低界面张力驱油表面活性剂的界面扩张流变研究

doi:10.3969/j.issn.2097-2806.2025.08.002

摘要/Abstract

摘要： 采用旋转滴法研究了阴离子表面活性剂重烷基苯磺酸盐（HABS）和石油磺酸盐（PS）的界面扩张流变特性。考察了振荡频率、表面活性剂浓度、油相、界面张力对界面模量的影响，比较了HABS和PS的界面膜强度和界面活性的差异。结果表明，HABS的亲水亲油平衡能力比PS强，能将癸烷-水界面张力和原油-水界面张力降低至0.01 mN/m数量级。HABS和PS分子间均以静电斥力为主，扩散-交换过程主导，界面膜黏性较大。在癸烷-水界面，分子尺寸较小的HABS扩散-交换更快，界面膜的黏性比PS高，扩张模量在高浓度时降低得更明显；原油中活性组分在原油-水界面上混合吸附，造成HABS和PS界面膜的黏弹特性相似。HABS与原油组分间存在协同效应，在将界面张力降低至0.01 mN/m数量级的同时，还能维持一定的界面膜强度，在提高原油采收率方面有较大潜力。

关键词: 旋转滴法, 界面张力, 界面扩张模量, 重烷基苯磺酸盐, 石油磺酸盐

Abstract:

The interfacial dilational rheological properties of anionic surfactants heavy alkylbenzene sulfonate （HABS） and petroleum sulfonate （PS） were studied by spinning drop method. The effects of oscillation frequency, surfactant concentration, oil phase and interfacial tension on the interfacial modulus were investigated. The differences of interfacial film strength and interfacial activity between HABS and PS were compared. The results showed that the hydrophilic-lipophilic balance of HABS was better than that of PS, which could reduce the interfacial tension to the magnitude order of 0.01 mN/m against decane and crude oil. Both HABS and PS molecules were dominated by electrostatic repulsion, in which the diffusion-exchange process was dominant, and the viscosity of interfacial film was high. At the decane-water interface, compared with PS, the diffusion-exchange of HABS who had smaller molecular size was faster, the viscosity of interface film was higher, and the dilational modulus decreased more significantly at high concentration. The surface-active components in crude oil adsorbed on the crude oil-water interface, resulting in similar viscoelastic properties of interfacial films of HABS and PS. There was synergistic effect between HABS and crude oil components. As a result, HABS could not only reduce the interfacial tension to the magnitude order of 0.01 mN/m, but also maintain certain interfacial film strength, which showed great potential in improving crude oil recovery.

Key words: spinning drop method, interfacial tension, interfacial dilational modulus, heavy alkylbenzene sulfonate, petroleum sulfonate

中图分类号:

TQ423

楚艳苹, 高峰, 张伟华, 张磊, 张路. 低界面张力驱油表面活性剂的界面扩张流变研究[J]. 日用化学工业（中英文）, 2025, 55(8): 961-968.

Yanping Chu, Feng Gao, Weihua Zhang, Lei Zhang, Lu Zhang. Study on interfacial dilational rheology of surfactant flooding with low-interfacial-tension surfactants[J]. China Surfactant Detergent & Cosmetics, 2025, 55(8): 961-968.

