Influence of physicochemical properties of coals on pore morphology and methane adsorption: a perspective

doi:10.16085/j.issn.1000-6613.2018-1948

Abstract

Abstract:

The coal-bed methane (CH₄) in coal reservoirs mainly exists in form of adsorbed state. Study on influences of physicochemical properties of coals on their pore morphology and CH₄ adsorption performance is important for effectively recovering CH₄. In this review, the influences of physicochemical properties of coals on their pore structure and CH₄ adsorption, and the future research trend were addressed. The results showed the positive linear correlation between coal micropore parameters and their CH₄ adsorption capacity. The meso- and macropores of coal mainly influenced the adsorption/diffusion rate of CH₄ within coals. The coals rich in ink-shaped pores or vitrinite always exhibited superior CH₄ adsorption performance. In general, the minerals and moisture decreased coal adsorption ability. The extraction of small organic compounds from coal matrix was helpful to increase pore surface area and volume of coals and further enhance their adsorption performance. To gain further insight into coal physicochemical properties dependences of pore morphology and CH₄ adsorption, the coupling relationship between coal pore structure parameters and fluid adsorption/desorption, and the elaboration of coal complex pore morphology based on multi-fractal theory were needed to study. Furthermore, to accurately estimate pore structure parameters of coal, the BET model and BJH model fully considering coal heterogeneity were needed. Study on occurrence space regarding oxygen-containing functional groups on coal matrix in coal pore space to address the cooperative effect of functional groups and pore morphology on CH₄ adsorption was also required. Finally, study on the influences of moisture on coal pore structure and adsorption performance for CH₄ from experiment and theory analysis, and experimental method for determining moisture-containing coal adsorption performance, should also be concentrated on.

Key words: coal, physicochemical properties, pore morphology, methane, adsorption

摘要：

煤层气主要成分为甲烷（CH₄），其主要以吸附态形式存在于煤层中。明确煤体理化性质和煤体孔隙结构及CH₄吸附性能间构效关系，对于高效开采CH₄资源至为关键。为此，本文阐明了煤体理化性质对其孔隙结构和CH₄吸附性能的作用规律，并指出了后续研究趋势。分析表明：煤体微孔结构和其CH₄吸附容量之间呈正线性相关性；煤体介/大孔主要影响CH₄在煤层内部的吸附/扩散速率。具有墨水瓶形孔或富含镜质体的煤体通常具有较强CH₄吸附性能。煤中矿物质和水分对煤体吸附性能产生不利影响。煤中小分子有机物的抽提能够提高煤体孔隙表面积和孔容积，进而提升煤体吸附性能。为了深入研究煤体理化性质及其吸附性能的作用规律，后续需开展以下工作：研究煤体孔隙结构参数和煤体吸附/解吸性能之间的耦合作用关系；利用多重分形理论精确揭示煤体内复杂的孔隙结构信息；优化并建立考虑煤体非均质性的BET和BJH等孔隙结构参数计算模型；以煤基质表面含氧官能团在煤体孔隙内部的赋存空间为切入点，阐明煤体官能团和孔隙结构对其CH₄吸附性能的协同作用规律；从理论模拟和实验科学入手，阐明煤层中水分对煤体孔隙结构的影响；建立更为科学的含水煤体吸附性能评价方法。

关键词: 煤, 理化性质, 孔隙结构, 甲烷, 吸附（作用）

CLC Number:

TE377

Xuexiang FU, Dengfeng ZHANG, Wenping JIANG, Zengmin LUN, Chunpeng ZHAO, Haitao WANG, Yanhong LI. Influence of physicochemical properties of coals on pore morphology and methane adsorption: a perspective[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2714-2725.

付学祥, 张登峰, 降文萍, 伦增珉, 赵春鹏, 王海涛, 李艳红. 煤体理化性质对其孔隙结构和甲烷吸附性能影响的研究进展[J]. 化工进展, 2019, 38(06): 2714-2725.

