甲烷在蒙脱石狭缝孔中吸附行为的分子模拟

doi:10.7623/syxb201608008

石油学报 ›› 2016, Vol. 37 ›› Issue (8): 1021-1029.DOI: 10.7623/syxb201608008

甲烷在蒙脱石狭缝孔中吸附行为的分子模拟

熊健, 刘向君, 梁利喜

西南石油大学油气藏地质及开发工程国家重点实验室四川成都 610500

收稿日期:2015-11-09 修回日期:2016-06-13 出版日期:2016-08-25 发布日期:2016-09-02
通讯作者: 熊健,男,1986年12月生,2009获长江大学石油工程专业学士学位,2015年获西南石油大学油气田开发专业博士学位,现为西南石油大学讲师,主要从事非常规页岩气吸附性能等方面的研究。
作者简介:熊健,男,1986年12月生,2009获长江大学石油工程专业学士学位,2015年获西南石油大学油气田开发专业博士学位,现为西南石油大学讲师,主要从事非常规页岩气吸附性能等方面的研究。Email:361184163@qq.com
基金资助:
国家自然科学基金联合基金重点项目（No.U1262209）和国家自然科学基金青年科学基金项目（No.41602155）资助。

Molecular simulation on the adsorption behaviors of methane in montmorillonite slit pores

Xiong Jian, Liu Xiangjun, Liang Lixi

State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Sichuan Chengdu 610500, China

Received:2015-11-09 Revised:2016-06-13 Online:2016-08-25 Published:2016-09-02

摘要/Abstract

摘要：

利用蒙特卡罗方法研究甲烷在蒙脱石中的吸附行为，构建了蒙脱石狭缝孔模型，讨论了不同孔径、温度、含水量和组成对甲烷在蒙脱石中吸附行为的影响，揭示了甲烷在蒙脱石中微观吸附机理。研究结果表明：甲烷平均等量吸附热随着孔径增大而下降，且小于42 kJ/mol，说明甲烷在蒙脱石中吸附属于物理吸附；随着压力增大或孔径减小，甲烷在孔中吸附逐渐由能量较高吸附位向能量较低吸附位转移，造成甲烷吸附量增加；蒙脱石微孔中，甲烷吸附量随着孔径增大而增大，而中孔中，随着孔径增大而减小；甲烷分子在蒙脱石孔中吸附气量所占比例随着压力增大或孔径增大而呈下降趋势，当孔径大于6 nm时，蒙脱石孔中以游离气为主；随着温度升高，甲烷等量吸附热减小，甲烷在孔中的吸附逐渐由能量较低吸附位向能量较高吸附位转移，造成蒙脱石对甲烷吸附能力降低；水分子在蒙脱石孔中受到范德华力和静电能共同作用使其以定向方式堆积在孔壁表面，且水分子占据了甲烷分子吸附位和吸附空间，造成蒙脱石对甲烷吸附能力降低；多元组成竞争吸附中，蒙脱石对气体吸附能力大小的顺序为二氧化碳、甲烷、氮气；氮气或二氧化碳的增加，会造成甲烷在气相中摩尔分数降低、甲烷吸附位的变化以及甲烷吸附空间减小，三者的综合作用导致了蒙脱石对甲烷吸附能力降低。

关键词: 蒙脱石, 甲烷, 蒙特卡罗, 吸附机理, 吸附行为

Abstract:

In this study, montmorillonite was taken as a research target to construct the montmorillonite slit pore model. Meanwhile, Monte Carlo method was used to investigate the adsorption behaviors of methane in montmorillonite pore. On this basis, the influences of different pore sizes, different temperatures, different water contents and different compositions on the adsorption behaviors of methane in montmorillonite pore was explored to reveal the micro-adsorption mechanism of methane in montmorillonite pore. The research results show that the isosteric adsorption heat of methane is less than the 42 kJ/mol and decreases with the increasing of pore size, indicating that the methane adsorption on the montmorillonite can be identified as physic adsorption. With the increasing of pressure or the decreasing of pore size, the adsorption of methane in pores is transferred from the adsorption site with higher energy towards that with lower energy, thus increasing the adsorption capacity of methane. In montmorillonite micro-pores, the adsorption capacity of methane increases with the increase of pore size; while in the meso-pores, it decreases with the increasing of pore size. The proportion of the adsorbed gas amount of methane molecules in montmorillonite pores presents a decline trend as the pressure or pore size increases. When the pore size was more than 6 nm, montmorillonite pores were mainly filled by free gas. With temperature rising, the isosteric adsorption heat of methane is decreased, and the adsorption of methane was transferred from the adsorption site with lower energy towards that with higher energy, thus decreasing the methane adsorption capacity. The water molecules in montmorillonite pores are influenced by the combined effect of Van der Waals force and electrostatic force, and thus can accumulate on pore walls in a directional way. Moreover, these water molecules occupy the adsorption site and space of methane molecules, thus decreasing the methane adsorption capacity. In the multi-composition competitive adsorption, the gas adsorption capacity of montmorillonite is sequenced as follows:carbon dioxide >methane >nitrogen. The increasing of nitrogen or carbon dioxide will cause the reduction in mole fraction of methane in gas phase, the changes in adsorption sites of methane and the decrease of methane adsorption space. The combined effect of three factors leads to a decrease in the methane adsorption capacity.

Key words: montmorillonite, methane, Monte Carlo, adsorption mechanism, adsorption behavior

中图分类号:

TE312

熊健, 刘向君, 梁利喜. 甲烷在蒙脱石狭缝孔中吸附行为的分子模拟[J]. 石油学报, 2016, 37(8): 1021-1029.

Xiong Jian, Liu Xiangjun, Liang Lixi. Molecular simulation on the adsorption behaviors of methane in montmorillonite slit pores[J]. Acta Petrolei Sinica, 2016, 37(8): 1021-1029.

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甲烷在蒙脱石狭缝孔中吸附行为的分子模拟

Molecular simulation on the adsorption behaviors of methane in montmorillonite slit pores

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