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荷正电导电纳滤膜的构建及其分离性能研究

作者：王建宇¹，²，焦瑶瑶³，⁴，崔振宇⁴

单位： 1. 凯里学院理学院，凯里 556011； 2. 浙江大学膜与水处理技术教育部工程研究中心，杭州 310030； 3. 日东电工(上海松江)有限公司，上海 201613； 4. 天津工业大学材料科学与工程学院，天津 300387

关键词：导电纳滤膜；铜离子；电场；选择性分离

DOI号： 10.16159/j.cnki.issn1007-8924.2025.04.007

分类号： TQ028.8

出版年,卷(期):页码： 2025,45(4):65-76

摘要：

为提高纳滤膜对多价离子的截留以及“多价/一价”离子的选择性分离效果，本研究采用热致相分离技术（TIPS）制备聚偏氟乙烯/苯乙烯-马来酸酐共聚物（PVDF/SMA）平板膜，通过SMA中的酸酐（MA）与聚乙烯胺（PVAM）交联后再与单宁酸（TA）进行共沉积，再通过TA的酚羟基与氨基化碳纳米管（n-CNT）发生反应形成荷正电杂化导电分离层。对膜表面及截面微观结构以及膜的亲水性、荷电性、导电性和分离性能等进行表征和测试，对比施加电场对Cu2+截留率、Na+/Cu2+的选择性分离以及通量的影响。结果表明，电压由0 V增加到2.5 V时，导电膜对Cu2+截留率由90.2％提高到99.3％，Na+/Cu2+分离因子从7.9升至114.57，而通量维持在36 L/(m2·h)左右基本不变。电压超过2.5 V时因发生析氢反应而降低膜对Cu2+的截留。提出施加适当的电压可显著提高导电膜对Cu2+的截留率以及Na+/Cu2+的选择性分离效果的“尺寸筛分+电场强化静电排斥”共同作用机制。本研究对制备面向从废水中回收有价资源的导电纳滤膜有一定的借鉴作用。

In order to improve the rejection of multivalent ions and the selective separation performance of “multivalent/monovalent” ions by nanofiltration membrane, in this work, polyvinylidene fluoride/styrene maleic anhydride (PVDF/SMA) flat membranes were prepared using thermally induced phase separation (TIPS) technology. After crosslinking with polyethyleneimine (PVAM) and anhydride (MA), it was co-deposited with tannic acid (TA), a positively charged hybrid conductive layer was formed on the membrane surface by the reaction between the phenolic hydroxyl group of TA and aminated carbon nanotubes (n-CNT). The changes in the microstructure of the membrane surface and cross-sectional separation layer, as well as the membrane surface properties such as hydrophilicity, charge and conductivity were characterized. The effects of electric field on Cu2+retention, Na+/Cu2+selective separation performance and permeability were compared. The results showed that when the voltage increased from 0 V to 2.5 V, the Cu2+rejection increased from 90.2% to 99.3%, and the separation factor of Na+/Cu2+ increased from 7.9 to 114.57 for conductive membrane, while the permeability basically unchanged. When the voltage exceeded 2.5 V, the Cu2+rejection decreased due to hydrogen evolution reaction. The combined mechanism of “size screening and electric field enhanced electrostatic repulsion” is proposed, which can significantly improve the retention of Cu2+and the selective separation performance of Na+/Cu2+by applying appropriate voltage. This study has a certain reference value for the preparation of conductive nanofiltration membrane for the recovery of valuable resources from wastewater.

基金项目：

凯里学院校级科研项目（2025ZD007）; 国家自然科学基金面上项目（21978213）

作者简介：

王建宇(1974-)，男，贵州望谟人，博士，高级工程师,主要从事膜材料与膜应用研究

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