干酪根与芳烃化合物固—液有机质相互作用机理研究

林晓慧; 梁天; 邹艳荣; 陶成; 王远

doi:10.11781/sysydz202403614

干酪根与芳烃化合物固—液有机质相互作用机理研究

doi: 10.11781/sysydz202403614

林晓慧^{1, 2,},
梁天³,
邹艳荣³,
陶成^{1, 2},
王远^{1, 2}

1.
中国石化油气成藏重点实验室, 江苏无锡 214126
2.
中国石化石油勘探开发研究院无锡石油地质研究所, 江苏无锡 214126
3.
中国科学院广州地球化学研究所, 广州 510640

基金项目:

中国石化科技部基础前瞻项目 P23092

中国石化石油勘探开发研究院2023年重点实验室专项 KLP23016

详细信息

作者简介:
林晓慧(1991—)，女，助理研究员，从事油气地球化学研究。E-mail: linxh032.syky@sinopec.com

中图分类号: TE121.1
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出版历程
- 收稿日期: 2023-05-31
- 修回日期: 2024-03-21
- 刊出日期: 2024-05-28

Solid-liquid organic matter interaction mechanism between kerogen and aromatic compounds

LIN Xiaohui^{1, 2
,},
LIANG Tian³,
ZOU Yanrong³,
TAO Cheng^{1, 2},
WANG Yuan^{1, 2}

1.
SINOPEC Key Laboratory of Petroleum Accumulation Mechanisms, Wuxi, Jiangsu 214126, China
2.
Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi, Jiangsu 214126, China
3.
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, Guangdong 510640, China

摘要

摘要: 地质条件下，烃源岩中最初生成的油气，达到饱和后，才能排出运移，而干酪根对烃类的吸附作用，是影响含油饱和度的重要因素。热解作用产生的烃类物质会与干酪根大分子发生相互作用，研究固体干酪根有机质对液态烃的溶解和吸附能力，可以明确烃源岩对烃类化合物的选择性滞留及生排烃特征。芳烃是石油烃类化合物的重要组成部分，在干酪根三维模型的基础上，利用Autodock软件将不同类型的芳烃化合物分子(包括苯、稠环芳烃和稠环芳烃衍生物)与不同成熟度的干酪根分子进行半柔性对接结算，计算两者结合所需的吉布斯自由能，研究芳烃化合物与干酪根结合的特征，从分子层面上研究干酪根吸附芳烃化合物的机理，揭示固—液有机质相互作用的本质。当与相同成熟度的干酪根结合时，稠环芳烃的分子质量越大、化合物中的甲基数量越多、分子缩合度越高，与干酪根分子结合所需的吉布斯自由能越低；芳烃化合物与干酪根分子之间相互作用受到芳烃的分子质量、分子缩合程度以及体系内甲基数量3个因素的影响。处于生烃高峰后，芳碳甲基含量较高的干酪根对芳烃的吸附能力较强；分子质量大、缩合度高的稠环芳烃及其衍生物与干酪根的结合能力较强；常规连接的小分子芳烃化合物在干酪根中的滞留能力较弱，更易发生排烃作用，运移富集成藏。
- 干酪根 /
- 芳烃化合物 /
- 分子对接 /
- 吸附作用 /
- 吉布斯自由能 /
- 生排烃作用
Abstract: Under geological conditions, the initial generation of oil and gas in source rocks reaches saturation before being expelled and migrating, with the adsorption of hydrocarbons by kerogen being a key factor influencing oil saturation. The hydrocarbons produced by pyrolysis interact with kerogen macromolecules. Understanding the solvency and adsorption capacities of solid kerogen organic matter for liquid hydrocarbons can clarify the selective retention of hydrocarbons by source rocks and their characteristics in hydrocarbon generation and expulsion. Aromatic hydrocarbons are crucial components of petroleum hydrocarbons. Based on a three-dimensional model of kerogen, this study employed Autodock software to perform semi-flexible docking calculations between different types of aromatic hydrocarbon molecules (including benzene, polycyclic aromatic hydrocarbons, and their derivatives) and kerogen molecules of varying maturities. The Gibbs free energy required for their binding was calculated to study the characte-risticsof the interaction between aromatic hydrocarbons and kerogen. This study investigated the mechanism of kerogen adsorption of aromatic hydrocarbons at the molecular level, revealing the nature of solid and liquid organic matter interactions. When binding with kerogen of the same maturity, the larger the molecular weight of the polycyclic aromatic hydrocarbons, the greater the number of methyl groups in the compound, and the higher the degree of molecular condensation, the lower the Gibbs free energy required for binding with kerogen molecules. The interaction between aromatic hydrocarbons and kerogen molecules was influenced by three factors: the molecular mass of the aromatic hydrocarbons, the degree of molecular condensation, and the number of methyl groups in the system. After reaching the peak of hydrocarbon generation, kerogen with higher content of aromatic carbon methyl groups showed a stronger adsorption capacity for aromatic hydrocarbons. Polycyclic aromatic hydrocarbons and their derivatives with larger molecular mass and higher degrees of condensation demonstrated stronger binding abilities with kerogen. Conversely, smaller aromatic molecules with conventional connectivity exhibited weaker retention capacities in kerogen, making them more prone to hydrocarbon expulsion, migration, and accumulation into reservoirs.
- kerogen /
- aromatic hydrocarbon /
- molecular docking /
- adsorption effect /
- Gibbs free energy /
- hydrocarbon generation and expulsion
注释:

