不同变质程度煤的孔隙-官能团协同作用对气体吸附的影响

doi:10.16265/j.cnki.issn1003-3033.2026.07.0402

中国安全科学学报 ›› 2026, Vol. 36 ›› Issue (7): 135-143.doi: 10.16265/j.cnki.issn1003-3033.2026.07.0402

不同变质程度煤的孔隙-官能团协同作用对气体吸附的影响

吴春雷¹^,²(), 史波波¹^,^**(), 李佳³, 薛勇²

¹ 中国矿业大学安全工程学院, 江苏徐州 221116
² 南京信息工程大学大气物理学院, 江苏南京 210044
³ 中国安全生产科学研究院, 北京 100012

收稿日期:2026-03-10 修回日期:2026-05-12 出版日期:2026-08-10
通信作者:
^**史波波(1987—),男,山西长治人,博士,教授,主要从事消防工程、惰气(液氮)防灭火、煤火防治与热能利用等方面的研究。E-mail: shibobo@cumt.edu.cn。
作者简介:
吴春雷 (1995—),男,安徽宿州人,博士,主要从事地下空间火灾防治、防灾减灾工程等方面的研究。E-mail:wuchunlei831@126.com。
薛勇, 教授
基金资助:
国家自然科学基金资助(42275147); 国家自然科学基金资助(52474262); 国家自然科学基金资助(52074277); 国家资助博士后研究人员计划项目(GZC20251245); 江苏省基础研究计划项目(BK20250745); 江苏省卓越博士后计划项目(2025ZB686)

Influence of pore-functional group synergy on gas adsorption in coals with different metamorphic degrees

Wu Chunlei¹^,²(), Shi Bobo¹^,^**(), Li Jia³, Xue Yong²

¹ School of Safety Engineering, China University of Mining and Technology, Xuzhou Jiangsu 221116, China
² School of Atmospheric Physics, Nanjing University of Information Sciences and Technology, Nanjing Jiangsu 210044, China
³ China Academy of Safety Science and Technology, Beijing 100012, China

Received:2026-03-10 Revised:2026-05-12 Published:2026-08-10

摘要/Abstract

摘要：

为揭示不同变质程度煤的孔隙结构、表面官能团与O₂、N₂和CO₂吸附特性的内在关联,选取长焰煤(DX)、气煤(TX)、烟煤(YCW)和无烟煤(XT)4种典型煤样,综合利用低温液氮/CO₂吸附、压汞、弗伦克尔-哈尔西-希尔(FHH)分形模型及傅里叶变换红外(FTIR)光谱技术表征煤的微观结构,并在20、30和40 ℃温度及0.1~1.0 MPa条件下开展O₂、N₂和CO₂的吸附试验。结果表明:随变质程度升高,微孔孔容和比表面积呈“先减小→后增加→再减小”的非单调演化,烟煤(YCW)微孔最发达且分形维数最高(2.68);含氧官能团含量随变质程度增加而降低,芳香度逐渐升高;非极性气体(O₂、N₂)的吸附能力严格受微孔体积控制,遵循YCW>XT>DX>TX的顺序;而极性气体(CO₂)的吸附受“孔隙-官能团”协同效应主导,呈现YCW>TX>XT>DX的差异化特征;3种气体均为物理吸附,等量吸附热大小顺序为CO₂>O₂>N₂。

关键词: 孔隙结构, 分形维数, 官能团特征, 气体吸附, 等量吸附热, 煤变质程度

Abstract:

To investigate the intrinsic relationship between pore structure, surface functional groups, and adsorption characteristics of O₂, N₂, and CO₂ in coals with different metamorphic degrees, four coal samples including long-flame coal, gas coal, bituminous coal, and anthracite were selected. The microscopic structures were characterized using low-temperature N₂/CO₂ adsorption, mercury intrusion porosimetry, the Frenkel-Halsey-Hill (FHH) fractal model, and Fourier Transform Infrared Spectroscopy (FTIR). Adsorption experiments of O₂, N₂, and CO₂ were conducted at 20, 30, and 40 ℃ under 0.1-1.0 MPa. The results indicate that micropore volume and specific surface area exhibit a non-monotonic evolution of "decrease-increase-decrease" with increasing coal rank, with bituminous coal (YCW) showing the most developed micropores and highest fractal dimension (2.68). Oxygen-containing functional groups decrease while aromaticity increases with coalification. The adsorption of non-polar gases (O₂, N₂) is strictly controlled by micropore volume, following the order YCW>XT>DX>TX, whereas the adsorption of polar gas (CO₂) is governed by the synergistic "pore-functional group" effect, yielding a distinct order of YCW>TX>XT>DX. All three gases undergo physical adsorption, with isosteric heats following CO₂>O₂>N₂.

