水蒸气诱导相分离构筑海绵孔结构超亲水聚醚砜膜及其油/水乳液分离性能研究

doi:10.11949/0438-1157.20241227

摘要/Abstract

摘要：

膜分离技术因高效率、低能耗、无须化学添加剂等优势已成为处理含油污水的重要手段。聚醚砜(PES)膜由于出色的热稳定性和机械强度被广泛应用于水处理，但制备具有高孔隙率海绵孔结构和稳定超亲水性的PES膜，实现含油污水高通量、抗污染分离仍是一个难题。在此，通过水蒸气诱导相分离(VIPS)方法，以PES为成膜材料、聚乙烯吡咯烷酮(PVP)为亲水添加剂、聚乙二醇(PEG)为制孔剂制备了海绵孔结构的超亲水PES膜。同时通过Na₂S₂O₈引发膜内PVP自由基交联反应抑制PVP溶出流失，使PES膜保持长时间稳定的超亲水性质和抗油污染性能。此PES膜分离油/水乳液时分离效率高于99.8%，水通量达到3900 L·m^-2·h^-1·bar^-1，并展现出优异的循环性能，通量衰减率低至5.4%，水冲洗后通量恢复率高于96.3%。

关键词: 膜, 制备, 污染, 油/水分离, 超亲水

Abstract:

Membrane separation has emerged as a critical technology for treating oily wastewater due to its high efficiency, low energy consumption, and elimination of chemical additives. Polyethersulfone (PES) membranes are widely applied in wastewater treatment owing to their excellent thermal stability and mechanical strength. However, it is still a difficult problem to prepare PES membranes with high porosity sponge pore structure and stable super-hydrophilicity to achieve high-flux and anti-pollution separation of oily wastewater. Herein, we report the vapor-induced phase separation (VIPS) method for the fabrication of PES membranes with sponge-like pores and stable super-hydrophilicity, using PES as the matrix, polyvinylpyrrolidone (PVP) as a hydrophilic additive, and polyethylene glycol (PEG) as a pore-forming agent. At the same time, the PVP free radical cross-linking reaction in the membrane induced by Na₂S₂O₈inhibited the dissolution and loss of PVP, so that the PES membrane maintained a long-term stable super-hydrophilic property and anti-oil pollution performance. The cross-linking of PVP effectively restrains the leaching of PVP during long-term use of the membranes. The PES membranes demonstrate an outstanding oil-in-water emulsion separation efficiency exceeding 99.8%, with a high water flux of 3900 L·m^-2·h^-1·bar^-1, and exhibits excellent cycle performance, with a flux attenuation rate as low as 5.4%, and a flux recovery rate of more than 96.3% after water washing.

Key words: membrane, fabrication, fouling, oil-water separation, super-hydrophilicity

中图分类号:

TQ 028.8

朱迪, 高守建, 方望熹, 靳健. 水蒸气诱导相分离构筑海绵孔结构超亲水聚醚砜膜及其油/水乳液分离性能研究[J]. 化工学报, 2025, 76(5): 2397-2409.

Di ZHU, Shoujian GAO, Wangxi FANG, Jian JIN. Construction of PES membranes with sponge-like pores and stable super-hydrophilicity through vapor-induced phase separation for oil-in-water emulsion separation[J]. CIESC Journal, 2025, 76(5): 2397-2409.

图/表 13

图1 海绵孔结构PES/PVP共混膜的制备过程示意图

Fig.1 Illustration showing the fabrication of the sponge-like PES/PVP blend membrane

图2 相对湿度对PES/PVP膜表面和截面形貌的影响

Fig.2 Effect of relative humidity on surface and cross section morphology of PES/PVP membranes

图3 相对湿度对PES/PVP膜孔径和水通量的影响

Fig.3 Effect of relative humidity on pore size and water flux of PES/PVP membranes

图4 蒸汽温度对PES/PVP膜表面和截面形貌的影响

Fig.4 Effect of vapor temperature on surface and cross section morphology of PES/PVP membranes

图5 蒸汽温度对PES/PVP膜孔径和水通量的影响

Fig.5 Effect of vapor temperature on pore size and water flux of PES/PVP membranes

图6 诱导时间对PES/PVP膜表面和截面形貌的影响

Fig.6 Effect of induction time on surface and cross section morphology of PES/PVP membranes

图7 诱导时间对PES/PVP膜孔径和水通量的影响

Fig.7 Effect of induction time on pore size and water flux of PES/PVP membranes

图8 PES/PVP膜的动态水接触角（a）、动态水下油接触角（b）表征以及水中抗大豆油（c）和二氯乙烷（d）污染能力

Fig.8 Dynamicwater contact angles (a), underwater oil contact angles (b), antifouling ability to soybean oil (c) and dichloroethane (d) of the PES/PVP membrane

图9 热活化Na2S2O8引发PVP分子间自由基交联反应的原理

Fig.9 Illustration for the radical crosslinking of PVP molecules initiated by thermally activated Na2S2O8

图10 PES/PVP膜和PES/PVPC膜的表面组成及形貌

Fig.10 Surface composition and morphology of PES/PVP membrane and PES/PVPC membrane

图11 PES/PVP膜与PES/PVPC膜在水冲刷7 d前后的表面组成和浸润性变化

Fig.11 Changes in surface composition and wettability of PES/PVP membrane and PES/PVPC membrane before and after water washing for 7 d

图12 PES/PVP膜与PES/PVPC膜的抗污染性能

Fig.12 Anti-pollution performance of PES/PVP membrane and PES/PVPC membrane

图13 PES/PVPC膜对不同种类油/水乳液的分离性能

Fig.13 Separation performance of PES/PVPC membrane for different kinds of oil/water emulsions

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