影响乳状液膜稳定的关键因素与微观机理研究进展
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青岛理工大学 环境与市政工程学院, 山东 青岛 266520

作者简介:

薛志潇(2000—),女,硕士研究生,主要研究方向为重金属污染废水处理与资源化。

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中图分类号:

TF01

基金项目:

国家自然科学基金资助项目(52174336);山东省自然科学基金资助项目(ZR2021MB051)


Review on key factors and microscopic mechanisms affecting the stability of emulsion liquid membrane
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School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266520 , China

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    摘要:

    乳状液膜因具有接触面积大、反应速率快以及能够同步实现萃取和反萃取等优点,被广泛应用于目标物质的提取分离。然而,在乳状液膜分离富集目标物质的过程中,常因液膜聚结、溶胀或泄漏等现象发生,导致液膜不稳定,阻碍了其在工业上的应用。本文系统综述了影响乳状液膜稳定性的关键因素及其微观作用机理,并提出未来研究方向。运载流体浓度存在明确的作用阈值,低浓度时促进金属-载体复合物形成以增强传质,高浓度则因膜相黏度剧增引发液滴聚并和渗透溶胀(水分子向膜内迁移稀释内相),导致稳定性与分离效率双降。表面活性剂体系中,Span 80通过强界面吸附构建弹性单分子膜;β-环糊精聚合物形成高机械强度界面层抵抗聚结;复配体系(如Span 80/Tween 80)则利用HLB值协同效应提升稳定性;但表面活性剂浓度超过临界胶束浓度(CMC)会因胶束增黏和传质阻力增大而削弱稳定效果。膜相添加剂(如异辛醇、两亲高分子P(LM-AA)、聚合物HPAM)通过调节HLB值、空间位阻效应及形成黏性网络显著强化界面膜。操作参数的失稳机制表现为:乳化过程存在临界能量阈值,过度乳化导致液滴过小与膜变薄;萃取时间延长加剧渗透溶胀,内相渗透压累积致膜破裂;温度升高则降低膜相黏度及界面膜强度,加速液滴聚结。微观机理研究揭示了稳定性本质源于动态界面行为:扩张流变特性中弹性模量(Span 80饱和吸附形成高模量膜)直接表征抗形变能力,其与D2EHPA复配时因磷酸基团亲水性增强降低膜刚性;剪切流变行为揭示高界面黏度通过剪切变稀效应耗散外力抑制液滴破裂。未来研究亟需聚焦两方面突破:一是开发绿色高效稳定剂,设计兼具高界面强度、低环境负荷及低传质阻力的新型材料;二是深入探究乳状液膜稳定性的微观机制,从原位界面处分子层面彻底弄清其微观机理,从根本上提高乳状液膜的稳定性,为专用稳定剂的定向设计提供理论依据。本综述为解决乳状液膜失稳难题、推动工业应用提供重要参考。

    Abstract:

    Emulsion liquid membranes (ELMs) are extensively utilized for the extraction and separation of target substances due to their large contact area, rapid reaction kinetics, and capacity for simultaneous extraction and stripping. However, industrial implementation is hindered by membrane instability resulting from phenomena such as coalescence, swelling, or leakage during separation and enrichment processes. This review systematically examines the critical factors influencing ELM stability, their microscopic mechanisms, and future research directions. Carrier concentration exhibits a distinct threshold: low concentrations promote metal-carrier complex formation to enhance mass transfer, while high concentrations induce a sharp increase in membrane-phase viscosity, triggering droplet coalescence and osmotic swelling (water migration into the membrane diluting the internal phase), thereby reducing both stability and separation efficiency. In surfactant systems, Span 80 forms elastic monomolecular films via robust interfacial adsorption; β-cyclodextrin polymers establish high-mechanical-strength interfacial barriers against coalescence; and blended systems (e.g., Span 80/Tween 80) improve stability through HLB synergy. Surfactant concentrations exceeding the critical micelle concentration (CMC) compromise stability due to increased micellar viscosity and mass transfer resistance. Membrane additives (e.g., iso-octanol, amphiphilic polymer P(LM-AA), polymer HPAM) significantly reinforce interfacial films by adjusting HLB values, providing steric hindrance, and forming viscous networks. Destabilization mechanisms in operational parameters manifest as follows: emulsification beyond critical energy thresholds causes excessively small droplets and membrane thinning; prolonged extraction exacerbates osmotic swelling, leading to internal phase osmotic pressure accumulation and rupture; elevated temperatures reduce membrane-phase viscosity and interfacial film strength, accelerating coalescence. Microscopic analyses reveal stability originates from dynamic interfacial behavior: dilatational rheology shows the elastic modulus directly characterizing deformation resistance (high-modulus films formed by Span 80 saturation, with D2EHPA blending reducing rigidity via enhanced hydrophilicity of phosphate groups); shear rheology demonstrates that high interfacial viscosity suppresses droplet rupture through shear-thinning energy dissipation. Future research must focus on two advances: developing green, efficient stabilizers combining high interfacial strength, low environmental impact, and minimal mass transfer resistance; and fundamentally elucidating microscopic mechanisms through in situmolecular-level interfacial characterization to enable rational design of specialized stabilizers. This review provides critical insights for addressing ELM instability and advancing industrial applications.

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薛志潇, 刘杰, 李倩婷, 等. 影响乳状液膜稳定的关键因素与微观机理研究进展[J].中国有色冶金,2025,54(6):52-68.

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  • 收稿日期:2025-04-16
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  • 在线发布日期: 2025-12-26
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