Figures/Tables 17

数学模型	数学形式	适用性	基于模型分析实例	参考文献
Avnir模型	V/V _m=K[ln(P ₀/P)]^- ^r D=3-r	P/P ₀>0.5时，拟合过程中会出现线性偏移	计算煤体内表面分形维数，定量描述煤体内部孔结构特征	[44]
FHH模型	ln(V)=Kln[ln(P ₀/P）]+C D=K+3	适于描述原生煤中8~217nm的孔隙非均质性	根据N₂吸附等温线确定了煤体在不同相对压力下的分形维数	[40]
修正的FHH模型	V/V _m=K[ln(P ₀/P)] ^A D=3+A	适用于0<P/P ₀<0.5范围	分形维数与煤层表面不规则性及煤体的CH₄吸附能力呈正线性	[30]
Neimark模型	lgS $P / P 0$ =Algr_k, $P / P 0$ +const D=2-A	适用于0<P/P ₀<0.5范围	计算得到煤体表面分形维数范围是2.57~2.80，意味着煤体表面不规则且具有分形特征	[2]
Menger模型	D={ln[dV_P ₍ _r ₎ /dP(r)]-lnα}lnP(r)+4	不适用煤体孔隙结构的非均质性	煤体在一定的孔径范围内才具有分形特征	[43]
Sierpinski模型	V=α(P-P_t )³ ^D	适合描述煤体纳米孔分形特征	表明不同类型构造煤体表面不连续性和粗糙度的差异性较大	[45]

数学模型	数学形式	适用性	基于模型分析实例	参考文献
Avnir模型	V/V _m=K[ln(P ₀/P)]^- ^r D=3-r	P/P ₀>0.5时，拟合过程中会出现线性偏移	计算煤体内表面分形维数，定量描述煤体内部孔结构特征	[44]
FHH模型	ln(V)=Kln[ln(P ₀/P）]+C D=K+3	适于描述原生煤中8~217nm的孔隙非均质性	根据N₂吸附等温线确定了煤体在不同相对压力下的分形维数	[40]
修正的FHH模型	V/V _m=K[ln(P ₀/P)] ^A D=3+A	适用于0<P/P ₀<0.5范围	分形维数与煤层表面不规则性及煤体的CH₄吸附能力呈正线性	[30]
Neimark模型	lgS $P / P 0$ =Algr_k, $P / P 0$ +const D=2-A	适用于0<P/P ₀<0.5范围	计算得到煤体表面分形维数范围是2.57~2.80，意味着煤体表面不规则且具有分形特征	[2]
Menger模型	D={ln[dV_P ₍ _r ₎ /dP(r)]-lnα}lnP(r)+4	不适用煤体孔隙结构的非均质性	煤体在一定的孔径范围内才具有分形特征	[43]
Sierpinski模型	V=α(P-P_t )³ ^D	适合描述煤体纳米孔分形特征	表明不同类型构造煤体表面不连续性和粗糙度的差异性较大	[45]

煤样	温度/^oC	n _L,dry/mL·g^-1	n _L,moist /mL·g^-1	含水率升幅/%	CH₄吸附量降幅/%
YZG2	30	39.97	27.07	2.01	32.27
YZG2	30	39.97	15.04	5.02	62.37
Lh7	30	23.22	19.99	0.66	13.91
Lh7	30	23.22	15.18	1.83	34.63
Yl10	30	26.99	22.93	0.88	15.04
Yl10	30	26.99	19.62	1.77	27.31
HZ29	30	32.86	28.29	1.01	13.91
HZ29	30	32.86	22.48	2.80	31.59
WLH8	30	52.80	48.01	1.38	9.07
WLH8	30	52.80	31.39	5.66	40.55
DFS4	25	12.164	11.563	5.09	49.41
DFS4	40	11.201	10.725	5.09	42.50
SP11	35	16.870	15.210	2.05	9.84
SP11	45	14.320	13.890	2.05	30.03
SH3	30	37.148	35.240	0.64	51.36
SH3	40	33.458	32.450	0.64	30.13

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