Key words: pore structure, fractal dimension, functional group characteristics, gas adsorption, isosteric heat of adsorption, coal metamorphic degree

中图分类号:

X937
TD752.2

吴春雷, 史波波, 李佳, 薛勇. 不同变质程度煤的孔隙-官能团协同作用对气体吸附的影响[J]. 中国安全科学学报, 2026, 36(7): 135-143.

Wu Chunlei, Shi Bobo, Li Jia, Xue Yong. Influence of pore-functional group synergy on gas adsorption in coals with different metamorphic degrees[J]. China Safety Science Journal, 2026, 36(7): 135-143.

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煤样	工业分析
煤样	M_ad	A_ad	V_daf	FC_ad
DX	6.68	10.97	45.96	36.39
TX	1.27	13.05	34.56	51.12
YCW	7.56	4.40	27.76	60.28
XT	2.16	11.64	4.68	81.52

煤样	总孔容 V/(cm³/g)	微孔孔容 V₁/(cm³/g)	(V₁/V)/ %	小孔孔容 V₂/(cm³/g)	中孔孔容 V₃/(cm³/g)	总孔比表面积 S/(m²/g)	微孔比表面积 S₁/(m²/g)	(S₁/S)/ %
DX	0. 131 7	0. 100 3	76.158	0. 026 6	0. 003 9	215.862	214.374	99.311
TX	0. 124 8	0. 093 6	75.000	0. 027 5	0. 003 3	155.532	154.288	99.200
YCW	0. 183 0	0. 136 0	74.317	0. 038 5	0. 007 1	301.098	299.256	99.388
XT	0. 131 5	0. 100 1	76.122	0. 026 8	0. 003 9	232.196	230.242	99.158

煤样	煤种	拟合斜率A	分形维数D	决定系数r²
DX	长焰煤	-0. 412 5	2. 587 5	0. 982 3
TX	气煤	-0. 489 2	2. 510 8	0. 975 6
YCW	烟煤	-0. 315 6	2. 684 4	0. 990 1
XT	无烟煤	-0. 453 4	2. 546 6	0. 986 7

煤样	I₃₄₀₀/ I₁₆₀₀	I₂₉₂₀/ I₁₆₀₀	I₁₇₀₀/ I₁₆₀₀	I₁₁₀₀/ I₁₆₀₀	I₈₅₀/ I₁₆₀₀	芳香度 f_a
DX	1.85	2.12	0.68	1.24	0.45	0.32
TX	1.23	1.45	0.35	0.89	0.62	0.48
YCW	1.56	1.78	0.42	1.08	0.71	0.41
XT	0.45	0.38	0.12	0.34	0.89	0.78

煤样	温度/ ℃	N₂			CO₂			O₂
煤样	温度/ ℃	V_L/ (cm³/g)	P_L/ MPa	r²	V_L/ (cm³/g)	P_L/ MPa	r²	V_L/ (cm³/g)	P_L/ MPa	r²
DX	20	12.691	2.640	0. 999 1	13.647	0.042	0. 939 0	16.947	1.532	0. 999 5
	30	11.596	3.745	0. 998 0	13.311	0.050	0. 958 3	15.748	1.705	0. 999 3
	40	10.700	3.894	0. 998 3	12.668	0.053	0. 960 5	15.072	2.274	0. 999 5
TX	20	12.023	0.919	0. 998 9	26.981	0.034	0. 924 3	13.158	1.023	0. 997 5
	30	10.142	2.376	0. 998 8	26.019	0.042	0. 974 1	12.681	1.375	0. 998 0
	40	9.579	3.594	0. 999 0	25.342	0.063	0. 985 8	11.879	1.517	0. 992 1
YCW	20	17.382	0.590	0. 998 8	28.355	0.049	0. 974 9	21.691	0.489	0. 996 3
	30	16.724	0.635	0. 998 6	26.976	0.058	0. 981 2	21.365	0.711	0. 998 0
	40	15.800	0.813	0. 998 7	26.555	0.082	0. 994 4	20.519	0.723	0. 997 5
XT	20	15.424	1.741	0. 998 1	16.284	0.050	0. 952 9	19.425	1.565	0. 999 3
	30	14.568	2.158	0. 999 4	15.626	0.062	0. 981 5	18.947	1.900	0. 999 4
	40	13.839	2.482	0. 998 7	15.021	0.078	0. 993 5	18.291	2.108	0. 999 1

不同变质程度煤的孔隙-官能团协同作用对气体吸附的影响

Influence of pore-functional group synergy on gas adsorption in coals with different metamorphic degrees

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