选择性电渗析：机遇与挑战

doi:10.11949/0438-1157.20221073

摘要/Abstract

摘要：

电渗析海水制盐、氯碱工业中的盐水精制、盐湖提锂以及冶金行业中的废酸废碱资源化，均要求实现相同电荷不同价态的离子分离，因此离子精准分离是化工生产中的重要一环。选择性电渗析是将电渗析中普通阴阳离子交换膜替换为具有一/多价分离特性的离子膜，进而实现离子的选择性分离。本文详细介绍了一/二价离子膜分离机理以及制备路线；同时也对选择性电渗析的主要膜堆结构以及工作原理进行了阐述；详细介绍了选择性电渗析目前在离子分离中的应用与机遇；指出了选择性电渗析在应用中面临着投资成本高、稳定性较差、容易发生浓差极化等挑战；最后在膜堆构造优化、多过程耦合以及工业化制膜等方面进行了展望。

关键词: 脱盐, 离子交换膜, 电渗析, 选择性, 分离

Abstract:

Precise ion fractionation for the same charge but different valences is crucial to various industrial sectors, such as electrodialytic seawater salt production, brine refining in the chlor-alkali industry, lithium extraction from salt lakes, and waste acid and alkali recycling in the metallurgical industry. Selective electrodialysis (SED) enables the selective separation of various ions by replacing the anion- or cation-exchange membranes with mono/multivalent selective ion exchange membranes in the conventional electrodialysis stack. This paper introduces the separation mechanism of monovalent ion/divalent ion membrane and the preparation route in detail. Meanwhile, the commonly used membrane stack configuration and its working principle are also described. Moreover, the challenges of the SED, including the high investment cost, poor stability, and occurrence of concentration polarization on the membrane surface, are discussed. Finally, the perspective of SED technology is proposed from the aspects of the optimization of membrane stack configuration, the improvement of ion separation selectivity through various process integrations, and large-scale mono/divalent selective ion membrane fabrication.

Key words: desalination, ion exchange membrane, electrodialysis, selectivity, separation

中图分类号:

TQ 028.8

闫军营, 王皝莹, 李瑞瑞, 符蓉, 蒋晨啸, 汪耀明, 徐铜文. 选择性电渗析：机遇与挑战[J]. 化工学报, 2023, 74(1): 224-236.

Junying YAN, Huangying WANG, Ruirui LI, Rong FU, Chenxiao JIANG, Yaoming WANG, Tongwen XU. Selective electrodialysis: opportunities and challenges[J]. CIESC Journal, 2023, 74(1): 224-236.

图/表 9

表1 典型膜分离技术对比

Table 1 Comparison of typical membrane separation technology

项目	ED	SED	NF	RO
主要用途	盐浓缩、脱盐	一/多价离子分离、浓缩	一/多价离子分离	有机物和微生物脱除、脱盐
驱动力	电势差	电势差	压力差	压力差
操作压力	低	低	高	高
膜污染	低	低	高	低
投资成本	较高	高	较低	高
优势	高倍率浓缩	分盐+一价盐高倍浓缩	分盐，技术成熟	离子去除率高，技术成熟
劣势	不能分盐	投资成本高	不能实现同时分盐和一价盐浓缩	抗污染能力差，水回收率低

图1 电渗析盐浓缩和选择电渗析分盐原理

Fig.1 Schematic diagram of salt concentration by electrodialysis and desalination by selective electrodialysis

表2 商业一/二价交换膜详细规格

Table 2 The properties of commercial mono/divalent ion exchange membranes

膜类型	名称	电阻/ （Ω·cm²）	破裂强度/ MPa	厚度/mm	离子交换容量/ (mmol·g^-1)	迁移数/%	厂家
一/二价阳离子交换膜	CIMS	1.8	≥0.1	0.15	—	—	Astom, Japan
	CSO	2.3	—	0.1	1.4~1.7	>97	AGC Engineering, Japan
	PC-MVK	—	≥0.3	0.1	—	>97	PCA GmbH, Germany
	K-102	1.8~2.3	—	0.21~0.23	1.8~2.0	>99	Asahi Chemical, Japan
一/二价阴离子交换膜	ACS	3.8	≥0.25	0.13	—	—	Astom, Japan
	ASV	4.0	≥0.2	0.1	1.8~2.2	>95	AGC Engineering, Japan
	PC-MVA	20	≥0.2	0.11	—	>97	PCA GmbH, Germany
	A-102	1.7~2.1	—	0.13~0.15	1.8~1.9	>99	Asahi Chemical, Japan

