页岩油在干酪根中吸附行为的分子动力学模拟与启示

doi:10.11743/ogg20230609

Abstract

Abstract:

Investigating the adsorption behavior in organic matter and its associated pores holds critical significance for revealing the occurrence states and mechanisms of shale oil. Differing from the previous method of replacing the organic matter model with the graphene model， a realistic kerogen molecular model， the Type Ⅱ-C model， is employed to simulate the adsorption behavior of multi-component shale oil within organic pores based on the general Amber force field （GAFF）. The results are as follows. （1） Unlike graphene， which can only be used to simulate surface adsorption， kerogen has the dual functions of both adsorption and absorption. Competitive shale oil adsorption transpires on kerogen walls， dominated by the adsorption of polarity and heavy components， while the kerogen skeleton is characterized by absorption of small molecules moving far away. The shale oil adsorption on the surface and absorption in the skeleton with migration are influenced by the interaction energy between shale oil and kerogen， as well as the molecular size. Specifically， heavy components of shale oil are subjected to strong adsorption but weak absorption， while its light components undergo weak adsorption but strong absorption；（2） The absorption of shale oil components leads to the deformation of the kerogen skeleton and pores， manifested as the formation of new pores and the expansion and partial collapse of original pores. The plasticity of kerogen plays a significant role in its shale oil absorption and further skeleton swelling. Highly plastic kerogen （with low maturity） is more prone to absorb shale oil and swell significantly in skeleton. In contrast， weakly plastic kerogen swells slightly with absorption；（3） An increase in temperature enhances the absorption of aromatic hydrocarbon molecules （like naphthalene） and non-polar molecules （e.g.， formic acid， ethanol， and thiophene） in kerogen skeleton， which reduces the adsorption on kerogen surface， and is conducive to the desorption of saturated hydrocarbon molecules. Additionally， pressure produces insignificant effects on the shale oil adsorption and absorption in kerogen. In this study， the realistic kerogen molecular model is innovatively applied to simulate kerogen’s adsorption and absorption of shale oil components， which is of great help in objectively revealing the shale oil occurrence state and mechanism in kerogen.

Key words: adsorption, absorption, occurrence state, kerogen model, molecular dynamics simulation, shale oil

CLC Number:

TE122.1

Min WANG, Changqi YU, Junsheng FEI, Jinbu LI, Yuchen ZHANG, Yu YAN, Yan WU, Shangde DONG, Yulong TANG. Molecular dynamics simulation of shale oil adsorption in kerogen and its implications[J]. Oil & Gas Geology, 2023, 44(6): 1442-1452.

