共沉积THAP/TEPA中间层复合纳滤膜的制备及截盐性能

doi:10.19965/j.cnki.iwt.2025-0262

摘要/Abstract

摘要：

针对纳滤膜固有的渗透性和截留率间存在的Trade-off效应带来的高能耗问题，采取构建中间层达到保持纳滤膜通量的稳定性并有效改善其截盐性能的目的。通过席夫碱反应将2，3，4-三羟基苯乙酮（THAP）与四乙烯五胺（TEPA）共沉积到聚砜（PSF）支撑层上作为中间层制备聚酰胺（PA）复合纳滤膜，以改善纳滤膜的截盐性能。傅里叶变换红外光谱（FTIR）和X射线光电子能谱（XPS）表明席夫碱反应成功构筑了具有高交联度的THAP/TEPA中间层，扫描电镜（SEM）和水接触角测试表明THAP/TEPA中间层显著改善了纳滤基膜的平整度和亲水性。通过调整m（THAP）∶m（TEPA）和沉积时间确定制备中间层的最佳条件为沉积时间10 min、m（THAP）∶m（TEPA）=1∶2，此时所制备的复合纳滤膜对MgCl₂的截留率高达92.23%，且改性前后纯水通量保持稳定。该研究可在较短的沉积时间内通过多酚与多胺间的席夫碱反应构筑复合纳滤膜中间层，为提升纳滤膜的截盐性能、增强纳滤膜通量的稳定性提供了一种简便有效的方法。

关键词: 纳滤膜, 中间层, 共沉积, 席夫碱反应, 哌嗪

Abstract:

To address the high energy consumption caused by the inherent trade-off effect between permeability and rejection in nanofiltration membranes, an interlayer was constructed to maintain the stability of flux and effectively improve the salt rejection performance of the membranes. In this study, a polyamide (PA) composite nanofiltration membrane was prepared by co-depositing 2,3,4-trihydroxyacetophenone (THAP) and tetraethylenepentamine (TEPA) onto the polysulfone (PSF) support layers via Schiff base reaction to serve as an interlayer, thereby enhancing the salt rejection performance of the nanofiltration membrane. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the successful construction of a highly cross-linked THAP/TEPA interlayer through the Schiff base reaction. Scanning electron microscopy (SEM) and water contact angle tests demonstrated that the THAP/TEPA interlayer significantly improved the smoothness and hydrophilicity of the nanofiltration substrate membrane. By adjusting the mass ratio of m(THAP)∶m(TEPA) and deposition time, the optimal preparation conditions for the interlayer were determined as deposition time of 10 minutes and m(THAP)∶m(TEPA)=1∶2. Under these conditions, the prepared composite nanofiltration membrane achieved a rejection rate of up to 92.23% for MgCl₂, while maintaining stable pure water flux before and after modification. This study presented a simple and effective method for constructing an interlayer for composite nanofiltration membranes via the Schiff base reaction between polyphenols and polyamines within a short deposition time, offering a promising approach to enhance the salt rejection performance and improve the flux stability of nanofiltration membranes.

Key words: nanofiltration membrane, interlayer, co-deposition, Schiff base reaction, piperazine

中图分类号:

TQ051.893

华纯, 张明铎, 孙孟超, 周学良, 孙雯, 刘大朋, 洪耀良. 共沉积THAP/TEPA中间层复合纳滤膜的制备及截盐性能[J]. 工业水处理, 2026, 46(3): 168-176.

Chun HUA, Mingduo ZHANG, Mengchao SUN, Xueliang ZHOU, Wen SUN, Dapeng LIU, Yaoliang HONG. Preparation and salt rejection properties of THAP/TEPA co-deposited interlayer composite nanofiltration membranes[J]. Industrial Water Treatment, 2026, 46(3): 168-176.

https://www.iwt.cn/CN/Y2026/V46/I3/168

图/表 10

图1 纳滤膜制备示意

Fig.1 Schematic diagram of the preparation of nanofiltration membrane

图2 PSF基膜和THAP/TEPA共沉积膜的SEM

Fig.2 SEM images of PSF substrate and THAP/TEPA co-deposited membranes

图3 PSF支撑层和THAP/TEPA共沉积膜的红外光谱（a）、表面能谱（b）以及PSF-0（c）、PSF-10（d）表面高分辨N 1s光谱

Fig.3 Infrared spectra （a） and surface energy spectra （b） of PSF support layer and THAP/TEPA co-deposited membrane，and high resolution N 1s spectra of PSF-0 （c） and PSF-10 （d） surfaces

图4 PSF支撑层及其改性膜的水接触角

Fig.4 Water contact angles of PSF support layer and its modified membrane

图5 基于不同沉积时间中间层改性支撑膜制备纳滤膜的SEM

Fig.5 SEM images of nanofiltration membranes prepared with support membranes modified by interlayers at different deposition time

图6 PSF、M0和M10膜的红外光谱（a），M0和M10膜的表面能谱（b），M0膜（c）和M10膜（d）表面高分辨C 1s光谱

Fig.6 Infrared spectra of PSF、M0 and M10 membrane（a）， surface energy spectra of M0 and M10 membrane（b），high resolution C 1s spectra of M0 （c） and M10 （d） membrane surface

图7 复合纳滤膜表面Zeta电位随pH的变化（a）及不同复合纳滤膜表面水接触角（b）

Fig.7 Variation in Zeta potential of composite nanofiltration membrane surfaces with pH（a） and water contact angles of different composite nanofiltration membranes（b）

图8 M0和M10膜对不同分子质量PEG的截留率

Fig.8 Rejection rates of M0 and M10 membranes for PEGs with different molecular weights

图9 THAP/TEPA质量比（a）和沉积时间（b）对膜性能的影响

Fig.9 Effect of THAP/TEPA mass rate （a） and reaction time （b） on membrane performance

图10 M10膜长期运行的稳定性

Fig.10 Long-term stability of M10 membrane

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