沥青质、胶质和石油酸对乳状液相变与界面性质的影响研究

doi:10.3969/j.issn.2097-2806.2025.09.006

摘要/Abstract

摘要： 研究了原油中沥青质（AS）、胶质（RE）和石油酸（PA）对乳状液界面行为的影响，重点分析了界面张力、扩张模量、相变点及乳状液粒径的变化规律。结果表明，AS的界面张力最高（25.1 mN/m），RE次之（23.7 mN/m），PA最低（4.8 mN/m），PA的快速吸附加速了界面张力的降低。AS具有最高的扩张模量（38.7 mN/m），有效增强了油水界面膜的强度，推迟了乳状液相变点的出现。PA扩张模量较低，仅为6.1 mN/m，降低了乳状液的稳定性，促使相变点含水率下降至60%。RE和AS的协同作用显著提高了乳状液黏度和稳定性，相变点含水率达70%~80%。研究结果为提高油田采收率及乳状液稳定性调控提供了理论依据。

关键词: 乳状液, 界面张力, 扩张模量, 相变点, 乳状液粒径

Abstract:

The effects of asphaltene （AS）, resin （RE） and petroleum acid （PA） in crude oil on the interfacial behavior of emulsions were investigated. The interfacial tension, dilational modulus, phase transition points and droplet size distribution were analyzed. The results showed that, among the components studied, AS exhibited the highest interfacial tension （25.1 mN/m）, followed by RE （23.7 mN/m）, while PA exhibited the lowest interfacial tension （4.8 mN/m）. The fast adsorption kinetics of PA at the oil-water interface significantly decreased the interfacial tension, highlighting its strong surface activity. AS exhibited the highest dilational modulus （38.7 mN/m）, which strengthened the elasticity of the oil-water interfacial film and postponed the phase transition point. In contrast, PA, with a low dilational modulus of 6.1 mN/m, reduced the emulsion stability by decreasing interfacial elasticity and promoting droplet coalescence, leading to an earlier phase transition at water content of 60%. The synergism between RE and AS significantly increased the viscosity and stability of the emulsion, whose water content at the phase transition point was between 70% and 80%. This work might provide theoretical basis for improving oil recovery efficiency and modulating emulsion stability in oilfield applications.

Key words: emulsion, interfacial tension, dilational modulus, phase transition point, emulsion droplet size

中图分类号:

TE39

汤超, 关娇娇, 张守平, 蔡文良, 林于廉, 谢水祥, 向云飞. 沥青质、胶质和石油酸对乳状液相变与界面性质的影响研究[J]. 日用化学工业（中英文）, 2025, 55(9): 1129-1136.

Chao Tang, Jiaojiao Guan, Shouping Zhang, Wenliang Cai, Yulian Lin, Shuixiang Xie, Yunfei Xiang. Effects of asphaltene, resin, and petroleum acid on the phase transition and interfacial properties of emulsions[J]. China Surfactant Detergent & Cosmetics, 2025, 55(9): 1129-1136.

