页岩干酪根吸附规律的分子模拟研究

doi:10.13809/j.cnki.cn32-1825/te.2022.03.007

油气藏评价与开发 ›› 2022, Vol. 12 ›› Issue (3): 455-461.doi: 10.13809/j.cnki.cn32-1825/te.2022.03.007

页岩干酪根吸附规律的分子模拟研究

李晶辉¹(),韩鑫³,黄思婧³,余洋阳³,强贤宇³,顾康福³,侯大力^2,³()

1. 中国石化西北油田分公司石油工程技术研究院,新疆乌鲁木齐 830011
2. 成都理工大学油气藏地质及开发工程国家重点实验室,四川成都 610059
3. 成都理工大学能源学院,四川成都 610059

收稿日期:2021-09-06 发布日期:2022-06-24 出版日期:2022-06-26
通讯作者: 侯大力 E-mail:lijh.xbsj@sinopec.com;houdali08@163.com
作者简介:李晶辉（1985—）,男,本科,高级工程师,主要从事油气田开发与管理工作。地址：新疆维吾尔自治区乌鲁木齐市长春南路466号石油工程技术研究院,邮政编码：830011。 E-mail： lijh.xbsj@sinopec.com
基金资助:
四川省科技厅应用基础研究项目“储层条件超临界CO2压裂液—页岩气—页岩多相相互作用复杂机理研究”(2021YJ0352)

Molecular simulation of adsorption law for shale kerogen

LI Jinghui¹(),HAN Xin³,HUANG Sijing³,YU Yangyang³,QIANG Xianyu³,GU Kangfu³,HOU Dali^2,³()

1. Research Institute of Petroleum Engineering Technology, Sinopec Northwest Oilfield Company, Urumqi, Xinjiang 830011, China
2. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Chengdu University of Technology, Chengdu, Sichuan 610059, China
3. College of Energy, Chengdu University of Technology, Chengdu, Sichuan 610059, China

Received:2021-09-06 Online:2022-06-24 Published:2022-06-26
Contact: HOU Dali E-mail:lijh.xbsj@sinopec.com;houdali08@163.com

摘要/Abstract

摘要：

页岩气是以CH₄为主赋存在有机质页岩的非常规天然气,其中的吸附气是页岩气后期产量的主要来源,因此,研究页岩的吸附机理对页岩气开发有重要作用。利用Ⅱ型（混合型干酪根,来源于浮游生物）干酪根分子建立Ⅱ型干酪根模型,采用蒙特卡洛方法和分子模拟方法研究CH₄在Ⅱ型干酪根中的微观吸附行为和机理,通过实验数据验证了该模型,并进一步探究了孔径、温度和压力对吸附行为的影响。研究取得的认识如下：①孔径越大,CH₄超额吸附量越大;温度越高,CH₄超额吸附量越低;压力越大,CH₄绝对吸附量先快速上升后逐渐平缓,CH₄超额吸附量先上升后下降;②随着孔径的增加,CH₄的吸附热越来越少,并从吸附热看,CH₄在干酪根的吸附行为是物理吸附;③孔径小于1 nm时,CH₄在干酪根中为吸附相;孔径大于1 nm时,CH₄在干酪根中为吸附相与游离相共存。

关键词: 分子模拟, 页岩气, 干酪根, 吸附, 吸附机理

Abstract:

Shale gas is unconventional natural gas, mainly CH_4, occurring in organic shale. The adsorbed gas is the main source for later production of shale gas. Therefore, studying the adsorption mechanism of shale plays an important role in shale gas development. By using type Ⅱ kerogen molecules, a type Ⅱ kerogen model is established. Then, Monte Carlo method and molecular simulation method are used to study the micro adsorption behavior and mechanism of CH₄ in type Ⅱ kerogen. Experimental data are used to verify this model, and the effects of pore size, temperature and pressure on the adsorption behavior are investigated. The findings are as follows: ① The higher the pore size, the greater the excess adsorption capacity of CH₄. The higher the temperature, the lower the excess adsorption capacity of CH₄. With the increase of pressure, the absolute adsorption amount of CH₄ increases rapidly at first and then gently, and the excess adsorption amount of CH₄ increases first and then decreases. ② The adsorption heat of CH₄ decreases with the increase of pore size. The adsorption of CH₄ in kerogen is physical adsorption. ③ When the pore size is smaller than 1 nm, CH₄ is the adsorption phase in kerogen; when the pore size is larger than one nanometer（1 nm）, CH₄ is the coexistence of adsorption phase and free phase in kerogen.

Key words: molecular simulation, shale gas, kerogen, adsorption, adsorption mechanism

中图分类号:

TE377

李晶辉,韩鑫,黄思婧等. 页岩干酪根吸附规律的分子模拟研究[J]. 油气藏评价与开发, 2022, 12(3): 455-461.

Jinghui LI,Xin HAN,Sijing HUANG, et al. Molecular simulation of adsorption law for shale kerogen[J]. Petroleum Reservoir Evaluation and Development, 2022, 12(3): 455-461.

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结构参数	数值
H/C	1.170
O/C	0.095
N/C	0.024
S/C	0.012
芳香度	0.410
羰基中的氧原子个数	7
羧基中的氧原子个数	4
醚基中的氧原子个数	13

	原子类型	势井深度（kcal/mol）	作用势为0时原子间的距离（nm）	原子电荷（e）
甲烷	CH₄	15.941	0.330	0.890
	C	3.016	0.424	0.651
	H	0	0	0.424
干酪根	O	0.957	0.341	-0.445
	N	0.774	0.366	0
	S	3.440	0.403	0

页岩干酪根吸附规律的分子模拟研究

Molecular simulation of adsorption law for shale kerogen

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