含氧官能团修饰的石墨表面润湿性及其对气水分布的影响

熊健; 唐俊方; 周雪; 刘向君; 梁利喜

doi:10.19509/j.cnki.dzkq.tb20210633

含氧官能团修饰的石墨表面润湿性及其对气水分布的影响

doi: 10.19509/j.cnki.dzkq.tb20210633

西南石油大学油气藏地质及开发工程国家重点实验室, 成都 610500

基金项目:

国家自然科学基金项目 41772151

国家自然科学基金项目 41872167

西南石油大学青年科技创新团队 2018CXTD13

详细信息

作者简介:
熊健(1986—)，男，研究员，主要从事岩石物理和岩石力学实验等方面研究。E-mail: 361184163@qq.com

中图分类号: P618.130.2⁺1
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出版历程
- 收稿日期: 2021-10-22

Surface wettability of oxygen-containing functional group-modified graphite and its effect on gas-water distribution

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

摘要

摘要:
润湿性是储层岩石表面重要的物理性质之一, 是影响毛细管力、相对渗透率、束缚水饱和度以及流体微观分布的关键因素。基于分子模拟方法, 研究了含氧官能团修饰的石墨表面(有机质表面)润湿行为及甲烷-水体系在有机质狭缝孔中的分布特征。结果表明：随着含氧官能团的增多, 水分子与有机质表面间相互作用能减小, 有机质表面润湿接触角增大；随着温度的升高, 有机质表面与水分子间的相互作用能增大, 润湿接触角减小；在对称C/O比的石墨狭缝孔模型中, 水分子对称分布在含氧官能团化的石墨壁面附近区域, 且随着C/O比的减小, 水分子的相对浓度增大、扩散系数减小, 而甲烷分子则聚集分布在孔中心区域；在不对称C/O比的石墨狭缝孔模型中, 水分子不对称分布在含氧官能团化的石墨壁面附近区域, 而甲烷分子仍聚集分布在孔中心区域, 其中C/O比低的一侧, 壁面亲水性强, 水分子的相对浓度高，而C/O比高的一侧，壁面疏水性强，水分子的相对浓度低。研究结果对于页岩储层特征影响研究有重要的意义。
- 甲烷 /
- 有机质 /
- 含氧官能团 /
- 润湿性 /
- 气水分布 /
- 石墨
Abstract:
Wettability is one of the important physical properties of reservoir rock surfaces, and it is a key factor affecting capillary force, relative permeability, bound water saturation and fluid micro-distribution. Based on the molecular simulation method, this paper made a study of the wetting behavior of a graphite surface (organic surface) modified by the oxygen-containing functional groups and the distribution characteristics of the methane-water system in organic slit pores. The results showed that the interaction energy between the water molecules and the surface decreased and the wetting contact angle of the organic matter surface increased with the increase in the oxygen-containing functional groups; with the increase in the temperature, the interaction energy between the organic matter surface and the water molecules increased, and the wetting contact angle decreased; in the graphite slit pore model with symmetrical C/O ratio, water molecules were symmetrically distributed near the wall of oxygen-containing functionalized graphite, and with the decreasing in the C/O ratio, the relative concentration of water molecules increased and the diffusion coefficient decreased, while methane molecules were clustered in the center of the pore. In the graphite slit pore model with asymmetric C/O ratio, the water molecules were asymmetrically distributed near the wall of the oxygenated functionalized graphite, while the methane molecules were clustered in the center of the pore, where the side with a low C/O ratio had strong hydrophilicity on the wall and a high relative concentration of water molecules, while the side with a high C/O ratio had strong hydrophobicity on the wall and a low relative concentration of water molecules. The research findings were extremely significant to make a study of the influences of shale reservoir characteristics.
- methane /
- organic matter /
- oxygen-containing functional group /
- wettability /
- gas-water distribution /
- graphite