图/表 9

表1

图1

图2

图3

图4

图5

表2

表3

图6

参考文献 27

[1]	Ravera F, Dziza K, Santini E, et al. Emulsification and emulsion stability: The role of the interfacial properties[J]. Advances in Colloid and Interface Science, 2021, 288: 102344.
[2]	周亚洲, 王德民, 王志鹏, 等. 多孔介质中孔喉级别乳状液的形成条件及黏弹性[J]. 石油勘探与开发, 2017, 44 (1) : 110-116.
[3]	Pu Wanfen, He Meiming, Yang Xuerui, et al. Experimental study on the key influencing factors of phase inversion and stability of heavy oil emulsion: Asphaltene, resin and petroleum acid[J]. Fuel, 2021, 311: 122631.
[4]	Arab D, Kantzas A, Bryant S L. Water flooding of oil reservoirs: effect of oil viscosity and injection velocity on the interplay between capillary and viscous forces[J]. Journal of Petroleum Science and Engineering, 2020, 186: 106691.
[5]	赵学松, 刘琦. 提高原油采收率中油包水乳状液的稳定性研究及其应用[J]. 油田化学, 2023, 40 (2) : 363-373.
[6]	文江波, 罗海军. 基于原油物性定量分析的原油乳状液转相点预测模型[J]. 石油学报(石油加工), 2022, 38 (4) : 910-916.
[7]	Perazzo A, Preziosi V, Guido S. Phase inversion emulsification: Current understanding and applications[J]. Advances in Colloid & Interface Science, 2015, 222: 581-599.
[8]	赖南君, 彭琴, 叶仲斌, 等. 重质组分对稠油乳状液稳定性的影响[J]. 西南石油大学学报(自然科学版), 2014, 36 (1) : 145-149.
[9]	Spiecker P M, Gawrys K L, Kilpatrick P K. Aggregation and solubility behavior of asphaltenes and their subfractions[J]. Journal of Colloid and Interface Science, 2003, 267 (1) : 178-193.
[10]	Liu Rui, Xu Yingxue, Pu Wanfen, et al. A universal route to deciphering the internal mechanism of crude oil self-emulsification[J]. Journal of Molecular Liquids, 2023, 383: 122165.
[11]	孙琳, 任梓寒, 石彦. 原油活性组分及相互作用对乳状液稳定性影响的研究进展[J]. 油田化学, 2022, 39 (2) : 373-380.
[12]	Mansoori G A. Modeling of asphaltene and other heavy organic depositions[J]. Journal of Petroleum Science and Engineering, 1997, 17 (1) : 101-111.
[13]	Yang Xiaoli, Verruto V J, Kilpatrick P K. Dynamic asphaltene-resin exchange at the oil/water interface: Time-dependent W/O emulsion stability for asphaltene/resin model oils[J]. Energy & Fuels, 2007, 21 (3) : 1343-1349.
[14]	Barrow M P, Headley J V, Peru K M, et al. Data visualization for the characterization of naphthenic acids within petroleum samples[J]. Energy & Fuels, 2009, 23 (5) : 2592-2599.
[15]	Flego C, Galasso L, Montanari L, et al. Evolution of naphthenic acids during the corrosion process[J]. Energy & Fuels, 2014, 28 (2) : 1701-1708.
[16]	田哲熙. 辽河油田稠油乳状液稳定性及破乳脱水机理研究[D]. 大庆: 东北石油大学, 2019: 38-40.
[17]	Brandal Ø, Sjöblom J, Øye G. Interfacial behavior of naphthenic acids and multivalent cations in systems with oil and water. I. A pendant drop study of interactions between n-dodecyl benzoic acid and divalent cations[J]. Journal of Dispersion Science & Technology, 2004, 25 (3) : 367-374.
[18]	Binks B P, Lumsdon S O, Catastrophic phase inversion of water-in-oil emulsionsstabilized by hydrophobic silica[J]. Langmuir, 2000, 16: 2539-2547.
[19]	Mohammadpour M, Malayeri M R, Kazemzadeh Y, et al. On the impact of oil compounds on emulsion behavior under different thermodynamic conditions[J]. Scientific Reports, 2023, 13 (1) : 1-11.
[20]	Lifshitz I M, Slyozov V V J. The kinetics of precipitation from supersaturated solid solutions[J]. Journal of Physics & Chemistry of Solids, 1961, 19 (1) : 35-50.
[21]	Adamson A W, Gast A P. Physical chemistry of surfaces, 6th Edition[M]. Wiley, 1997.
[22]	Zolfaghari R, Fakhru’l-Razi, Ahmadun, et al. Demulsification techniques of water-in-oil and oil-in-water emulsions in petroleum industry[J]. Separation & Purification Technology, 2016: 377-407.
[23]	贾雪梅. 胶质及其亚组分结构表征及其对烷基苯磺酸盐溶液界面性能的影响[D]. 长春: 吉林大学, 2020.
[24]	Peter K K. Water-in-crude oil emulsion stabilization: review and unanswered questions[J]. Energy & Fuels, 2012, 26 (7) : 4017-4026.
[25]	Tchoukov P, Yang F, Xu Z, et al. Role of asphaltenes in stabilizing thin liquid emulsion films[J]. Langmuir the Acs Journal of Surfaces & Colloids, 2014, 30 (11) : 3024-3033.
[26]	Israelachvili J N. Intermolecular and surface forces, 3th Edition[M]. Quarterly Review of Biology, 2011.
[27]	Liu Daiwei, Zhang Hao, Li Yujiang, et al. Co-adsorption behavior of asphaltenes and carboxylic acids with different alkyl chain lengths and its effects on the stability of water/model oil emulsion[J]. Fuel, 2021, 295: 120603.

组分	平均粒径/μm
组分	40%	50%	60%	70%	80%
AS	6.3	7.2	8.2	7.8	8.0
RE	5.4	7.2	8.4	8.3	8.3
PA	4.5	5.6	5.2	4.8	4.2
m（AS） ∶m（RE）=1∶1	7.4	8.2	8.1	6.9	6.9
m（AS） ∶m（PA）=1∶1	4.9	4.9	4.7	7.6	6.4
m（AS） ∶m（RE） ∶m（PA）= 1∶1∶1	4.4	5.4	5.6	5.4	5.1
m（AS） ∶m（RE） ∶m（PA）= 1∶5∶1	5.6	5.1	4.4	4.7	4.3