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基于热力学和动力学的温度对甲烷解吸影响的研究

Study for the Effect of Temperature on Methane Desorption Based on Thermodynamics and Kinetics.

作者信息

Gao Zheng, Ma Dongmin, Chen Yue, Zheng Chao, Teng Jinxiang

机构信息

College of Geology and Environment, Xi'an University of Science and Technology, Xi'an 710054, China.

Key Laboratory of Coal Resources Exploration and Comprehensive Utilization, Ministry of Natural Resources, Xi'an 710021, China.

出版信息

ACS Omega. 2020 Dec 29;6(1):702-714. doi: 10.1021/acsomega.0c05236. eCollection 2021 Jan 12.

Abstract

Desorption hysteresis is important for primary gas production. Temperature may cause serious changes in the methane adsorption/desorption behaviors. In order to study the mechanism of methane desorption and desorption hysteresis, three sets of samples of long-flame coal, coking coal, and anthracite were collected, and experiments such as microscopic composition determination, liquid nitrogen adsorption, and isothermal adsorption/desorption were performed. From the perspectives of desorption kinetics, desorption thermodynamics, and methane occurrence state, the differences in methane and methane desorption characteristics and the desorption hysteresis mechanism are discussed. The results show that at the same temperature, anthracite (SH3#) has the largest saturated adsorption capacity and residual adsorption capacity, followed by coking coal (SGZ11#), and long-flame coal (DFS4#) has the smallest. As the temperature increases, the theoretical desorption rate and residual adsorption capacity of anthracite (SH3#) and coking coal (SGZ11#) will increase first and then decrease. Temperature and methane desorption do have positive effects, but temperature may have a threshold for promoting methane desorption. It is necessary to comprehensively consider the influence of temperature on the activation of gas molecules and the pore structure of coal. Under the premise of a certain temperature, as the pressure increases, the desorption hysteresis rate changes in a logarithmic downward trend, the methane desorption hysteresis rate in the low-pressure stage ( < 4 MPa) is large, and the methane desorption hysteresis rate in the high-pressure stage ( > 4 MPa) is lower; during the isobaric adsorption process, the adsorption capacity of anthracite (SH3#) increases the fastest, followed by SGZ11#, and that of DFS4# is the smallest. In the low-pressure stage ( < 4 MPa), the adsorption capacity increases significantly with the increase in pressure, but in the high-pressure stage ( > 4 MPa), the adsorption capacity does not change significantly with pressure, instead gradually stabilizes. Under the same pressure, the molecular free path of methane increases with temperature. Under the premise of constant temperature, in the low-pressure stage (0 < < 4 MPa), when the pressure continues to decrease, the free path of methane molecules increases significantly, resulting in a decrease in diffusion capacity. In the high-pressure stage (4 < < 8 MPa), when the pressure continues to decrease, the free path of methane molecules does not change significantly; the sample desorption process of three sets of samples DFS4#, SGZ11#, and SH3# occurs, and the intermediate adsorption heat is greater than the isometric adsorption heat during the adsorption process, indicating that the desorption process needs to continuously absorb heat from outside the system. The energy difference produced in the process of adsorption and desorption causes the desorption hysteresis effect. The greater the difference in the isometric heat value of adsorption, the more significant the hysteresis is.

摘要

解吸滞后对一次瓦斯抽采很重要。温度可能会导致甲烷吸附/解吸行为发生严重变化。为了研究甲烷解吸及解吸滞后机理,采集了长焰煤、焦煤和无烟煤三组样品,并进行了微观成分测定、液氮吸附及等温吸附/解吸等实验。从解吸动力学、解吸热力学以及甲烷赋存状态等角度,探讨了甲烷及甲烷解吸特征差异和解吸滞后机理。结果表明,在相同温度下,无烟煤(SH3#)的饱和吸附量和残余吸附量最大,其次是焦煤(SGZ11#),长焰煤(DFS4#)最小。随着温度升高,无烟煤(SH3#)和焦煤(SGZ11#)的理论解吸率和残余吸附量先增大后减小。温度与甲烷解吸确实存在正效应,但温度对甲烷解吸的促进可能存在阈值。有必要综合考虑温度对气体分子活化及煤孔隙结构的影响。在一定温度前提下,随着压力增加,解吸滞后率呈对数下降趋势变化,低压阶段(<4MPa)甲烷解吸滞后率大,高压阶段(>4MPa)甲烷解吸滞后率较低;在等压吸附过程中,无烟煤(SH3#)的吸附量增加最快,其次是SGZ11#,DFS4#最小。在低压阶段(<4MPa),吸附量随压力增加显著增大,但在高压阶段(>4MPa),吸附量随压力变化不显著,反而逐渐趋于稳定。在相同压力下,甲烷的分子自由程随温度升高而增大。在恒温前提下,在低压阶段(0<<4MPa),当压力继续降低时,甲烷分子自由程显著增大,导致扩散能力下降。在高压阶段(4<<8MPa),当压力继续降低时,甲烷分子自由程变化不显著;三组样品DFS4#、SGZ11#和SH3#的样品解吸过程中,中间吸附热大于吸附过程中的等量吸附热,表明解吸过程需要不断从系统外吸收热量。吸附和解吸过程中产生的能量差导致了解吸滞后效应。吸附等量热值差异越大,滞后越显著。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c8bc/7807784/cdb1fd0197f6/ao0c05236_0002.jpg

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