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参考文献 32

[1]	刘必心, 侯吉瑞, 张宁. 氢氧化钠对重烷基苯磺酸钠水溶液/油体系界面张力的影响[J]. 日用化学工业, 2014, 44 (4) : 200-203, 221.
[2]	Xiao Baoqing, Qu Jingkui.Synthesis and interfacial properties of alkylbenzene sulfonates for flooding[G]//Institute of Electrical and Electronics Engineers. 2010 International Conference on Mechanic Automation and Control Engineering. Wuhan: Institute of Electrical and Electronics Engineers, 2010: 1701-1705.
[3]	Niu R X, He J Y, Long B, et al. Adsorption, wetting, foaming, and emulsification properties of mixtures of nonylphenol dodecyl sulfonate based on linear alpha-olefin and heavy alkyl benzene sulfonate[J]. Journal of Dispersion Science and Technology, 2018, 39 (8) : 1108-1114.
[4]	Li G, Zhou Z, Fan J, et al. Study on microscopic oil displacement mechanism of alkaline-surfactant-polymer ternary flooding[J]. Materials, 2024.
[5]	Liu B, Hou J, Tang H, et al. Experimental study of the effect of strong alkali on lowering the interfacial tension of oil/heavy alkylbenzene sulfonates system[J]. Chinese Journal of Chemistry, 2011, 29 (11) : 2315-2319.
[6]	王伟, 岳湘安, 张立娟, 等. 超低界面张力石油磺酸盐复配驱油剂研究[J]. 日用化学工业, 2011, 41 (5) : 334-337.
[7]	Luan H, Zhou Z, Xu C, et al. Study on the synergistic effects between petroleum sulfonate and a nonionic-anionic surfactant for enhanced oil recovery[J]. Energies, 2022, 15 (3) : 1177.
[8]	Zhao Y, Xu Z, Li Z, et al. Synthesis and interfacial tension behavior of heavy alkyl benzene sulfonates[J]. Petroleum Science and Technology, 2006, 24 (7) : 821-827.
[9]	Li X, Yue X A, Wang Z, et al. Role of emulsification and interfacial tension of a surfactant for oil film displacement[J]. Energy & Fuels, 2021, 35 (4) : 3032-3041.
[10]	Mahboob A, Kalam S, Kamal M S, et al. EOR Perspective of microemulsions: A review[J]. Journal of Petroleum Science and Engineering, 2022, 208: 109312.
[11]	Zhao H, Kang W, Yang H, et al. Emulsification and stabilization mechanism of crude oil emulsion by surfactant synergistic amphiphilic polymer system[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 609: 125726.
[12]	Sun Q, Zhou Z H, Han L, et al. How to regulate the migration ability of emulsions in micro-scale pores: droplet size or membrane strength?[J]. Molecules, 2023, 28 (4) : 1672.
[13]	Marquez R, Ontiveros J F, Barrios N, et al. Advantages and limitations of different methods to determine the optimum formulation in surfactant-oil-water systems: a review[J]. Journal of Surfactants and Detergents, 2024, 27 (1) : 5-36.
[14]	张磊, 宫清涛, 周朝辉, 等. 旋转滴方法测量界面扩张流变性质[J]. 物理化学学报, 2009, 25 (1) : 41-46.
[15]	Alvarado J G, Bullón J, Salazar-Rodríguez F, et al. n-C7 Asphaltenes characterization as surfactants and polar oil from the HLDN model perspective[J]. Industrial & Engineering Chemistry Research, 2023, 62 (30) : 11872-11884.
[16]	Marquez R, Antón R, Vejar F, et al. New interfacial rheology characteristics measured using a spinning drop rheometer at the optimum formulation. Part 2. Surfactant-oil-water systems with a high volume of middle-phase microemulsion[J]. Journal of Surfactants and Detergents, 2019, 22 (2) : 177-188. doi: 10.1002/jsde.12245
[17]	Marquez R, Acevedo N, Rondón M, et al. Breaking of water-in-crude oil emulsions. 10. Experimental evidence from a quartz crystal resonator sensor and an oscillating spinning drop interfacial rheometer[J]. Energy & Fuels, 2023, 37 (4) : 2735-2749.
[18]	Ma G, Gong Q, Xu Z, et al. The interfacial dilational rheology of surfactant solutions with low interfacial tension[J]. Molecules, 2025, 30 (3) : 447.
[19]	Zhang L, Luo L, Zhao S, et al. Studies of synergism/antagonism for lowering dynamic interfacial tensions in surfactant/alkali/acidic oil systems. Part 1: synergism/antagonism in surfactant/model oil systems[J]. Journal of Colloid and Interface Science, 2002, 249 (1) : 187-193. pmid: 16290585
[20]	Gao S T. Generation of low interfacial tension and determination of the EACN of Daqing crude oil[J]. Oilfield Chemistry, 1985, 2 (2) : 96-102.
[21]	Sun H Q, Guo Z Y, Cao X L, et al. Interfacial interactions between oleic acid and betaine molecules at decane-water interface: a study of dilational rheology[J]. Journal of Molecular Liquids, 2020, 316: 113784.
[22]	Jiang Q, Zhu Y W, Liu Y, et al. Studies on interfacial interactions between extended surfactant and betaine by dilational rheology[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2025, 710: 136245.
[23]	Liu K X, Yin H J, Zhang L, et al. Effect of EO group on the interfacial dilational rheology of fatty acid methyl ester solutions[J]. Colloids and Surfaces A, 2018, 553: 11-19.
[24]	Liu K X, Yin H J, Zhang L, et al. Interfacial dilational rheology of fatty acid methyl ester and alkyl benzene sulfonate mixed solutions[J]. Journal of Molecular Liquids, 2018, 269: 335-343.
[25]	Xin X, Zhang H, Xu G, et al. Influence of CTAB and SDS on the properties of oil-in-water nano-emulsion with paraffin and Span 20/Tween 20[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 418: 60-67.
[26]	Chen Z, Zhang P, Sun Y, et al. Interfacial dilational rheology of sodium lauryl glycine and mixtures with conventional surfactants[J]. Journal of Surfactants and Detergents, 2019, 22 (6) : 1477-1485.
[27]	Marquez R, Bullon J, Forgiarini A, et al. The oscillatory spinning drop technique. An innovative method to measure dilational interfacial rheological properties of brine-crude oil systems in the presence of asphaltenes[J]. Colloids and Interfaces, 2021, 5 (3) : 42.
[28]	Marquez R, Meza L, Alvarado J G, et al. Interfacial rheology measured with a spinning drop interfacial rheometer: particularities in more realistic surfactant-oil-water systems close to optimum formulation at HLD= 0[J]. Journal of Surfactants and Detergents, 2021, 24 (4) : 587-601. doi: 10.1002/jsde.12502
[29]	Marquez R, Forgiarini A M, Langevin D, et al. Breaking of water-in-crude oil emulsions. Part 9. New interfacial rheology characteristics measured using a spinning drop rheometer at optimum formulation[J]. Energy & Fuels, 2019, 33 (9) : 8151-8164.
[30]	Zamora J M, Marquez R, Forgiarini A M, et al. Interfacial rheology of low interfacial tension systems using a new oscillating spinning drop method[J]. Journal of Colloid and Interface Science, 2018, 519: 27-37. doi: S0021-9797(18)30155-3 pmid: 29477897
[31]	Marquez R, Forgiarini A M, Fernández J, et al. New interfacial rheology characteristics measured using a spinning-drop rheometer at the optimum formulation of a simple surfactant-oil-water system[J]. Journal of Surfactants and Detergents, 2018, 21 (5) : 611-623.
[32]	Marquez R, Forgiarini A M, Langevin D, et al. Instability of emulsions made with surfactant-oil-water systems at optimum formulation with ultralow interfacial tension[J]. Langmuir, 2018, 34 (31) : 9252-9263. doi: 10.1021/acs.langmuir.8b01376 pmid: 29986590