CO<sub>2</sub>封存过程煤分子结构演化规律的光谱研究

doi:10.3964/j.issn.1000-0593(2025)06-1791-10

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摘要：为研究CO₂封存于不可开采煤层后对煤的孔隙结构和分子结构造成的影响，采用低温液氮吸附、低温CO₂吸附、傅里叶红外光谱（FTIR）、X射线衍射（XRD）和拉曼光谱（Raman）实验，探究了煤吸附不同压力CO₂后的孔隙结构、表面官能团、微晶结构及大分子结构的演变规律。结果表明：煤吸附CO₂后微孔的累积比表面积与累积孔体积呈减小趋势，介孔、大孔的累积比表面积与累积孔体积呈增大趋势，微孔的平均孔径整体增大，孔隙结构中微孔向介孔和大孔的方向转变。同时煤芳香烃总体含量减少，芳香层间距d₀₀₂增加，微晶堆积高度L_c、晶体堆叠平均层数n、芳香度f_a减小，含氧官能团与羟基含量升高，—CH₂—含量减小，—CH₃含量小幅度升高，CH₃/CH₂值升高，说明煤吸附CO₂后大芳香结构向小芳香结构发展，芳环上的支链逐渐变短且增多，芳香微晶结构被破坏，芳香层堆积的更加松散，导致晶体化程度减小。随着煤吸附CO₂压力的升高，D峰和G峰的峰位差d_（G-D）减小，强度比I_D/I_G、D峰半峰宽（FWHM-D）、G峰半峰宽（FWHM-G）与W_D/W_G值增加，代表缺陷结构的峰面积比A_S/A_total、A_S/A_D、A_D/A_G、A_(GR+VL+VR)/A_D值也均增大，这说明煤吸附不同压力的CO₂后，煤中大分子结构发生胀裂，石墨结构占比减少且杂质结构占比增加，煤结构整体上朝无序化增强的方向发展。研究结果可为CO₂地质封存技术提供理论支撑。

关键词：碳封存；孔隙结构；大分子结构；傅里叶红外光谱；X射线衍射；拉曼光谱

Abstract：This study examines the impact of CO₂ storage on the pore and molecular structures of coal in unminable coal seams. Low-temperature liquid nitrogen adsorption, low-temperature CO₂ adsorption, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and Raman spectroscopy (Raman) experiments were employed. The evolution rules of pore structure, surface functional groups, macromolecular structure, and microcrystalline structure of coal after CO₂ adsorption at different pressures were investigated. The results showed that, after CO₂ adsorption, the cumulative specific surface area and cumulative pore volume of micropores decreased. In contrast, the cumulative specific surface area and cumulative pore volume of mesopores and macropores increased. The average pore size of micropores increases overall, and the micropores in the pore structure transition to a direction that favors mesopores and macropores. At the same time, the total content of aromatic hydrocarbons in coal decreased, the aromatic layer spacing d₀₀₂ increased, the microcrystalline stacking height L_c, the average number of crystal stacking layers n, the aromaticity f_a decreased, the content of oxygen-containing functional groups and hydroxyl groups increased, the content of —CH₂— decreased, the content of —CH₃ increased slightly, and the CH₃/CH₂ value increased. It shows that after the adsorption of CO₂ by coal, the large aromatic structure developed to the small aromatic structure, the branched chain on the aromatic ring gradually became shorter and increased, the aromatic microcrystalline structure was destroyed, and the aromatic layer was more loosely accumulated, resulting in a decrease in the degree of crystallization. With the increase of CO₂ adsorption pressure of coal, the peak position difference d_(G-D) between D peak and G peak decreases, the intensity ratio I_D/I_G, half peak width of D peak (FWHM-D), half peak width of G peak (FWHM-G) and W_D/W_G values increased, and the peak area ratio A_S/A_total, A_S/A_D, A_D/A_G, A_(GR+VL+VR)/A_D values representing the defect structure also increased, it indicates that after coal adsorbed CO₂ under different pressure, the macromolecular structure in coal expanded and cracked, the proportion of graphite structure decreased and the proportion of impurity structure increased. The coal structure as a whole develops in the direction of increasing disorder. The research results provide a theoretical basis for the influence of geological storage of CO₂ on the microscopic properties of coal. The research results provide a theoretical foundation for understanding the impact of geological CO₂ storage.

