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胺化哌嗪羧酸聚酰胺纳滤膜的制备及性能研究

作者：宋刚福¹，胡智媛¹，高亚伟²，王小亻毛²

单位： 1. 华北水利水电大学环境与市政工程学院，郑州 450000； 2. 清华大学环境学院，环境模拟与污染控制国家重点联合实验室，北京 100084

关键词：聚酰胺纳滤膜；哌嗪2羧酸；表面电荷调控；胺化改性

DOI号： 10.16159/j.cnki.issn1007-8924.2025.03.005

分类号： TQ028.8

出版年,卷(期):页码： 2025,45(3):44-53

摘要：

研究了基于哌嗪2羧酸聚酰胺膜的胺化改性方法及对膜性能的影响。采用界面聚合技术，以哌嗪2羧酸和均苯三甲酰氯分别为两相单体制备负电性纳滤初始膜，并通过有机环境胺化进行二次改性，明显提升了负电性纳滤膜表面的正电荷密度。其中，多乙烯多胺直接表面改性法显著提升膜表面正电荷密度和水渗透系数[最高170.0 L/（m2·h·MPa）]，增加MgCl2截留（60.3%）和降低Na2SO4截留（27.4%）；而有机环境层状界面聚合法可使纳滤膜具备适中的水渗透系数[75.0 L/（m2·h·MPa)]、减小的膜孔径(0.37 nm)和近电中性的膜表面 (MgCl2和Na2SO4截留率分别为71.5%和78.3%)。同时，利用孔径相异/相近和电性不同的纳滤膜截留全氟化合物，并结合膜结构表征，显示膜表面位置的电荷对截留发挥关键作用，是尺寸筛分效应的有力补充。

The amination modification strategies for polyamide nanofiltration (NF) membranes based on piperazine-2-carboxylic acid (PIP-COOH) were systematically investigated. The negatively charged NF membrane was first prepared via interfacial polymerization of PIP-COOH in aqueous phase and trimesoyl chloride (TMC) in organic phase, followed by modification through two methods: surface modification and layer-by-layer interfacial polymerization (LIP) using polyethylene polyamine (PEPA). The surface modification increased membrane surface positive charge density and water permeability [up to 170.0 L/（m2·h·MPa）], enhancing MgCl2 rejection (60.3%) but reducing Na2SO4 rejection (27.4%). However, the LIP produced membranes with moderate water permeability [75.0 L/（m2·h·MPa）], reduced pore size (0.37 nm), and near-neutral membrane surface, achieving the rejection of 71.5% for MgCl2 and 78.3% for Na2SO4. Perfluorinated compound rejection experiments highlighted the importance of charge effects stemming from membrane top surface under similar pore sizes. Characterization confirmed that the amination in organic milieu changed the membrane surface structure, charge distribution, and active layer thickness.

基金项目：

国家自然科学青年基金项目（52300095）

作者简介：

宋刚福（1977-），男，辽宁营口人，教授，博士研究生，研究方向为膜法水处理、饮用水安全与评价及河流生态研究等

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