Figures/Tables 8

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References 38

1	孙龙德，刘合，何文渊，等. 大庆古龙页岩油重大科学问题与研究路径探析［J］. 石油勘探与开发， 2021， 48（3）： 453-463.
	SUN Longde， LIU He， HE Wenyuan， et al. An analysis of major scientific problems and research paths of Gulong shale oil in Daqing Oilfield， NE China［J］. Petroleum Exploration and Development， 2021， 48（3）： 453-463.
2	王永诗，李政，王民，等. 渤海湾盆地济阳坳陷陆相页岩油吸附控制因素［J］. 石油与天然气地质， 2022， 43（3）： 489-498.
	WANG Yongshi， LI Zheng， WANG Min， et al. Factors controlling lacustrine shale oil adsorption in the Jiyang Depression， Bohai Bay Basin［J］. Oil & Gas Geology， 2022， 43（3）： 489-498.
3	王学军，宁方兴，郝雪峰，等. 古近系页岩油赋存特征——以济阳坳陷为例［J］. 科学技术与工程， 2017， 17（29）： 39-48.
	WANG Xuejun， NING Fangxing， HAO Xuefeng， et al. Paleogene shale oil occurrence features： A case of Jiyang Depression［J］. Science Technology and Engineering， 2017， 17（29）： 39-48.
4	吴松涛，邹才能，朱如凯，等. 鄂尔多斯盆地上三叠统长7段泥页岩储集性能［J］. 地球科学（中国地质大学学报）， 2015， 40（11）： 1810-1823.
	WU Songtao， ZOU Caineng， ZHU Rukai， et al. Reservoir quality characterization of Upper Triassic Chang 7 shale in Ordos Basin［J］. Earth Science（Journal of China University of Geosciences）， 2015， 40（11）： 1810-1823.
5	CHEN Guohui， LU Shuangfang， ZHANG Junfang， et al. A method for determining oil-bearing pore size distribution in shales： A case study from the Damintun Sag， China［J］. Journal of Petroleum Science and Engineering， 2018， 166： 673-678.
6	李吉君，史颖琳，黄振凯，等. 松辽盆地北部陆相泥页岩孔隙特征及其对页岩油赋存的影响［J］. 中国石油大学学报（自然科学版）， 2015， 39（4）： 27-34.
	LI Jijun， SHI Yinglin， HUANG Zhenkai， et al. Pore characteristics of continental shale and its impact on storage of shale oil in northern Songliao Basin［J］. Journal of China University of Petroleum（Edition of Natural Science）， 2015， 39（4）： 27-34.
7	王民，马睿，李进步，等. 济阳坳陷古近系沙河街组湖相页岩油赋存机理［J］. 石油勘探与开发， 2019， 46（4）： 789-802.
	WANG Min， MA Rui， LI Jinbu， et al. Occurrence mechanism of lacustrine shale oil in the Paleogene Shahejie Formation of Jiyang Depression， Bohai Bay Basin， China［J］. Petroleum Exploration and Development， 2019， 46（4）： 789-802.
8	钱门辉，蒋启贵，黎茂稳，等. 湖相页岩不同赋存状态的可溶有机质定量表征［J］. 石油实验地质， 2017， 39（2）： 278-286.
	QIAN Menhui， JIANG Qigui， LI Maowen， et al. Quantitative characterization of extractable organic matter in lacustrine shale with different occurrences［J］. Petroleum Geology and Experiment， 2017， 39（2）： 278-286.
9	蒋启贵，黎茂稳，钱门辉，等. 不同赋存状态页岩油定量表征技术与应用研究［J］. 石油实验地质， 2016， 38（6）： 842-849.
	JIANG Qigui， LI Maowen， QIAN Menhui， et al. Quantitative characterization of shale oil in different occurrence states and its application［J］. Petroleum Geology and Experiment， 2016， 38（6）： 842-849.
10	田善思. 页岩储层孔隙微观特征及页岩油赋存与可动性评价［D］. 青岛：中国石油大学（华东）， 2019.
	TIAN Shansi. Micro-pore characteristics of shale reservoirs and evaluation of shale oil occurrence and movability［D］. Qingdao： China University of Petroleum（East China）， 2019.
11	张世明. 东营凹陷页岩油赋存特征分子动力学模拟［J］. 油气地质与采收率， 2021， 28（5）： 74-80.
	ZHANG Shiming. Molecular dynamics simulation of shale oil occurrence in Dongying Depression［J］. Petroleum Geology and Recovery Efficiency， 2021， 28（5）： 74-80.
12	王森，冯其红，查明，等. 页岩有机质孔缝内液态烷烃赋存状态分子动力学模拟［J］. 石油勘探与开发， 2015， 42（6）： 772-778.
	WANG Sen， FENG Qihong， ZHA Ming， et al. Molecular dynamics simulation of liquid alkane occurrence state in pores and fractures of shale organic matter［J］. Petroleum Exploration and Development， 2015， 42（6）： 772-778.
13	HU Yinan， DEVEGOWDA D， SIGAL R. A microscopic characterization of wettability in shale kerogen with varying maturity levels［J］. Journal of Natural Gas Science and Engineering， 2016， 33： 1078-1086.
14	YANG Yongfei， LIU Jie， YAO Jun， et al. Adsorption behaviors of shale oil in kerogen slit by molecular simulation［J］. Chemical Engineering Journal， 2020， 387： 124054.
15	UNGERER P， COLLELL J， YIANNOURAKOU M. Molecular modeling of the volumetric and thermodynamic properties of kerogen： Influence of organic type and maturity［J］. Energy & Fuels， 2015， 29（1）： 91-105.
16	ZHOU Juan， JIN Zhehui， LUO K H. The role of brine in gas adsorption and dissolution in kerogen nanopores for enhanced gas recovery and CO₂ sequestration［J］. Chemical Engineering Journal， 2020， 399： 125704.
17	WANG Sen， YAO Xinyu， FENG Qihong， et al. Molecular insights into carbon dioxide enhanced multi-component shale gas recovery and its sequestration in realistic kerogen［J］. Chemical Engineering Journal， 2021， 425： 130292.
