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中高挥发烟煤孔隙结构表征及其与甲烷吸附的关系:基于核磁共振的实验研究

Characterization of Pore Structure and Its Relationship with Methane Adsorption on Medium-High Volatile Bituminous Coal: An Experimental Study Using Nuclear Magnetic Resonance.

作者信息

Zhang Baoxin, Fu Xuehai, Deng Ze, Hao Ming

机构信息

Key Laboratory of Coalbed Methane Resources and Dynamic Accumulation Process, Ministry of Education, China University of Mining and Technology, Xuzhou 221008, China.

China National Petroleum Corporation Key Laboratory of Unconventional Oil & Gas, Beijing 102249, China.

出版信息

J Nanosci Nanotechnol. 2021 Jan 1;21(1):515-528. doi: 10.1166/jnn.2021.18512.

Abstract

A number of studies have used the nuclear magnetic resonance (NMR) technique to analyse pore characteristics and to discuss the influencing mechanisms of pore structure on methane adsorption. However, there are few studies on the dynamic characteristics of methane adsorption over time under the same temperature and pressure conditions, especially by using the cylindrical coal samples. In this study, scanning electron microscopy (SEM), mercury injection porosimetry (MIP), isothermal adsorption and NMR techniques were carried out on the four medium-high volatile bituminous coal samples from Shanxi Province, China. The simulation of methane adsorption was carried out with the custom adsorption instruments. Based on the experimental results and the Hodot pore size classification standard, the pore size distribution of the samples was analysed. In addition, the influence of nanopore structure and water content on methane adsorption was discussed. The results show that the ₂ relaxation diagram of the four coal samples has a bimodal-triple peak, which reflects the complexity of the pore structure. Due to the clay minerals filling microfractures in the sample HX, the connectivity of the nanopores is reduced, in addition there is an obvious gap between the peaks in the relaxation diagram. After calculation of the ₂ relaxation diagrams of the coals, the results can be converted into the pore size distribution map. The pores in the four samples are mainly composed of the macropores, followed by the mesopores, and the ratio of micropores and transition pores is relatively small. At (saturated in 5% brine for 24 h) and (dried at 333 K for 3 h) conditions, the adsorption capacity of the four samples presented a positive correlation with the effective porosity and the ratio of micropores, and presented a negative correlation with the ratio of mesopores, while the macropores contribute less to the adsorption. Compared with samples at conditions, the adsorption capacity of the samples at conditions shows an overall increasing trend, which is approximately 1.6 times that of the samples at conditions on average. When a large amount of liquid water invades the nanopores and fractures, the water occupies the adsorption space of the methane due to the wettability effects and capillary pressure, which reduces the adsorption capacity.

摘要

许多研究已使用核磁共振(NMR)技术来分析孔隙特征,并探讨孔隙结构对甲烷吸附的影响机制。然而,在相同温度和压力条件下,关于甲烷吸附随时间变化的动态特性的研究很少,特别是使用圆柱形煤样的研究。在本研究中,对来自中国山西省的四个中高挥发烟煤样品进行了扫描电子显微镜(SEM)、压汞法(MIP)、等温吸附和NMR技术。使用定制吸附仪器进行了甲烷吸附模拟。基于实验结果和霍多特孔径分类标准,分析了样品的孔径分布。此外,还讨论了纳米孔隙结构和含水量对甲烷吸附的影响。结果表明,四个煤样的₂弛豫图具有双峰-三峰,这反映了孔隙结构的复杂性。由于粘土矿物填充了样品HX中的微裂缝,纳米孔隙的连通性降低,此外弛豫图中的峰之间存在明显间隙。对煤的₂弛豫图进行计算后,结果可转换为孔径分布图。四个样品中的孔隙主要由大孔组成,其次是中孔,微孔和过渡孔的比例相对较小。在(在5%盐水中饱和24小时)和(在333K下干燥3小时)条件下,四个样品的吸附容量与有效孔隙率和微孔比例呈正相关,与中孔比例呈负相关,而大孔对吸附的贡献较小。与条件下的样品相比,条件下样品的吸附容量总体呈增加趋势,平均约为条件下样品的1.6倍。当大量液态水侵入纳米孔隙和裂缝时,由于润湿性效应和毛细管压力,水占据了甲烷的吸附空间,从而降低了吸附容量。

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