化，以及随之而来的CO₂封存安全性问题，仍是一个令人关注的研究领域。为此，本研究选取陕西黄陵矿区某关闭采空区作为案例，系统探究了CO₂与水和煤岩体反应的化学固碳机制及其安全性问题，并创新提出了防沉阻漏的注浆协同充填技术及CO₂化学封存容量的估算模型。本研究取得的主要成果如下：

搭建了关闭采空区CO₂化学反应实验平台，可以实现高温高压反应装置-离子色谱系统联用，有效观测了CO₂-H₂O-煤岩体相互作用的整个水化学过程。通过开展关闭采空区化学模拟实验，从煤岩矿物组分的变化特征、水化学变化特征及反应过程中的化学动力学分析等不同角度，对煤矿采空区CO₂封存过程中破碎煤岩体的固碳效应进行了深入研究，进一步的分析揭示了采空区煤岩体的孔隙结构、有机结构变化及其分形特征，提出了一个表征多因素影响下的煤岩体孔隙演变的概念模型。

在整个CO₂-H₂O-煤岩体相互作用过程中起固碳作用的主要金属阳离子（Mg²⁺和Ca²⁺）的浓度趋势首先迅速增加后渐趋平稳直至达到新的化学平衡状态。Ca²⁺的浓度变化最为显著，不同压力条件下初始浓度为124.17ppm、164.38ppm、194.71ppm，而监测的最终浓度为293.92ppm、294.55ppm、301.95ppm。在此过程中，水化学环境也发生了变化，由于CO₂的溶解和煤岩体相互作用，pH和TDS（溶解性固体总量）也呈现出随反应时间逐渐变缓的趋势。同时观察到作用前后矿物组分含量发生了变化，主要是次生矿物高岭石的增长和方解石的溶解，煤样中Ca元素和氧化物含量分别减少76.52%和79.9%，岩样中Ca、Mg元素含量分别降低了20.4%和7.1%，这凸显了在CO₂注入初期对矿物溶解-沉淀动力学的显著影响。

通过扫描电镜、压汞测试和傅里叶红外光谱相关实验对比分析，发现CO₂-H₂O-煤岩体相互作用后破碎煤岩体的孔隙体积与孔隙率均分别增加了10.8%、4.5%和1.41%、5.59%。样品表面矿物颗粒分布和矿物簇的溶蚀，同时表面的原有裂隙扩展，并伴随新的表面裂隙的生成等现象，说明了反应过程中无机矿物组分对孔裂隙发育的影响。煤样的有机结构特征在反应前后发生了变化，在最大反应压力条件下矿物吸收峰、芳香族和脂肪族结构的含量分别减少71.97%、70.97%和83.23%，反应过后含氧官能团含量增长了216.38%，导致了煤体表面的吸附特性发生了改变。

基于溶解和矿化两种形态，构建了关闭煤矿采空区CO₂化学封存储量的估算模型，并对案例关闭煤矿采空区进行了CO₂化学封存潜力评估。由于采空区应力分布的不均匀性，在深部关闭煤矿采空区压实区和非压实区及覆岩裂隙中CO₂将分别以超临界态和气态的形式存在。基于此，提出了根据CO₂不同区域的赋存相态的差异计算CO₂储量的方法，得到了案例关闭煤矿采空区的CO₂溶解态的理论储量为3.9×10⁵t，通过矿化作用固定的CO₂理论储量为6.42×10⁵t，整个采空区的化学封存潜力为1.03×10⁶t。针对化学固碳过程中可能出现的封存安全问题，提出了顶部注浆-底部充填技术构想。

本研究增强了对采空区作为CO₂地质储层的认识，通过建立科学的估算模型和提出针对性的技术方案，为安全地利用煤矿关闭采空区进行CO₂地质储存提供了重要的理论基础和技术支撑。

China is the world 's largest producer of coal, and many untapped underground goafs have low utilization efficiency of resources. Especially in the current situation of China 's active response to the ' double carbon ' policy, the development of CO₂ geological storage technology is particularly urgent. The huge potential of the abandoned goaf in the coal mine makes it a strong candidate for unconventional CO₂ storage geological bodies, and the accurate evaluation of its CO₂ storage capacity is of great significance. However, the mechanism of carbon fixation such as dissolution and mineralization caused by CO₂ injection and the change of pore structure of coal and rock mass under the influence of multiple factors, as well as the safety of CO₂ storage, are still a research field of concern. Therefore, this study selected a closed goaf in Huangling mining area of Shaanxi Province as a case to systematically explore the chemical carbon fixation mechanism and safety problems of CO₂ reaction with water and coal rock mass, and innovatively proposed a grouting collaborative filling technology to prevent subsidence and leakage and an estimation model of CO₂ chemical storage capacity. The main results of this study are as follows :

