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化学进展 2020, Vol. 32 Issue (9): 1344-1351 DOI: 10.7536/PC200104 前一篇   后一篇

• 综述 •

电控离子(交换)膜分离技术——从ESIX到ESIPM

高凤凤1, 杨言言1, 杜晓1, 郝晓刚1,**(), 官国清2, 汤兵3   

  1. 1. 太原理工大学化学化工学院 太原 030024
    2. 日本国立弘前大学地域战略研究所 青森 030-0813
    3. 广东工业大学环境科学与工程学院 广州 510006
  • 收稿日期:2020-01-02 修回日期:2020-04-23 出版日期:2020-09-24 发布日期:2020-06-30
  • 通讯作者: 郝晓刚
  • 作者简介:
    ** Corresponding author e-mail: ;
  • 基金资助:
    * 国家重点研发计划政府间国际科技创新合作重点专项项目(2017YFE0129200); 国家自然科学基金项目(21276173, 21476156, 21576184, 21706181, 21776191); 山西省自然科学基金项目(201901D211054)
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Electrically Switched Ion Membrane for Ion Selective Separation and Recovery: From ESIX to ESIPM

Fengfeng Gao1, Yanyan Yang1, Xiao Du1, Xiaogang Hao1,**(), Guoqing Guan2, Bing Tang3   

  1. 1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
    2. Institute of Regional Innovation(IRI), Hirosaki University, Aomori 030-0813, Japan
    3. College of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, China
  • Received:2020-01-02 Revised:2020-04-23 Online:2020-09-24 Published:2020-06-30
  • Contact: Xiaogang Hao
  • Supported by:
    the National Key Research and Development Program with Key Special Project of Intergovernmental Cooperation on International Science and Technology Innovation(2017YFE0129200); the National Natural Science Foundation of China(21276173, 21476156, 21576184, 21706181, 21776191); the Natural Science Foundation of Shanxi Province(201901D211054)

电控离子膜(Electrically Switched Ion Membrane, ESIM)分离是近年来发展起来的一种新型离子选择性高效分离技术,已被用于多种金属阳离子及阴离子的选择性分离与回收。电控膜分离源于电控离子交换(Electrically Switched Ion Exchange, ESIX)技术,其高效运行依赖于具有离子交换功能的电活性材料(Electroactive Ion Exchange Material, EIXM)。EIXM既能传递电子又能传递离子,通过调节其氧化/还原电位可以控制离子的可逆置入/释放,同时实现目标离子的高效分离和EIXM的再生,因而不产生二次污染。本文从EIXM简介、结构设计与可控合成、各种电控离子选择性分离机制的研究进展以及新型ESIX-ESIM膜组件开发和应用几个方面,分析总结了从最初的ESIX技术到基于ESIX原理的电控离子选择渗透膜(Electrically Switched Ion Permselective Membrane, ESIPM)分离的发展历程。展望未来ESIM分离技术,应针对目标离子的选择性分离要求,设计合成新型结构ESIM材料和研发相关膜组件系统,可望最终实现ESIM技术的工业应用。

关键词： 电控离子膜, 离子交换, 电活性材料, 选择渗透性, 膜分离, 分离机理, 膜组件

Electrically switched ion membrane(ESIM) separation is a novel ion selective separation and recovery technology developed in recent years. To date, the target ion species separated by using ESIM have involved various metal cations and anions. ESIM separation is originated from electrically switched ion exchange(ESIX) technology, whose highly efficient operation depends on the electroactive ion exchange material(EIXM) with unique ion exchange function. Reversible ion loading/unloading can be easily controlled by modulating the redox states of the EIXM with both electronic and ionic conductivity to perform the separation of target ions from mixed solution and regeneration of the matrix. Therefore, the secondary waste is eliminated due to that the chemical regeneration of the ion-exchange matrix is not necessary. This paper begins with a brief introduction of EIXM to the structure design and controllable preparation of membrane/film materials, then the research progress of various mechanisms of ESIX and the development and application of some novel ESIX-ESIM modules are outlined. The development course from intermittent operation of ESIX to electrically switched ion permselective membrane(ESIPM) based on the ESIX principle is summarized. It is necessary to emphasize the design and synthesis of novel structural ESIM materials and the development of the corresponding membrane modules focused on the selective separation of target ions, then finally the industrial application of ESIM could be realized.

Contents

1 Introduction

2 Design, structure and controllable preparation of EIXM

3 Electrically switched ion exchange/separation mechanism

3.1 Traditional ESIX mechanism

3.2 ESIX-PTPS mechanism

3.3 ESIX-IIP coupling mechanism

3.4 ESIX-pH conversion mechanism

3.5 Electrically switched ion permselective membrane separation mechanism

4 Membrane modules development and application

5 Conclusion and outlook

Key words: electrically switched ion membrane, ion exchange, electroactive material, permselectivity, membrane separation, separation mechanism, membrane module
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图1 NiHCF的电控离子交换过程
Fig.1 The ESIX process of NiHCF
图2 α-ZrP/PANI复合膜的电控离子交换-质子内部自交换机理图[33, 34]
Fig.2 The ESIX-PTPS mechanism of α-ZrP/PANI complex film[33, 34]
图3 Ni2+印迹-FCN/PPy的制备方法[12]
Fig.3 Strategy for the preparation of Ni2+ ion imprinted ferricyanide/PPy[12]. Copyright 2015, ACS
图4 碳基双电层-电控离子选择渗透膜的离子分离机理[55]
Fig.4 The EDL-ESIPM mechanism of carbon-based membrane[55]. Copyright 2017, Elsevier
图5 电控离子选择渗透膜分离工艺图[66]
Fig.5 Schematic for the process of ESIPM[66]. Copyright 2012, Taiyuan University of Technology
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