HTML全文

图 1 不同C/O比的石墨层状结构模型

a. 不含氧; b. C/O=16;c. C/O=11;d. C/O=8;e. C/O=6;f. C/O=4;g. C/O=3;h=g

Figure 1. Laminar structure model of graphite with different C/O ratios

下载: 全尺寸图片幻灯片

图 2 不同C/O比的石墨狭缝模型

a. CC6狭缝模型; b. C3-C11狭缝模型

Figure 2. Slit pore model of graphite with different C/O ratios

下载: 全尺寸图片幻灯片

图 3 接触角计算示意图

θ为接触角；h为水滴高度；r为水滴与表面接触圆面的半径; R是水滴(球)的半径

Figure 3. Schematic diagram of calculation of the contact angle

下载: 全尺寸图片幻灯片

图 4 表面上不同方向水分子的相对浓度分布曲线

h为水滴高度；r₁, r₂分别为水滴与x, y轴表面接触圆面的半径

Figure 4. Distribution curve of relative concentrations of water molecules in different directions on the surface

下载: 全尺寸图片幻灯片

图 5 纳米水滴模拟体系的平衡构型

Figure 5. Equilibrium configuration of the nano water drop simulation system

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图 6 纳米水滴在不同表面的润湿接触角

Figure 6. Wetting contact angle of nano water drop on different surfaces

下载: 全尺寸图片幻灯片

图 7 不同C/O比的石墨结构表面水的扩散系数

Figure 7. Self diffusion coefficient of surface water of the graphite structure with different C/O ratios

下载: 全尺寸图片幻灯片

图 8 甲烷和水分子的平衡时构型(对称狭缝孔隙)

Figure 8. Equilibrium configuration of methane and water molecules (symmetrical slit pores)

下载: 全尺寸图片幻灯片

图 9 甲烷分子的相对浓度分布(a)和径向分布(b)函数(对称狭缝孔隙)

Figure 9. Relative concentration distribution (a) and radial distribution function (b) of methane molecules

下载: 全尺寸图片幻灯片

图 10 水分子的相对浓度分布(a)和径向分布(b)函数(对称狭缝孔隙)

Figure 10. Relative concentration distribution (a) and radial distribution function (b) of water molecules

下载: 全尺寸图片幻灯片

图 11 甲烷分子和水分子的扩散系数

Figure 11. Diffusion coefficients of methane and water molecules

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图 12 甲烷和水分子平衡时的瞬时构型(不对称狭缝孔隙)

Figure 12. Equilibrium configuration of methane and water molecules

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图 13 甲烷分子的相对浓度分布(a)和径向分布函数(b) (不对称狭缝孔隙)

Figure 13. Relative concentration distribution (a) and radial distribution function (b) of methane molecules

下载: 全尺寸图片幻灯片

图 14 水分子的相对浓度分布(a)和径向分布函数(b) (不对称狭缝孔隙)

Figure 14. Relative concentration distribution (a) and radial distribution function (b) of water molecules

下载: 全尺寸图片幻灯片

表 1 水滴与不同C/O比的石墨结构表面的相互作用能

Table 1. Interaction energy between water drop and graphite structure surface with different C/O ratio

表面C/O比	温度/T/K	E_total	E_vdW	E_elec	表面C/O比	温度/T/K	E_total	E_vdW	E_elec
表面C/O比	温度/T/K	E/(KJ·mol^-1)			表面C/O比	温度/T/K	E/(KJ·mol^-1)
4	313	-4 722.7	856.2	-5 579.0	4	353	-4 772.3	874.3	-5 646.6
8		-4 680.7	825.7	-5 506.4	8		-4 719.6	843.2	-5 562.8
16		-4 633.4	785.8	-5 419.1	16		-4 654.9	816.6	-5 471.4
32		-4 585.7	763.9	-5 349.6	32		-4 624.2	799.1	-5 423.3
4	333	-4 744.8	864.8	-5 609.6	4	373	-4 784.1	884.6	-5 668.6
8		-4 683.9	839.7	-5 523.5	8		-4 742.8	855.0	-5 597.7
16		-4 643.4	813.6	-5 457.0	16		-4 683.3	833.7	-5 517.0
32		-4 608.7	793.6	-5 402.2	32		-4 660.9	816.3	-5 477.2
注：E_total为体系的相互作用能；E_vdW为体系的范德华能；E_elec为体系的静电能

下载: 导出CSV

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