我国是世界煤炭第一生产大国，地下煤炭资源经长壁法开采、自然垮落管理顶板后形成大量的采动空间（采空区），这些地下采动空间资源开发少、利用率低。同时，在“双碳”背景下，我国CO₂地质储存技术需大力发展，煤矿老采空区作为一种潜在的非常规CO₂储存地质体，对其CO₂储存潜力评估具有非常重要的意义，而储层CO₂储存量估算是其关键部分。为了准确估算煤矿老采空区CO₂储存量，此课题以陕西黄陵某矿老采空区为研究对象，以游离态和吸附态两种储存机制为出发点，对老采空区分别以这两种物理储存机制CO₂储存量开展一系列实验研究。

针对案例老采空区裂隙空间CO₂储存可行性，搭建试验工作面地层二维物理相似模型，明确了老采空区进行CO₂储存的裂隙圈闭结构，根据盖层厚度及渗透特性分析案例老采空区CO₂储存可行性。发现采空区发育稳定后，盖层具有厚度大和渗透性低的特点；盖层下“连通裂隙”、“封闭裂隙”和“微小裂隙”面积分别占总面积的85.5%、8.5%和6%。表明案例老采空区内至少有85.5%的裂隙空间可储存CO₂，说明其储存CO₂可行性较好。

基于物理相似模拟试验结果，提取连通裂隙网络开展CO₂试注数值模拟试验，构建了CO₂注入有效性模型，揭示了CO₂注入过程中老采空区CO₂/CH₄运移扩散规律。发现CO₂在注入后首先快速向连通裂隙底部运移，抵达底部后开始水平扩散，充满整个连通裂隙底部后才开始缓慢的纵向扩散，但注入完成后CO₂并不能完全充满连通裂隙，当注入完成时，注入CO₂体积仅占总连通裂隙体积的59%。该模型能准确地量化老采空区注入有效性对游离态CO₂储存量的影响。

提出井下拍照+取样筛分的老采空区采落遗煤全粒径统计方法，明确了老采空区采落遗煤粒径分布特征。统计样品中煤粒径级配良好，粒径范围在0~130mm之间，其中不同粒径颗粒质量占比差别较大，70%质量占比的粒径大于20.19mm。考虑到老采空区压实区采落遗煤再破碎情况，开展模拟实际压实作用下煤颗粒的破碎试验，发现混合粒径（现场采样）压缩后试样的相对破碎率为29%，压缩后新增的0~5mm范围粒径增加较多。为构建煤矿老采空区全粒径段煤体吸附态储存CO₂估算模型奠定了基础。

针对老采空区内采落遗煤CO₂吸附储存量估算问题，开展煤CO₂吸附-解吸实验，明确了采落遗煤粒径、环境温度和注气压力对老采空区采落遗煤以吸附态储存CO₂量的影响，发现煤中CO₂常压吸附量与先加压后解吸至常压CO₂存留量相对误差小于3%，煤粒径和环境温度对老采空区CO₂吸附储存量影响较大，而注气压力影响较小。为构建温度、注气压力和粒径影响下遗煤以吸附态储存CO₂估算模型奠定了基础。

基于CO₂地质储存金字塔理论和体积守恒理论，构建了老采空区游离态和吸附态CO₂储存量估算模型，并对案例老空区CO₂物理储存量进行估算。得出案例老采空区常温常压游离态CO₂理论储存量为9423t，吸附态CO₂理论储存量为10393t；案例老采空区常温常压游离态CO₂有效储存量为4035t，吸附态CO₂有效储存量为7228t；案例井田待全部开采后老采空区游离态CO₂有效储存量为91221t，吸附态CO₂有效储存量为164525t。实现了老采空区CO₂物理储存量的准确计算。

China is the world's largest coal producer, and the underground coal resources have formed a large amount of mining space (goafs) after long-wall mining and natural collapse management of the roof, and these underground mining space resources are less developed and less utilized. At the same time, in the context of "double carbon", China's CO₂ geological storage technology needs to be vigorously developed. As a potential unconventional CO₂ storage geological body, it is very important to evaluate the CO₂ storage potential of old goaf, and the estimation of reservoir CO₂ storage capacity is a key part. To accurately estimate the CO₂ storage capacity of old goaf, this project takes an old goaf in Huangling, Shaanxi Province as the research object, and carries out a series of experimental studies on the CO₂ storage capacity of these two storage mechanisms, respectively, taking the free and adsorption state as the starting point.