利益冲突声明/Conflict of Interests

所有作者声明不存在利益冲突。

All authors disclose no relevant conflict of interests.

作者贡献/Authors’Contributions

林晓慧和梁天参与实验设计；林晓慧和王远完成实验操作；林晓慧、邹艳荣和陶成参与论文写作和修改。所有作者均阅读并同意最终稿件的提交。

The experiment was designed by LIN Xiaohui and LIANG Tian. The experimental operation was completed by LIN Xiaohui and WANG Yuan. The manuscript was drafted and revised by LIN Xiaohui, ZOU Yanrong and TAO Cheng. All authors have read the last version of the paper and consented to its submission.

HTML全文

图 1 准噶尔盆地二叠系芦草沟组干酪根大分子不同成熟度三维空间结构

Figure 1. 3D molecular structure of kerogen molecules of different maturity in Permian Lucaogou Formation from Junggar Basin

下载: 全尺寸图片幻灯片

图 2 多环芳烃稠合方式

Figure 2. Different condensation ways of polycyclic aromatic hydrocarbons

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图 3 准噶尔盆地二叠系芦草沟组干酪根分子与不同类型稠环芳烃分子间吉布斯自由能变化

Figure 3. Changes in Gibbs free energy between kerogen molecules and different types of polycyclic aromatic hydrocarbon molecules from Permian Lucaogou Formation in Junggar Basin

下载: 全尺寸图片幻灯片

图 4 准噶尔盆地二叠系芦草沟组干酪根分子与不同类型芳烃衍生物分子间吉布斯自由能变化

Figure 4. Changes in Gibbs free energy between kerogen molecules and different types of aromatic derivatives molecules from Permian Lucaogou Formation in Junggar Basin

下载: 全尺寸图片幻灯片

图 5 准噶尔盆地二叠系芦草沟组干酪根分子不同芳烃化合物分子间吉布斯自由能变化

Figure 5. Changes in Gibbs free energy between kerogen molecules and different aromatic hydrocarbon molecules from Permian Lucaogou Formation in Junggar Basin