The experimental platform of CO₂ chemical reaction in closed goaf was built, which can realize the combination of high temperature and high pressure reaction device and ion chromatography system, and effectively observe the whole water chemical process of CO₂-H₂O-coal rock interaction. Through the chemical simulation experiment of closed goaf, the carbon sequestration effect of broken coal and rock mass in the process of CO₂ storage in coal mine goaf was studied from different angles, such as the variation characteristics of coal and rock mineral composition, the characteristics of water chemical change and the chemical kinetic analysis in the reaction process. Further analysis revealed the pore fracture structure, organic structure change and fractal characteristics of coal and rock mass in goaf, and put forward a conceptual model to characterize the pore evolution of coal and rock mass under the influence of multiple factors.

The concentration trend of the main metal cations (Mg²⁺ and Ca²⁺) that play a role in carbon sequestration during the whole CO₂-H₂O-coal-rock interaction process first increases rapidly and then gradually stabilizes until it reaches a new chemical equilibrium state. The concentration of Ca²⁺ changes most significantly. The initial concentration under different pressure conditions is 124.17ppm, 164.38ppm, 194.71ppm, while the final concentration monitored is 293.92ppm, 294.55ppm, 301.95ppm. During this process, the hydrochemical environment also changed. Due to the dissolution of CO₂ and the interaction between coal and rock, pH and TDS ( Total Dissolved Solids ) also showed a trend of gradually slowing down with the reaction time. At the same time, it was observed that the content of mineral components changed before and after the action, mainly the growth of secondary mineral kaolinite and the dissolution of calcite. The contents of Ca and oxides in coal samples decreased by 76.52 % and 79.9 %, respectively, and the contents of Ca and Mg in rock samples decreased by 20.4 % and 7.1 %, respectively, which highlighted the significant effect of CO₂ injection on the dissolution-precipitation kinetics of minerals at the initial stage of CO₂ injection.

Through the comparative analysis of scanning electron microscopy, mercury intrusion test and Fourier transform infrared spectroscopy, it was found that the pore volume and porosity of broken coal and rock mass increased by 10.8%, 4.5% and 1.41%, 5.59% respectively after the interaction of CO₂-H₂O-coal and rock mass. The distribution of mineral particles and the dissolution of mineral clusters on the surface of the sample, as well as the expansion of the original cracks on the surface, accompanied by the formation of new surface cracks, illustrate the influence of inorganic mineral components on the development of pores and cracks in the reaction process. The organic structure characteristics of coal samples changed before and after the reaction. Under the condition of maximum reaction pressure, the content of mineral absorption peak, aromatic and aliphatic structure decreased by 71.97 %, 70.97 % and 83.23 % respectively. After the reaction, the content of oxygen-containing functional groups increased by 216.38 %, which led to the change of adsorption characteristics on the surface of coal.

Based on the two forms of dissolution and mineralization, an estimation model of CO₂ chemical storage reserves in closed coal mine goafs was constructed, and the potential of CO₂ chemical storage in closed coal mine goafs was evaluated. Due to the non-uniformity of the stress distribution in the goaf, CO₂ will exist in the form of supercritical and gaseous state in the compacted and non-compacted areas of the deep closed coal mine goaf and in the overlying rock fissures, respectively. Based on this, we propose a method to calculate CO₂ reserves based on the difference in the occurrence phase of CO₂ in different regions. The theoretical reserves of CO₂ dissolved state in the closed coal mine goaf are 3.9×10⁵t. The theoretical reserves of CO₂ fixed by mineralization are 6.42×10⁵t, and the chemical storage potential of the entire goaf is 1.03×10⁶t. Aiming at the possible storage safety problems in the process of chemical carbon sequestration, the idea of top grouting-bottom filling technology is put forward.

This study enhances the understanding of the goaf as a CO₂ geological reservoir. By establishing a scientific estimation model and proposing targeted technical solutions, it provides an important theoretical basis and technical support for the safe use of coal mines to close goafs for CO₂ geological storage.

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