双极膜电渗析在醇水体系的应用研究进展

doi:10.11949/0438-1157.20241308

摘要/Abstract

摘要：

双极膜作为一种高性能复合膜，在盐制酸碱、能量存储与转化、酸碱液流电池等领域得到了广泛应用。在反向偏压下，水体系中双极膜中间层的水分子可解离成H⁺和OH^-，与阴阳离子交换膜配合构成双极膜电渗析广泛应用于高盐废水脱盐同时酸碱化。除水体系外，双极膜电渗析也可应用于水-醇体系，生产水溶性较差的有机酸。同时，双极膜也可实现醇的解离，使其解离为氢离子和烷氧根离子，应用于金属醇盐生产、有机物绿色合成等。目前醇水体系研究较少，因此，本文聚焦于醇水体系双极膜电渗析研究进展，深度比较水、醇解离的机理和电化学性质。同时也指出双极膜应用于醇体系的瓶颈问题，包括解离电阻高、双极膜溶胀造成同离子泄漏严重等，最后分析为实现双极膜水-醇混合体系以及醇体系更广泛的应用，仍需积极探索其混合体系的解离机理，制备适合醇体系的双极膜等。

关键词: 双极膜, 醇体系, 水-醇混合体系, 电渗析

Abstract:

As a high-performance composited membrane, bipolar membrane has been widely used for the conversion of salt into acid and alkali, energy storage and conversion, and acid-base flow battery. Under reverse voltage bias, water molecules in the middle layer of bipolar membrane in aqueous system can be dissociated into H⁺ and OH^-, and cooperate with anion and cation exchange membrane to form bipolar membrane electrodialysis, which is widely used in the desalination and acidification of high-salt wastewater. In addition to the aqueous system, bipolar membrane electrodialysis can also be used in water-alcohol system, such as the production of water insoluble organic acids. Meanwhile, the bipolar membrane can also realize the dissociation of alcohols into hydrogen ions and alkoxide ions, which is applied to the production of metal-alkoxides and green synthesis of organic chemicals. However, there are fewer studies that summarize the application of bipolar membrane in alcohol water systems. This review focuses on the progress of bipolar membranes electrodialysis in alcohol water systems, comparing the mechanism and electrochemical properties of water and alcohol dissociation. Moreover, it also points out the bottlenecks of alcohol dissociation in bipolar membranes, including high dissociation resistance, serious coion leakage caused by the swelling of membrane layers, etc. Finally, it is necessary to in-depth elucidate the dissociation mechanism of the mixed system and to prepare alcohol-tolerance bipolar membranes to realize the wider application of the bipolar membrane water-alcohol mixed and the alcohol system.

Key words: bipolar membrane, alcohol system, water-alcohol mixed system, electrodialysis

中图分类号:

TQ 028.8

程刘惠美, 闫军营, 刘慧情, 王治澎, 王报英, 徐铜文, 汪耀明. 双极膜电渗析在醇水体系的应用研究进展[J]. 化工学报, 2025, 76(5): 1960-1972.

Liuhuimei CHENG, Junying YAN, Huiqing LIU, Zhipeng WANG, Baoying WANG, Tongwen XU, Yaoming WANG. Progress of bipolar membrane electrodialysis for non-aqueous systems[J]. CIESC Journal, 2025, 76(5): 1960-1972.

图/表 10

图1 （a）双极膜界面层水/醇缔合/解离示意图；（b）醇盐生产；（c）葡萄糖酸生产[12]；（d）氢氧化锂生产示意图[8]

Fig. 1 (a) Schematic diagram of water/alcohol conjugation/dissociation at the interfacial layer of the bipolar membrane; (b) Schematic diagram of alkoxides production; (c) Gluconic acid production; (d) Lithium hydroxide production[8]

图2 双极膜水解离模型（图中显示了 CEL和 AEL上离子的电荷密度，以及BPM IL 上的静电势）

Fig. 2 Water dissociation model of the bipolar membranes （the plots show the charge density of the ions on the CEL and AEL, and the electrostatic potential on the BPM IL）

图3 双极膜醇解离模型

Fig. 3 Alcohol dissociation model of the bipolar membranes

表1 溶剂性质汇总［47］

Table 1 Summary of the main properties of different solvents［47］

溶剂	化学式	介电常数	pK_SH	黏度
水	H₂O	78.4	14.00	1.00
甲醇	CH₃OH	32.7	16.71	0.611
乙醇	CH₃CH₂OH	24.6	18.90	1.19
丙醇	CH₃CH₂CH₂OH	20.5	19.43	2.20

图4 （a）水/甲醇[49]和（b）水-甲醇体系的I-V曲线示意图；（c）电流-电压曲线划分示意图[49]

Fig. 4 (a) I-V plot for water/methanol[49]； (b) I-V curve schematic for water-methanol system; (c) Schematic of current-voltage curve division[49]

图5 （a）双极膜典型Nyquist谱图及等效电路（EEC）；（b）、（c）水/甲醇阻抗谱图[32]；（d）、（e）水/甲醇Bode谱图[32];（f）水-醇阻抗变化图[54]

Fig. 5 (a) Typical Nyquist spectroscopy and equivalent circuits (EECs) of bipolar membranes; (b)，(c) Water/methanol impedance profiles[32]; (d)，(e) Water/methanol Bode profiles[32]; (f) Water-alcohol impedance spectroscopy[54]

图6 BMED典型膜堆构型图：（a）三隔室BP-A-C；（b）两隔室BP-C；（c）两隔室BP-A

Fig. 6 Typical membrane stack configuration of BMED: (a) three-compartment BP-A-C; (b) two-compartment BP-C; (c) two-compartment BP-A

图7 水-醇混合体系生产癸二酸（a）和阿魏酸（b）[30]的膜堆构型

Fig.7 Membrane stack configurations of water-alcohol mixed solutions for the production of arachidonic acid (a) and ferulic acid (b)[30]

图8 醇体系中甲醇解离（a）、乙醇解离（b）、绿色化学合成甲氧基乙酸甲酯（c）和甲醇锂生产（d）[32]的膜堆构型

Fig.8 Membrane stack configurations for methanol dissociation (a), ethanol dissociation (b)， green chemistry synthesis of methyl methoxyacetate (c) and lithium methanol production in alcohol system (d)[32]

图9 醇体系BMED的应用挑战性

Fig. 9 Challenge of the applications of BMED in alcohol systems

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