Molecular dynamics investigation on the solubility parameters of supercritical CO2 and petroleum hydrocarbon

doi:10.11949/0438-1157.20250326

Abstract

Abstract:

In the process of oil exploitation, some crude oil will be difficult to extract clearly, resulting in a reduced recovery rate and waste of resources. Supercritical CO₂ is a green solvent with excellent properties. The use of supercritical CO₂ to drive oil flow can enhance oil extraction and improve oil recovery. It is important to investigate the microscopic mechanism of petroleum hydrocarbon extraction by supercritical CO₂ at the molecular level. The compatibility between supercritical CO₂ and various petroleum components was studied using molecular dynamics simulations. The dissolution process of petroleum molecules in supercritical CO₂ was analyzed, and the strengthening effect of cosolvents on the dissolution process was discussed. The results show that the solubility parameter value of supercritical CO₂ is less sensitive to pressure changes under low temperature conditions than to pressure changes under high temperature conditions. For different kinds of petroleum hydrocarbons, the solubility parameters of alkane and aromatic hydrocarbons gradually increased with the increase in carbon number. The solubility parameters of naphthene didn't change significantly with the increase in carbon number. Furthermore, the addition of cosolvent in supercritical CO₂ could effectively improve the solubility of petroleum hydrocarbon molecules, among which methanol has the best solubilization effect. Adding 10% methanol can reduce the solubility parameter difference between supercritical CO₂ and benzopyrene by 25.49%.

Key words: petroleum, supercritical CO₂, dissolution, solubility parameter, molecular simulation, cosolvent

摘要：

石油在开采过程中会出现部分原油难以被提取的问题，造成采收率降低和资源浪费。使用超临界CO₂这一绿色溶剂驱动石油流动可以强化石油开采，提高油田采收率。使用分子动力学模拟研究了超临界CO₂与石油各个组分之间的相容性，并对溶解过程进行了详细分析，同时研究了助溶剂对溶解过程的强化作用。结果表明，超临界CO₂的溶解度参数值在低温条件下对压力变化的敏感性低于在高温条件下对压力变化的敏感性。随着碳数的增加，烷烃和芳香烃的溶解度参数逐渐升高，而环烷烃的溶解度参数并不随碳数的增加发生明显变化。此外，添加助溶剂可有效提升超临界CO₂对石油烃的溶解能力，其中甲醇的助溶效果最好，加入10%的甲醇可使超临界CO₂与苯并芘的溶解度参数差值降低25.49%。

关键词: 石油, 超临界二氧化碳, 溶解, 溶解度参数, 分子模拟, 助溶剂

CLC Number:

TQ 028.8

Junying WANG, Hui JIN. Molecular dynamics investigation on the solubility parameters of supercritical CO₂ and petroleum hydrocarbon[J]. CIESC Journal, 2025, 76(11): 5788-5798.

王俊英, 金辉. 超临界CO₂与石油烃溶解度参数的分子动力学研究[J]. 化工学报, 2025, 76(11): 5788-5798.

Figures/Tables 14

References 35

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类型	名称	分子式	摩尔质量/(g/mol)
烷烃	正己烷	C₆H₁₄	86.178
	正癸烷	C₁₀H₂₂	142.286
	正二十烷	C₂₀H₄₂	282.556
环烷烃	环己烷	C₆H₁₂	84.162
环烷烃	十氢萘	C₁₀H₁₈	138.254
芳香烃	苯	C₆H₆	78.114
	萘	C₁₀H₈	128.174
	苯并芘	C₂₀H₁₂	252.316
树脂/沥青质		C₂₆H₃₂S	376.602

类型	名称	分子式	摩尔质量/(g/mol)
烷烃	正己烷	C₆H₁₄	86.178
	正癸烷	C₁₀H₂₂	142.286
	正二十烷	C₂₀H₄₂	282.556
环烷烃	环己烷	C₆H₁₂	84.162
环烷烃	十氢萘	C₁₀H₁₈	138.254
芳香烃	苯	C₆H₆	78.114
	萘	C₁₀H₈	128.174
	苯并芘	C₂₀H₁₂	252.316
树脂/沥青质		C₂₆H₃₂S	376.602

压力/MPa	δ_实验/MPa^1/2	δ_模拟/MPa^1/2	相对误差/%
8.5	4.9	4.997	1.983
10	7.7	8.148	5.819
20	14.3	14.189	0.777
25	15	14.619	2.537
30	15.6	15.143	2.931
40	16.4	15.802	3.645

压力/MPa	δ_实验/MPa^1/2	δ_模拟/MPa^1/2	相对误差/%
8.5	4.9	4.997	1.983
10	7.7	8.148	5.819
20	14.3	14.189	0.777
25	15	14.619	2.537
30	15.6	15.143	2.931
40	16.4	15.802	3.645

甲醇摩尔分数	δ_实验/MPa^1/2	δ_模拟/MPa^1/2	相对误差/%
0	14.5	14.242	1.782
0.1	15.8	15.481	2.021
0.2	17.4	16.955	2.557
0.3	18.9	18.526	1.979

Molecular dynamics investigation on the solubility parameters of supercritical CO₂ and petroleum hydrocarbon

超临界CO₂与石油烃溶解度参数的分子动力学研究

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Figures/Tables 14

References 35

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温度/K	压力/MPa	总能/(J/m³)	范德华能/(J/m³)	静电能/(J/m³)	其他/(J/m³)
313	10	1.34×10⁸	7.68×10⁷	5.45×10⁷	2.92×10⁶
	15	1.63×10⁸	9.28×10⁷	6.65×10⁷	3.57×10⁶
	20	1.82×10⁸	1.03×10⁸	7.47×10⁷	3.99×10⁶
	25	1.96×10⁸	1.11×10⁸	8.10×10⁷	4.32×10⁶
	30	2.07×10⁸	1.16×10⁸	8.63×10⁷	4.57×10⁶
333	10	2.44×10⁷	1.43×10⁷	9.56×10⁶	5.00×10⁵
	15	1.11×10⁸	6.43×10⁷	4.38×10⁷	2.44×10⁶
	20	1.37×10⁸	7.90×10⁷	5.48×10⁷	3.05×10⁶
	25	1.60×10⁸	9.19×10⁷	6.45×10⁷	3.58×10⁶
	30	1.73×10⁸	9.90×10⁷	7.03×10⁷	3.89×10⁶
353	10	1.30×10⁷	7.75×10⁶	4.98×10⁶	2.67×10⁵
	15	5.18×10⁷	3.07×10⁷	1.99×10⁷	1.13×10⁶
	20	9.73×10⁷	5.73×10⁷	3.78×10⁷	2.20×10⁶
	25	1.20×10⁸	7.03×10⁷	4.70×10⁷	2.73×10⁶
	30	1.39×10⁸	8.08×10⁷	5.48×10⁷	3.18×10⁶
373	10	9.11×10⁶	5.50×10⁶	3.42×10⁶	1.92×10⁵
	15	2.88×10⁷	1.73×10⁷	1.09×10⁷	6.37×10⁵
	20	6.18×10⁷	3.69×10⁷	2.34×10⁷	1.41×10⁶
	25	8.84×10⁷	5.26×10⁷	3.37×10⁷	2.04×10⁶
	30	1.10×10⁸	6.54×10⁷	4.24×10⁷	2.57×10⁶

温度/K	压力/MPa	溶解度参数/MPa^1/2
313	20	22.97
333	20	22.78
353	20	22.65
373	20	22.38
333	10	22.76
333	15	22.79
333	25	22.82
333	30	22.82

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