分子视角下煤对O2/CH4混合气体的竞争吸附研究

doi:10.16265/j.cnki.issn1003-3033.2025.01.0485

摘要/Abstract

摘要：

为深刻理解煤表面对O₂/CH₄混合气体的竞争吸附特性,基于巨正则蒙特卡罗法(GCMC)分析煤表面孔隙分布和化学结构;采用分子模拟研究不同浓度、不同压力、不同温度下O₂/CH₄混合气体竞争吸附过程中的吸附量和吸附热变化特征,并通过吸附选择性揭示O₂/CH₄混合气体在煤表面的竞争吸附机制。结果表明: O₂与CH₄浓度比为7/3时,二者的等温吸附曲线接近;不同条件下O₂与CH₄的积分吸附热相差不大,O₂约19.5~20.0 J/g,CH₄约24.0~24.8 J/g;当O₂与CH₄浓度比为7/3~2/8时,O₂的积分吸附热大于CH₄;随着温度升高,O₂与CH₄的吸附量均减少,且O₂对CH₄的吸附选择性增大,气体压力对竞争吸附的影响减弱;低气体压力条件下,CH₄比O₂吸附速率更快,当混合气体总压增加时,CH₄比O₂先达到饱和吸附;随着混合气体中O₂浓度的增加,O₂对CH₄的吸附选择性呈现降低趋势,但CH₄的吸附竞争力始终优先于O₂。

关键词: 煤, O₂/CH₄混合气体, 竞争吸附, 吸附热, 分子模拟

Abstract:

To deeply understand the competitive adsorption characteristics of O₂/CH₄ gas mixtures on the coal surface, the pore distribution and chemical structure of the coal surface were analyzed using the Grand Canonical Monte Carlo(GCMC) method. Molecular simulation was used to investigate adsorption capacity and heat variations during the competitive adsorption of O₂/CH₄ gas mixtures under varying concentrations, pressures, and temperatures. Moreover, the competitive adsorption mechanism of O₂/CH₄ gas mixtures on the coal surface was revealed by adsorption selectivity. The results indicated that the isothermal adsorption curves were identical when the concentration ratio of O₂ to CH₄ was 7/3. The integrated adsorption heat under different conditions was approximately 19.5-20.0 J/g for O₂ and 24.0-24.8 J/g for CH₄. When the concentration ratio of O₂ to CH₄ ranged between 7/3 and 2/8, the integrated adsorption heat of O₂ was higher than that of CH₄. The increased temperature decreased the adsorption capacity of both gases but increased the adsorption selectivity of O₂ to CH₄. Moreover, the effect of gas pressure on competitive adsorption weakened with pressure increase. CH₄ adsorbed faster than O₂under low gas pressures, and CH₄ reached saturation adsorption earlier than O₂when the total pressure increased. When the O₂ concentration in the gas mixtures increased, the adsorption selectivity of O₂ for CH₄ decreased. However, CH₄ consistently showed higher adsorption competitiveness than O₂.

Key words: coal, O₂/CH₄ gas mixtures, competitive adsorption, adsorption heat, molecular simulation

中图分类号:

X936

贺姝静, 彭程阳, 康建宏, 张耕显. 分子视角下煤对O₂/CH₄混合气体的竞争吸附研究[J]. 中国安全科学学报, 2025, 35(1): 137-145.

HE Shujing, PENG Chengyang, KANG Jianhong, ZHANG Gengxian. Study on competitive adsorption of O₂/CH₄ mixed gas by coal from molecular perspective[J]. China Safety Science Journal, 2025, 35(1): 137-145.