For the feasibility of CO₂ storage in the fracture space of the old goaf, a two-dimensional physical similarity model of the stratum at the test working face was built to clarify the fracture trap structure of the old goaf for CO₂ storage. The feasibility of CO₂ storage in the old goaf was analyzed according to the thickness and permeability of the cover layer. The area of "connected fissures", "closed fissures" and "micro fissures" under the cover accounted for 85.5%, 8.5% and 6% of the total area, respectively. It shows that at least 85.5% of the fissures space in the old goaf can store CO₂, which indicates that the feasibility of storing CO₂ is good.

Based on the results of physically similar simulation tests, a numerical simulation test of CO₂ trial injection was conducted by extracting the connected fracture network, and a CO₂ injection effectiveness model was constructed to reveal the CO₂/CH₄ transport and diffusion law in the old goaf during CO₂ injection. It is found that CO₂ first moves rapidly to the bottom of the connected fracture after injection, and then starts to diffuse horizontally after reaching the bottom, and only starts to diffuse slowly longitudinally after filling the whole bottom of the connected fracture, but CO₂ does not completely fill the connected fracture after injection is completed, and when injection is completed, the volume of injected CO₂ only accounts for 59% of the total connected fracture volume. This model can accurately quantify the effect of injection effectiveness on the free CO₂ storage volume in the old goaf.

The whole particle size statistics method of downhole photography + sampling and sieving in the old goaf is proposed, and the particle size distribution characteristics of the old goaf are clarified. Considering the re-crushing of the coal mined in the compaction area of the old goaf, the crushing test was carried out to simulate the crushing of coal particles under the actual compaction, and it was found that the relative crushing rate of the specimen after the compression of the mixed particle size (field sampling) was 29%. The relative fragmentation rate of the mixed grain size (field sampling) specimens after compression was found to be 29%, and the new particle size in the range of 0~5mm increased more after compression. It is found that the relative fragmentation rate is 29%, and the increase of 0~5mm particle size is more.

In order to estimate the amount of CO₂ adsorption and storage in the old goaf, CO₂ adsorption-desorption experiments were conducted to clarify the effects of coal particle size, ambient temperature and gas injection pressure on the amount of CO₂ storage in the old goaf in the adsorption state, and it was found that the relative error of CO₂ adsorption in coal at atmospheric pressure and the amount of CO₂ stored in coal after desorption to atmospheric pressure is less than 3%. The influence of coal particle size and ambient temperature on the amount of CO₂ adsorbed and stored in the old goaf is larger, while the influence of gas injection pressure is smaller. It is the basis for the estimation model of CO₂ storage by adsorption of legacy coal under the influence of temperature, gas injection pressure and particle size.

Based on the CO₂ geological storage pyramid theory and volume conservation theory, a model was constructed to estimate the storage capacity of free and adsorbed CO₂ in the old goaf, and the CO₂ storage capacity in the old goaf of the case was estimated. The theoretical storage capacity of free CO₂ in the old goaf is 9423t and the theoretical storage capacity of adsorbed CO₂ is 10,393t; the effective storage capacity of free CO₂ in the old goaf is 4035t and the effective storage capacity of adsorbed CO₂ is 7228t; the effective storage capacity of free CO₂ in the old goaf is 91,221t and the effective storage capacity of adsorbed CO₂ in the old goaf is 91,221t after all the well in the case field are mined. The physical storage capacity of CO₂ in the old goaf has been accurately calculated.

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