油气藏评价与开发 >
2023 , Vol. 13 >Issue 5: 636 - 646
DOI: https://doi.org/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
收稿日期: 2022-08-10
网络出版日期: 2023-11-01
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
Received date: 2022-08-10
Online published: 2023-11-01
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。
侯大力 , 韩鑫 , 唐洪明 , 郭建春 , 龚凤鸣 , 孙雷 , 强贤宇 . 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 . DOI: 10.13809/j.cnki.cn32-1825/te.2023.05.011
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.
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