图/表 11

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表1

O2/CH4混合气体竞争吸附的Langmuir模型拟合参数

$φ O 2$	p/MPa	$n O 2$ / (mmol·g^-1)	$n C H 4$ / (mmol·g^-1)	$b O 2$ / MPa	$b C H 4$ / MPa	$ε O 2$ / (J·g^-1)	$ε C H 4$ / (J·g^-1)	R²
0.1	0~10	0.155 47	1.614 21	0.275 07	0.798 56	19.690 3	24.778 8	0.999 68
0.2	0~10	0.232 28	1.477 19	0.191 59	0.804 22	19.785 3	24.098 4	0.999 74
0.3	0~10	0.353 45	1.452 39	0.185 14	0.827 03	19.908 1	24.254 2	0.999 87
0.4	0~10	0.486 36	1.308 22	0.122 18	0.843 09	19.989 7	24.087 6	0.999 36
0.5	0~10	0.564 87	1.239 57	0.099 36	0.877 93	19.983 7	24.459 8	0.999 33
0.6	0~10	0.663 54	1.060 65	0.089 94	0.935 41	19.605 0	24.370 0	0.999 94
0.7	0~10	0.978 43	0.966 40	0.071 59	0.984 22	19.877 3	24.404 6	0.999 89
0.8	0~10	1.222 20	0.595 67	0.068 76	0.997 85	19.909 8	24.039 7	0.999 87
0.9	0~10	1.399 78	0.398 41	0.023 58	1.122 94	19.756 7	24.778 6	0.999 51