18	LI Zheng， YAO Jun， FIROOZABADI A. Kerogen swelling in light hydrocarbon gases and liquids and validity of Schroeder’s paradox［J］. The Journal of Physical Chemistry C， 2021， 125（15）： 8137-8147.
19	YU Xinran， LI Jing， CHEN Zhangxin， et al. Determination of CH₄， C₂H₆ and CO₂ adsorption in shale kerogens coupling sorption-induced swelling［J］. Chemical Engineering Journal， 2021， 410： 127690.
20	TISSOT B P， WELTE D H. Petroleum formation and occurrence［M］. 2nd ed. Berlin： Springer， 1984.
21	HAN Qiuya， LI Meijun， LIU Xiaoqiang， et al. A maturation scale for molecular simulation of kerogen thermal degradation［J］. Organic Geochemistry， 2023， 175： 104507.
22	TIAN Shansi， ERASTOVA V， LU Shuangfang， et al. Understanding model crude oil component interactions on kaolinite silicate and aluminol surfaces： Toward improved understanding of shale oil recovery［J］. Energy & Fuels， 2018， 32（2）： 1155-1165.
23	FEI Junsheng， WANG Min， LI Jinbu， et al. Molecular dynamics simulation of adsorption and absorption behavior of shale oil in realistic kerogen slits［J］. Energy & Fuels， 2023， 37（5）： 3654-3671.
24	BAYLY C I， CIEPLAK P， CORNELL W， et al. A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges： The RESP model［J］. The Journal of Physical Chemistry， 1993， 97（40）： 10269-10280.
25	LORENTZ H A. Ueber die anwendung des satzes vom virial in der kinetischen theorie der gase［J］. Annalen der Physik， 1881， 248（1）： 127-136.
26	SANDVIK E I， YOUNG W A， CURRY D J. Expulsion from hydrocarbon sources： The role of organic absorption［J］. Organic Geochemistry， 1992， 19（1/3）： 77-87.
27	HO T A， WANG Yifeng， XIONG Yongliang， et al. Differential retention and release of CO₂ and CH₄ in kerogen nanopores： Implications for gas extraction and carbon sequestration［J］. Fuel， 2018， 220： 1-7.
28	陈晓明，李建忠，郑民，等. 干酪根溶解理论及其在页岩气评价中的应用探索［J］. 天然气地球科学， 2012， 23（1）： 14-18.
	CHEN Xiaoming， LI Jianzhong， ZHENG Min， et al. Kerogen solution theory and its exploratory application in shale gas assessment［J］. Natural Gas Geoscience， 2012， 23（1）： 14-18.
29	TESSON S， FIROOZABADI A. Deformation and swelling of kerogen matrix in light hydrocarbons and carbon dioxide［J］. The Journal of Physical Chemistry C， 2019， 123（48）： 29173-29183.
30	KELEMEN S R， WALTERS C C， ERTAS D， et al. Petroleum expulsion Part 2. Organic matter type and maturity effects on kerogen swelling by solvents and thermodynamic parameters for kerogen from regular solution theory［J］. Energy & Fuels， 2006， 20（1）： 301-308.
31	WANG Sen， FENG Qihong， JAVADPOUR F， et al. Oil adsorption in shale nanopores and its effect on recoverable oil-in-place［J］. International Journal of Coal Geology， 2015， 147/148： 9-24.
32	TESSON S， FIROOZABADI A. Methane adsorption and self-diffusion in shale kerogen and slit nanopores by molecular simulations［J］. The Journal of Physical Chemistry C， 2018， 122（41）： 23528-23542.
33	FALK K， PELLENQ R， ULM F J， et al. Effect of chain length and pore accessibility on alkane adsorption in kerogen［J］. Energy & Fuels， 2015， 29（12）： 7889-7896.
34	李明，王民，张金友，等. 中国典型盆地陆相页岩油组分评价及意义［J］. 石油与天然气地质， 2023， 44（6）： 1479-1498.
	LI Ming， WANG Min， ZHANG Jinyou， et al. Evaluation and significance of continental shale oil composition in typical basins of China［J］. Oil & Gas Geology， 2023， 44（6）： 1479-1498.
35	HUANG Liang， KHOSHNOOD A， FIROOZABADI A. Swelling of kimmeridge kerogen by normal-alkanes， naphthenes and aromatics［J］. Fuel， 2020， 267， 117155.
36	LIANG Tian， ZHAN Zhaowen， ZOU Yanrong， et al. Interaction between organic solvents and three types of kerogen investigated via X-ray diffraction［J］. Energy & Fuels， 2022， 36（3）： 1350-1357.
37	LIANG Tian， ZHAN Zhaowen， ZOU Yanrong， et al. Interaction between organic solvents and three types of kerogen investigated via X-ray diffraction［J］. Energy & Fuels， 2022， 36（3）： 1350-1357.
38	李进步，王民，卢双舫，等. 页岩吸附油定量评价模型——以松辽盆地北部白垩系青山口组一段为例［J］. 石油勘探与开发， 2023， 50（5）： 990-1002.
	LI Jinbu， WANG Min， LU Shuangfang， et al. Quantitative evaluation model of shale oil adsorption： A case study of the first member of Cretaceous Qingshankou Formation in northern Songliao Basin， NE China［J］. Petroleum Exploration and Development， 2023， 50（5）： 990-1002.

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Molecular dynamics simulation of shale oil adsorption in kerogen and its implications

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