Key words：Carbon sequestration; Pore structure; Macromolecular structure; FTIR; XRD; Raman

收稿日期: 2024-07-15 修订日期: 2025-01-08

中图分类号:

X936

基金资助: 国家自然科学基金面上项目(52074147)，2024年辽宁省教育厅基本科研项目（创新发展项目）(LJ242410147082)资助

作者简介: 高飞，女，1984年生，辽宁工程技术大学安全科学与工程学院副教授 e-mail: gfgf2001@163.com

引用本文:

高飞，林菀，贾喆，白企慧，刘婧，王一凡，李伟英. CO₂封存过程煤分子结构演化规律的光谱研究[J]. 光谱学与光谱分析, 2025, 45(06): 1791-1800.
GAO Fei, LIN Wan, JIA Zhe, BAI Qi-hui, LIU Jing, WANG Yi-fan, LI Wei-ying. Spectroscopic Study on the Evolution of Coal Molecular Structure During CO₂ Storage. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(06): 1791-1800.

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[1] Weniger P, Francu J, Hemza P, et al. International Journal of Coal Geology, 2012, 93: 23.
[2] Kang J H, Wan R, Zhou F B, et al. Chemical Engineering Journal, 2020, 388: 123449.
[3] Yin T T, Liu D M, Cai Y D, et al. International Journal of Coal Geology, 2020, 220: 103415.
[4] Wang X L, Liu H H, Zhang D M, et al. Fuel, 2022, 321: 124155.
[5] LIN Bai-quan, ZHOU Shi-ning（林柏泉, 周世宁）. Journal of China University of Mining and Technology（中国矿业大学学报）, 1986, (3): 9.
[6] LI Xiang-chun, NIE Bai-sheng, HE Xue-qiu, et al（李祥春, 聂百胜, 何学秋, 等）. Journal of China Coal Society（煤炭学报）, 2011, 36(12): 2035.
[7] CHEN Xiao-zhen, LI Mei-fen, ZENG Fan-gui, et al（陈小珍, 李美芬, 曾凡桂, 等）. Journal of China Coal Society（煤炭学报）, 2022, 47(7): 2678.
[8] Chen M, Hosking L J, Sandford R J, et al. International Journal of Coal Geology, 2019, 205: 115.
[9] Li W, Liu Z D, Su E L, et al. Energy & Fuels, 2018, 33(1): 503.
[10] Song Y, Zou Q L, Su E L, et al. Fuel, 2020, 279: 118493.
[11] Wang X L, Zhang D M, Geng J B, et al. Journal of Natural Gas Science and Engineering, 2022, 108: 104808.
[12] Jiang R X, Yu H G. International Journal of Coal Geology, 2019, 202: 1.
[13] Wang K, Du F, Wang G D. Journal of Natural Gas Science and Engineering, 2017, 45: 358.
[14] Li J X, Pan J N, Wang X L, et al. International Journal of Coal Geology, 2023, 265: 104169.
[15] Wang K, Pan J N, Wang E Y, et al. Chemical Engineering Journal, 2020, 401: 126071.
[16] Thitame P V, Shukla S R. Chemical Engineering Communications, 2016, 203(6): 791.
[17] Tian B, Qiao Y Y, Tian Y Y, et al. Fuel Processing Technology, 2016, 154: 210.
[18] Li X J, Hayashi J, Li C Z, et al. Fuel, 2006, 85(12-13): 1700.
[19] Wang Y, Alsmeyer D C, McCreery R L. Chemistry of Materials, 1990, 2(5): 557.
[20] Ulyanova E V, Molchanov A N, Prokhorov I Y, et al. International Journal of Coal Geology, 2014, 121: 37.
[21] Potgieter-Vermaak S, Maledi N, Wagner N, et al. Journal of Raman Spectroscopy, 2011, 42(2): 123.
[22] Xu J, Tang H, Su S, et al. Applied Energy, 2018, 212: 46.
[23] Seong H J, Boehman A L. Energy & Fuels, 2013, 27(3): 1613.
[24] Jiang J Y, Yang W H, Cheng Y P, et al. Fuel, 2019, 239: 559.
[25] Henry D G, Jarvis I, Gillmore G, et al. International Journal of Coal Geology, 2019, 203: 87.
[26] Morga R, Jelonek I, Kruszewska K. International Journal of Coal Geology, 2014, (134-135): 17.
[27] YANG He, XIE Zhou-wei, SHANG Yan, et al(杨赫, 谢周伟, 尚妍, 等). Journal of Fuel Chemistry and Technology(燃料化学学报), 2021, 49(1): 1667.
[28] Chen X Z, Li M F, Zeng F G. Fuel Processing Technology, 2022, 228: 107162.
[29] Song Y, Jiang B, Qu M J. Fuel, 2019, 236: 1432.
[30] XU Yan-mei, PAN Zhi-yan, HU Hao-quan(徐艳梅, 潘志彦, 胡浩权). Journal of Fuel Chemistry and Technology(燃料化学学报), 2021, 49(11): 1656.