下载: 全尺寸图片幻灯片

表 1 吉布斯自由能计算中采用的分子对接配体

Table 1. Ligand of molecular docking used in calculating Gibbs free energy

	配位体	分子模型	分子缩合度（X_bp）
稠环芳烃	苯(C₆H₆)		0
	萘(C₁₀H₈)		0.25
	蒽(C₁₄H₁₀)		0.40
	并四苯(C₁₈H₁₂)		0.50
	芘(C₁₆H₁₀)		0.60
	并五苯(C₂₂H₁₄)		0.57
	苯并芘(C₂₀H₁₂)		0.67
	并六苯(C₂₆H₁₆)		0.63
	C₂₂H₁₂		0.83
	蔻(C₂₄H₁₂)		0.50
	并七苯(C₃₀H₁₈)		0.67
	C₂₆H₁₄		0.86
萘衍生物	甲基萘(C₁₁H₁₀)		0.25
	丙基萘(C₁₃H₁₄)		0.25
	戊基萘(C₁₅H₁₈)		0.25
	三甲基萘(C₁₃H₁₄)		0.25
	五甲基萘(C₁₅H₁₈)		0.25

下载: 导出CSV

表 2 准噶尔盆地二叠系芦草沟组干酪根与稠环芳烃对接结果

Table 2. Molecular docking results of kerogen with polycyclic aromatic hydrocarbons from Permian Lucaogou Formation in Junggar Basin

化合物	分子质量	连接方式	吉布斯自由能/(kJ/mol)
化合物	分子质量	连接方式	原始干酪根	300 ℃, Easy R_o=0.56%	340 ℃, Easy R_o=0.79%	370 ℃, Easy R_o=0.95%	400 ℃, Easy R_o=1.27%
苯(C₆H₆)	78	常规连接芳碳簇	-3.36	-3.59	-4.26	-4.36	-4.05
萘(C₁₀H₈)	128		-5.14	-5.56	-6.62	-5.74	-5.71
蒽(C₁₄H₁₀)	182		-6.62	-7.40	-7.74	-7.36	-7.08
并四苯(C₁₈H₁₂)	228		-8.16	-8.86	-8.79	-8.92	-8.46
并五苯(C₂₂H₁₄)	278		-8.74	-9.67	-9.62	-10.08	-9.31
并六苯(C₂₆H₁₆)	328		-10.01	-10.49	-10.22	-11.01	-9.94
并七苯(C₃₀H₁₈)	378		-10.79	-11.25	-10.62	-11.94	-10.23
芘(C₁₆H₁₀)	202	环状连接芳碳簇	-7.01	-7.83	-7.89	-7.94	-7.45
苯并芘(C₂₀H₁₂)	252		-8.41	-9.54	-9.44	-9.75	-9.17
C₂₂H₁₂	276		-8.94	-10.05	-9.65	-10.06	-9.54
C₂₆H₁₄	326		-9.98	-11.23	-10.71	-11.99	-10.72
蔻(C₂₄H₁₂)	300		-8.65	-10.43	-10.05	-10.94	-9.30

下载: 导出CSV

表 3 准噶尔盆地二叠系芦草沟组干酪根与萘系物对接结果

Table 3. Molecular docking results of kerogen and naphthalene derivatives from Permian Lucaogou Formation in Junggar Basin

化合物	分子质量	结构特征	吉布斯自由能/(kJ/mol)
化合物	分子质量	结构特征	原始干酪根	300 ℃，Easy R_o=0.56%	340 ℃，Easy R_o=0.79%	370 ℃，Easy R_o=0.95%	400 ℃，Easy R_o=1.27%
甲基萘(C₁₁H₁₀)	142	烷基萘	-5.6	-6.13	-6.75	-6.11	-5.99
丙基萘(C₁₃H₁₄)	160		-6.02	-6.61	-7.11	-6.58	-6.36
戊基萘(C₁₅H₁₈)	198		-6.41	-6.99	-7.09	-6.9	-6.94
三甲基萘(C₁₃H₁₄)	170	多甲基萘	-6.15	-6.88	-7.17	-6.71	-6.71
五甲基萘(C₁₅H₁₈)	198	多甲基萘	-6.56	-7.11	-7.38	-7.34	-6.97

下载: 导出CSV

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