表1

图9

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参考文献 20

[1]	袁亮. 煤炭工业碳中和发展战略构想[J]. 中国工程科学, 2023, 25(5): 103-110. doi: 10.15302/J-SSCAE-2023.05.009
	YUAN Liang. Strategic Conception of carbon neutralization in coal industry[J]. China Academic Journal Electronic Publishing House, 2023, 25(5): 103-110.
[2]	程远平, 付建华, 俞启香. 中国煤矿瓦斯抽采技术的发展[J]. 采矿与安全工程学报, 2009, 26(2): 127-139.
	CHENG Yuanping, FU Jianhua, YU Qixiang. Development of gas extraction technology in coal mines of China[J]. Journal of Mining &Safety Engineering, 2009, 26(2):127-139.
[3]	李沛, 马东民, 张辉, 等. 高、低阶煤润湿性对甲烷吸附/解吸的影响[J]. 煤田地质与勘探, 2016, 44(5): 80-85.
	LI Pei, MA Dongmin, ZHANG Hui, et al. Influence of high and low rank coal wettability and methane adsorption / desorption characteristics[J]. Coal Geology & Exploration, 2016, 44(5):80-85.
[4]	田富超, 贾东旭, 陈明义, 等. 采空区复合灾害环境下含瓦斯煤自燃特征研究进展[J]. 煤炭学报, 2024, 49(6): 2711-2727.
	TIAN Fuchao, JIA Dongxu, CHEN Mingyi, et al. Research progress of spontaneous combustion of coal containing gas under the compound disaster environment in the goaf[J]. Journal of China Coal Society, 2024, 49(6): 2711-2727.
[5]	ASKALANY A A, SAHA B B. Derivation of isosteric heat of adsorption for non-ideal gases[J]. International Journal of Heat and Mass Transfer, 2015, 89: 186-192.
[6]	XU Tang, RIPEPI N, STADIE N P, et al. Thermodynamic analysis of high pressure methane adsorption in Longmaxi shale[J]. Fuel, 2017, 193: 411-418.
[7]	刘志祥, 冯增朝. 煤体对瓦斯吸附热的理论研究[J]. 煤炭学报, 2012, 37(4):647-653.
	LIU Zhixiang, FENG Zengchao. Theoretical study on adsorption heat of methane in coal[J]. Journal of China Coal Society, 2012, 37(4): 647-653.
[8]	KLOUTSE A F, ZACHARIAL R, COSSEMENT D, et al. Isosteric heat of hydrogen adsorption on MOFs: comparison between adsorption calorimetry, sorption isosteric method, and analytical models[J]. Applied Physics A, 2015, 121(4): 1417-1424.
[9]	申晓静, 岳基伟, 梁跃辉, 等. 高温高压氛围下煤体吸附瓦斯特性研究[J]. 中国安全科学学报, 2024, 34(2):176-184. doi: 10.16265/j.cnki.issn1003-3033.2024.02.1453
	SHEN Xiaojing, YUE Jiwei, LIANG Yuehui, et al. Study on gas adsorption characteristics of coal under high temperature and high pressure atmosphere[J]. China Safety Science Journal, 2024, 34(2):176-184. doi: 10.16265/j.cnki.issn1003-3033.2024.02.1453
[10]	娄和壮, 贾廷贵. 惰性气氛对煤自燃过程的竞争吸附差异性研究[J]. 中国安全科学学报, 2020, 30(4):60-67. doi: 10.16265/j.cnki.issn1003-3033.2020.04.010
	LOU Hezhuang, JIA Tinggui. Competitive adsorption differences during coal spontaneous combustion process in noble gas Atmosphere[J]. China Safety Science Journal, 2020, 30(4):60-67. doi: 10.16265/j.cnki.issn1003-3033.2020.04.010
[11]	仇悦, 龙航, 白杨, 等. 温度效应下煤体吸附瓦斯热力学及动力学特征[J]. 中国安全科学学报, 2023, 33(7):147-155. doi: 10.16265/j.cnki.issn1003-3033.2023.07.1934
	QIU Yue, LONG Hang, BAI Yang, et al. Thermodynamicand kinetic characteristics of gas adsorption by coal under temperature effect[J]. China Safety Science Journal, 2023, 33(7):147-155. doi: 10.16265/j.cnki.issn1003-3033.2023.07.1934
[12]	DANG Yong, ZHAO Lianming, LU Xiaoqing, et al. Molecular simulation of CO₂/CH₄ adsorption in brown coal: effect of oxygen-, nitrogen-, and sulfur-containing functional groups[J]. Applied Surface Science, 2017, 423: 33-42.
[13]	王宝俊, 凌丽霞, 赵清艳, 等. 气体与煤表面吸附作用的量子化学研究[J]. 化工学报, 2009, 60(4): 196-201.
	WANG Baojun, LING Lixia, ZHAO Qingyan, et al. Quantum chemistry study on adsorption of gases on coal surface[J]. CIESC Journal, 2009, 60(4): 196-201.
[14]	YOU Jing, TIAN Li, ZHANG Chao, et al. Adsorption behavior of carbon dioxide and methane in bituminous coal: a molecular simulation study[J]. Chinese Journal of Chemical Engineering, 2016, 24(9): 1275-1282.
[15]	林柏泉, 何学秋, 王佳新. 气体吸附性与煤和瓦斯突出的机理[J]. 江苏煤炭, 1990(2): 11-15.
	LIN Baiquan, HE Xueqiu, WANG Jiaxin. Gas adsorption and the mechanism of coal and gas protrusion[J]. Jiangsu Coal, 1990 (2): 11-15.
[16]	JIA Chengxia, YOU Chun, PAN Gang. Effect of temperature on the sorption and desorption of perfluorooctane sulfonate on humic acid[J]. Journal of Environmental Sciences, 2010, 22(3): 355-361. pmid: 20614776
[17]	杨雪莹, 朱一民, 李艳军, 等. 捕收剂DXY-1在石英表面的捕收性能及机理研究[J]. 金属矿山, 2020(6): 110-113.
	YANG Xueying, ZHU Yimin, LI Yanjun, et al. Collecting performance and mechanism of collector DXY-1 on quartz surface[J]. Metal Mine, 2020(6): 110-113.
[18]	张景奇, 张覃, 卯松. 油酸根离子在氟磷灰石和白云石表面吸附动力学与吸附热力学研究[J]. 矿冶工程, 2024, 44(1): 60-67. doi: 10.3969/j.issn.0253-6099.2024.01.014
	ZHANG Jingqi, ZHANG Qin, MAO Song. Study on adsorption kinetics and adsorption thermodynamics of oleic acid ions on the surface of fluorapatite and dolomite[J]. Mining and Metallurgical Engineering, 2024, 44(1): 60-67. doi: 10.3969/j.issn.0253-6099.2024.01.014
[19]	任鸣. 无定形纳米多孔材料的气体吸附仿真研究[D]. 北京: 北京化工大学, 2021.
	REN Ming. Study on the adsorption of amorphous porous nanomaterials[D]. Beijing: Beijing University of Chemical Technology, 2021.
[20]	王学斌, 周澳, 杨明辉, 等. 燃煤电厂200 t/d生活垃圾无氧热解耦合协同处置优化[J]. 煤炭学报, 2022, 47(11): 3897-3905.
	WANG Xuebin, ZHOU Ao, YANG Minghui, et al. Optimization on 200 t/ d garbage co-utilisation in a coal-fired power plant through air-free pyrolysis process[J]. Journal of China Coal Society, 2022, 47(11): 3897-3905.

分子视角下煤对O₂/CH₄混合气体的竞争吸附研究

Study on competitive adsorption of O₂/CH₄ mixed gas by coal from molecular perspective

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