龙马溪组页岩干酪根表征初探及干酪根吸附特征研究

doi:10.13809/j.cnki.cn32-1825/te.2023.05.011

油气藏评价与开发 ›› 2023, Vol. 13 ›› Issue (5): 636-646.doi: 10.13809/j.cnki.cn32-1825/te.2023.05.011

龙马溪组页岩干酪根表征初探及干酪根吸附特征研究

侯大力^1,^2,³(),韩鑫^2,⁵,唐洪明¹,郭建春⁴,龚凤鸣²,孙雷⁴,强贤宇²

1.西南石油大学地球科学与技术学院，四川成都 610500
2.成都理工大学能源学院，四川成都 610059
3.油气藏地质及开发工程国家重点实验室（成都理工大学），四川成都 610059
4.油气藏地质及开发工程国家重点实验室（西南石油大学），四川成都 610500
5.中国石油长庆油田第四采油厂，陕西榆林 718599

收稿日期:2022-08-10 发布日期:2023-11-01 出版日期:2023-10-26
作者简介:侯大力（1983—），男，博士，副教授，主要从事油气藏流体相态、注CO₂提高采收率及CO₂埋存、油气藏数值模拟等方面研究。地址：四川省成都市成华区二仙桥东三路1号，邮政编码：610059。E-mail：houdali08@163.com
基金资助:
中国博士后基金项目“高温高压下CO₂-近临界原油-地层水三相相平衡表征模型”(2017M612995);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);油气藏地质及开发工程国家重点实验室自由探索项目“储层条件超临界CO₂-地层水-页岩气-页岩多相相互作用复杂机理研究”(CZ201910)

Primary research on expression of kerogen in Longmaxi Shale and its adsorption characteristics

HOU Dali^1,^2,³(),HAN Xin^2,⁵,TANG Hongming¹,GUO Jianchun⁴,GONG Fengming²,SUN Lei⁴,QIANG Xianyu²

1. School of Geoscience and Technology, Southwest Petroleum University, Chengdu, Sichuan 610500, China
2. College of Energy, Chengdu University of Technology, Chengdu, Sichuan 610059, China
3. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Chengdu University of Technology, Chengdu, Sichuan 610059, China
4. State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, Sichuan 610500, China
5. No.4 Production Plant of Changqing Oilfield, Petrochina, Yulin, Shaanxi 718599, China

Received:2022-08-10 Online:2023-11-01 Published:2023-10-26

摘要/Abstract

摘要：

吸附气是页岩气赋存在页岩中的主要方式之一，而且吸附气是页岩气后期产量的主要来源。吸附气主要赋存在页岩有机质干酪根和黏土矿物中，而有机质干酪根中吸附比例较大。因此，研究页岩有机质干酪根的特征及其吸附机理对页岩气开发有重要作用。以四川盆地龙马溪组页岩干酪根为研究对象，通过固体核磁共振谱分析实验、傅里叶变换红外光谱（FTIR）分析实验、X射线光电子能谱（XPS）实验相结合的方法表征干酪根的微观结构，构建了干酪根的分子结构模型。利用磁悬浮重量法实验、巨正则系综蒙特卡洛（GCMC）和分子动力学（MD）的分子模拟方法，分析CH₄在龙马溪组页岩干酪根的吸附机理及特征。研究结果表明：龙马溪组页岩实验样品干酪根的分子式为C₂₃₇H₂₁₉O₂₁N₅S₄；CH₄在干酪根中的超额吸附量随着压力的增加先升高后降低；相同孔径和压力条件下，随着温度的升高，CH₄的超额吸附量和总气量逐渐变小；干酪根中的C原子和S原子是造成CH₄吸附的主要原因；靠近干酪根孔壁的CH₄呈现吸附态，远离干酪根孔壁的CH₄呈现游离态，随着孔径的增加，CH₄密度的两峰之间的距离逐渐变宽，峰值逐渐下降。

关键词: 页岩干酪根, 分子结构, 吸附特征, 分子模拟, 龙马溪组

Abstract:

Adsorbed gas represents a primary mode of shale gas occurrence and is a major source of shale gas production in the later stages of development. It primarily resides within the organic kerogen and clay minerals of shale formations, with organic kerogen being the dominant host. Consequently, the study of organic kerogen characteristics and its adsorption mechanisms is crucial for understanding shale gas development. In this paper, the kerogen of Longmaxi Shale in the Sichuan Basin is taken as the research object. The microstructure of kerogen is expressed by combining methods through the solid-state NMR experiment, Fourier transform infrared spectroscopy experiment, X-ray photoelectron spectroscopy experiment, and the molecular structure model of kerogen is constructed. The adsorption mechanism and characteristics of CH₄ in kerogen of Longmaxi Shale are analyzed by magnetic levitation weight experiment, molecular simulation methods of the Grand Canonical Monte Carlo（GCMC）, and Molecular Dynamics（MD）. The results show that the molecular formula of the kerogen of shale experimental sample of Longmaxi Formation is C₂₃₇H₂₁₉O₂₁N₅S₄. The excess adsorption gas volume of CH₄ in kerogen increase first and then decreased with the increase of pressure. Under the same pore size and pressure, the excess adsorption gas volume and total gas volume of CH₄ decrease with the increase in temperature. The C and S atoms in kerogen are the main cause of CH₄ adsorption. The CH₄ near the kerogen pore wall presents an adsorption state, while the CH₄ far from the kerogen pore wall presents a free state. As the pore size increase, the distance between the two peaks of CH₄ density gradually increases, and the peak value decreases gradually.

Key words: shale kerogen, molecular structure, adsorption characteristics, molecular simulation, Longmaxi Formation

中图分类号:

TE377

侯大力,韩鑫,唐洪明等. 龙马溪组页岩干酪根表征初探及干酪根吸附特征研究[J]. 油气藏评价与开发, 2023, 13(5): 636-646.

Dali HOU,Xin HAN,Hongming TANG, et al. Primary research on expression of kerogen in Longmaxi Shale and its adsorption characteristics[J]. Petroleum Reservoir Evaluation and Development, 2023, 13(5): 636-646.

图/表 18

图1

图2

图3

表1

表2

长宁地区龙马溪组页岩干酪根骨架参数"

骨架参数	物理意义	定义	小数
$f a l$	脂化度	$f a l M + f a l A + f a l B + f a l H + f a l D + f a l O$	0.153 6
$f a r$	芳香度	$f a r A + f a r H + f a r B + f a r C + f a r O$	0.673 6
$X B P$	桥周比	$f a r B / f a r A + f a r H + f a r C + f a r O$	0.160 0
BI	脂肪分支系数	$f a l D + C H - O / f a l$	0.140 0
δ	芳香取代度	$1 - f a r H / f a r$	0.270 0

表2

图4

图5

表3

图6

图7

图8

图9

图10

图11

图12

图13

图14

图15

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碳官能团	面积分数/%
脂甲基	2.31
芳甲基	1.41
脂C（2）碳	2.90
亚甲基	2.47
次甲基，季sp³碳	0.77
氧—亚甲基	1.37
氧—次甲基	1.43
氧—脂肪环	2.70
氧—芳香环	1.45
质子化芳香碳	48.95
桥联芳香碳	9.13
支链芳香碳	5.36
氧—芳香碳	2.47
羧基，羰基	17.29

元素	归属	结合能/eV	面积分数/%
C1s	C—C，C—H	284.6	55.90
	C—O，C—OH	285.4	20.40
	C=O	287.1	6.60
	O—C=O	288.5	17.10
F1s	F^-	684.4	100.00
N1s	吡啶	398.8	6.50
	吡咯	400.2	64.60
	季氮	401.7	24.50
	氮氧化物	403.0	2.30
S2p	噻吩型硫	162.4	30.16
	亚砜型硫	165.4	33.47
	砜型硫	168.6	36.37

龙马溪组页岩干酪根表征初探及干酪根吸附特征研究

Primary research on expression of kerogen in Longmaxi Shale and its adsorption characteristics

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