Noria-PEI共沉积技术构筑高抗油污染氟化超滤膜

doi:10.19965/j.cnki.iwt.2024-0916

摘要/Abstract

摘要：

膜分离技术由于占地面积小、操作简单、分离效率高等优势，被认为是有效处理油水混合物的方法之一，具有极大的工业应用潜力。为解决油水分离过程中油滴黏附导致的膜污染及渗透通量下降的问题，以聚乙烯亚胺（PEI）、Noria水轮酚为亲水改性溶液，通过PEI-Noria共沉积对聚砜（PSF）超滤膜进行氨基化处理，随后利用氨基和酰氯的高反应活性将全氟辛酰氯（PFOC）接枝到膜上，制备高抗油污染氟化超滤膜。通过系统评价PEI相对分子质量及其在改性溶液中的质量分数对复合膜界面疏油性能和分离性能的影响，筛选得到最佳制膜条件为PEI相对分子质量600、改性溶液中PEI质量分数为0.8%。该功能氟化涂层赋予复合膜优异的膜通量和抗油污染性能，十二烷、石油醚、汽油、十六烷等不同种类油水乳液通量分别为（45±5）、（65±5）、（50±5）、（40±5） kg/（m²·h），截留均为98%以上。经过循环水洗后，纯水通量恢复率（FRR）可高达90%。该高抗油污染氟化超滤膜可应用于各种含油污水净化处理，具有抗污染性好、连续运行稳定性好的特点，具有较大的工业应用潜力。

关键词: 膜分离, 油水混合物, 原位氟化技术, 抗油污染

Abstract:

Membrane separation technology is considered as an effective method to treat oil-water emulsion due to its small footprint, simple operation and high separation efficiency, and has great industrial application potential. To mitigate membrane fouling and the concomitant decline in permeation flux caused by oil droplet adhesion, a polysulfone (PSF) ultrafiltration membrane was first aminated via co-deposition of polyethyleneimine (PEI) and Noria. Perfluorooctanoyl chloride (PFOC) was then grafted onto the aminated surface through the high reactive amino-acyl chloride reaction, fabricating a fluorinated ultrafiltration membrane with high oil-fouling resistance. The effects of PEI molecular weight and its mass fraction in the modification solution on the oil repellency and separation performance of the composite membrane were systematically evaluated. The optimal preparation conditions were identified as a PEI molecular weight of 600 and a PEI mass fraction of 0.8%. The resulting functional fluorinated coating endowed the composite membrane with excellent performance. For various oil-in-water emulsions (dodecane, petroleum ether, gasoline, and cetane), the membrane demonstrated stable fluxes of (45±5), (65±5), (50±5), and (40±5) kg/(m²·h), respectively, with all rejection rates exceeding 98%. After cyclic water cleaning, the pure water flux recovery rate (FRR) reached as high as 90%. This developed fluorinated ultrafiltration membrane, characterized by its superior antifouling property and operational stability, shows great promise for the purification of various oily wastewaters.

Key words: membrane separation, oil-water emulsion, in-situ fluorination, anti-oil-fouling

中图分类号:

王梓诚, 王明, 王昊龙, 南军, 孙彦民, 冷晓燕, 李文轩, 温燕军, 侯影飞. Noria-PEI共沉积技术构筑高抗油污染氟化超滤膜[J]. 工业水处理, 2025, 45(11): 151-157.

Zicheng WANG, Ming WANG, Haolong WANG, Jun NAN, Yanmin SUN, Xiaoyan LENG, Wenxuan LI, Yanjun WEN, Yingfei HOU. Construction of a high anti-oil-fouling fluorinated ultrafiltration membrane via Noria-PEI co-deposition technique[J]. Industrial Water Treatment, 2025, 45(11): 151-157.

https://www.iwt.cn/CN/Y2025/V45/I11/151

图/表 9

图1 合成Noria的反应方程

Fig.1 Reaction equation for the synthesis of Noria

图2 氟化超滤膜制膜过程

Fig.2 Preparation process of fluorinatedultrafiltration membrane

图3 膜性能评价装置示意

Fig.3 Schematic of membrane performance evaluation device

图4 PEI相对分子质量对F-PSF膜界面性质（a）及分离性能（b）影响

Fig.4 Effect of PEI molecular weight on the interfacial properties（a） and separation performance（b） of the F-PSF membrane

图5 PEI质量分数对F-PSF膜界面性质（a）及分离性能（b）影响

Fig.5 Effect of PEI mass fraction on the interfacial properties（a） and separation performance（b） of the F-PSF membrane

图6 PSF、mPSF和F-PSF复合膜的红外光谱图（a）和表面ζ电位（b）

Fig.6 Infrared spectra （a） and surface ζ-potential （b） of PSF，mPSF，and F-PSF composite membranes

图7 PSF、mPSF和F-PSF的XPS总谱和F-PSF C分峰谱图

Fig.7 XPS survey scans of PSF，mPSF，F-PSF and high-resolution C spectrum of F-PSF

图8 空气中（a）和水下（b）不同油滴在F-PSF膜表面的接触角

Fig.8 Contact angles of different oil droplets on the F-PSF membrane surface in air（a） and underwater （b）

图9 F-PSF膜对不同种类油水乳液的分离性能和抗污染性能（a）十二烷油水乳液的分离性能；（b）石油醚油水乳液的分离性能；（c）汽油油水乳液的分离性能；（d）十六烷油水乳液的分离性能；（e）F-PSF膜的抗污染性能；（f）F-PSF与其他膜的FRR对比。

Fig.9 Separation performance and anti-pollution performance of F-PSF membranes for different types of oil-water emulsions

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