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不同煤级煤的纳米孔结构及其定量表征。

Nanopore Structure of Different Rank Coals and Its Quantitative Characterization.

机构信息

School of Emergency Management and Safety Engineering, China University of Mining & Technology (Beijing), Beijing 100083, China.

出版信息

J Nanosci Nanotechnol. 2021 Jan 1;21(1):22-42. doi: 10.1166/jnn.2021.18728.

Abstract

Based on gas adsorption theory, high-pressure mercury intrusion (HPMI), low-temperature liquid nitrogen gas adsorption (LT-N₂GA), CO₂ adsorption, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and small-angle X-ray scattering (SAXS) techniques were used to analyze the pore structures of six coal samples with different metamorphisms in terms of pore volume, specific surface area (SSA), pore size distribution (PSD) and pore shape. Combined with the gas adsorption constant a, the influence and mechanism of the pore structure of different coal ranks on gas adsorption capacity were analyzed. The results show that there are obvious differences in the pore structure of coals with different ranks, which leads to different adsorption capacities. To a large extent, the pore shapes observed by SEM are consistent with the LT-N₂GA isotherm analysis. The pore morphology of coal samples with different ranks is very different, indicating the heterogeneity among the coal surfaces. Adsorption analysis revealed that mesopore size distributions are multimodal and that the pore volume is mainly composed of mesopores of 2-15 nm. The adsorption capacity of the coal body micropores depends on the 0.6-0.9 nm and 1.5-2.0 nm aperture sections. The influence of coal rank on gas desorption and diffusion is mainly related to the difference in pore structure. The medium metamorphic coal sample spectra show that the number of peaks in the high-wavenumber segment is small and that it is greater in the high metamorphic coal. The absorption intensity of the C-H stretching vibration peak of naphthenic or aliphatic hydrocarbons varies significantly among the coal samples. Over a small range of angles, as the scattering angle increases, the scattering intensity of each coal sample gradually decreases, and as the degree of metamorphism increases, the scattering intensity gradually increases. That is, the degree of metamorphism of coal samples is directly proportional to the scattering intensity. The influence of coal rank on gas adsorption capacity is mainly related to the difference in pore structure. The gas adsorption capacity shows an asymmetric U-shaped relationship with coal rank. For higher rank coals ( < 15%), the gas adsorption consistently decreases significantly with increasing . In the middle and low rank coal stages ( > 15%), it increases slowly with the increase of . We believe that the results of this study will provide a theoretical basis and practical reference value for effectively evaluating coal-rock gas storage capacity, revealing the law of CBM enrichment and the development and utilization of CBM resources.

摘要

基于气体吸附理论,采用高压汞(HPMI)、低温液氮(LT-N₂GA)吸附、CO₂吸附、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)和小角 X 射线散射(SAXS)技术,对六种不同变质程度的煤样的孔体积、比表面积(SSA)、孔径分布(PSD)和孔形状进行了分析。结合气体吸附常数 a,分析了不同煤级的孔结构对气体吸附能力的影响和机理。结果表明,不同煤级的煤样在孔结构上存在明显差异,导致吸附能力不同。在很大程度上,SEM 观察到的孔形态与 LT-N₂GA 等温线分析一致。不同煤级煤样的孔隙形态差异很大,表明煤表面存在不均匀性。吸附分析表明,介孔分布呈多峰型,孔体积主要由 2-15nm 的中孔组成。煤体微孔的吸附量取决于 0.6-0.9nm 和 1.5-2.0nm 的孔径段。煤级对气体解吸和扩散的影响主要与孔结构的差异有关。中变质煤样的光谱表明,高波数段的峰数较少,而高变质煤的峰数较多。环烷烃或脂肪烃的 C-H 伸缩振动峰的吸收强度在煤样之间差异显著。在小角度范围内,随着散射角的增加,各煤样的散射强度逐渐降低,随着变质程度的增加,散射强度逐渐增大。也就是说,煤样的变质程度与散射强度成正比。煤级对气体吸附能力的影响主要与孔结构的差异有关。气体吸附容量与煤级呈不对称 U 型关系。对于较高煤级(<15%)的煤,随着 的增加,气体吸附量明显显著下降。在中低煤级阶段(>15%),随着 的增加,气体吸附量缓慢增加。我们相信,本研究的结果将为有效评价煤岩储气能力、揭示煤层气富集规律和煤层气资源开发利用提供理论依据和实践参考价值。

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