图2 一/二价离子膜传质过程示意图

Fig.2 Schematic diagram of mass transfer process of mono/divalent ion exchange membrane

表3 国产一/二价离子膜详细规格

Table3 The properties of domestic mono/divalent ion exchange membranes

膜类型	自制膜	分离体系	电流密度/ (mA·cm^-2)	商业膜	选择性（自制膜/商业膜）	通量/ (mmol·(m²·s)^-1)	文献
一/多价阳离子交换膜	SCEM	0.02 mol·L^-1 Na⁺/Mg²⁺	5	CIMS	1.64/1.51	$J N a + = 5.01$	[31]
	PANi	0.05 mol·L^-1 Na⁺/Mg²⁺	5.1	CIMS	4.1/3.56	$J N a + = 4.48$	[32]
	PPy	0.05 mol·L^-1 Na⁺/Mg²⁺	5.1	CIMS	12.95/2.46	$J N a + = 3.02$	[33]
	ICM	0.1 mol·L^-1 K⁺/Mg²⁺	20	CIMS	7.91/—	$J K + = 0.62$	[34]
	EDNF	0.46/0.052 mol·L^-1 Na⁺/Mg²⁺	20	CSO	7.0/4.0	$J N a + = 2.27$	[35]
	ENF	0.1 mol·L^-1 Li⁺/Mg²⁺	10	CSO	11.3/1.62	$J L i + = 57.9$	[36]
	NQS	0.1 mol·L^-1 Na⁺/Mg²⁺	14	CSO	1.6/1.55	$J N a + = 29.6$	[37]
	MCPM	0.1 mol·L^-1 Na⁺/Mg²⁺	14	CSO	3.3/1.7	$J N a + = 42.7$	[28]
	MCMX	0.1 mol·L^-1 Na⁺/Mg²⁺	5	CIMS	35.13/—	$J N a + = 15.0$	[38]
	PDA-mil	0.34/0.021 mol·L^-1 Na⁺/Mg²⁺	恒压-20 V	—	3.3/—	$J N a + = 220.0$	[39]
	Modified SPPO	0.46/0.052 mol·L^-1Na⁺/Mg²⁺	20	CSO	15.5/2.58	$J N a + = 165.0$	[40]
一/多价阴离子交换膜	MAEM	0.1 mol·L^-1 Cl^-/SO $4 2 -$	20	ACS	52.44/—	$J C l - = 79.0$	[41]
	PAES	0.05 mol·L^-1 Cl^-/SO $4 2 -$	5	ACS	12.5/5.27	$J C l - = 37.0$	[29]
	S-rGO	0.05 mol·L^-1 Cl^-/SO $4 2 -$	5	—	2.25/—	—	[30]

表3 国产一/二价离子膜详细规格

Table3 The properties of domestic mono/divalent ion exchange membranes

膜类型	自制膜	分离体系	电流密度/ (mA·cm^-2)	商业膜	选择性（自制膜/商业膜）	通量/ (mmol·(m²·s)^-1)	文献
一/多价阳离子交换膜	SCEM	0.02 mol·L^-1 Na⁺/Mg²⁺	5	CIMS	1.64/1.51	$J N a + = 5.01$	[31]
	PANi	0.05 mol·L^-1 Na⁺/Mg²⁺	5.1	CIMS	4.1/3.56	$J N a + = 4.48$	[32]
	PPy	0.05 mol·L^-1 Na⁺/Mg²⁺	5.1	CIMS	12.95/2.46	$J N a + = 3.02$	[33]
	ICM	0.1 mol·L^-1 K⁺/Mg²⁺	20	CIMS	7.91/—	$J K + = 0.62$	[34]
	EDNF	0.46/0.052 mol·L^-1 Na⁺/Mg²⁺	20	CSO	7.0/4.0	$J N a + = 2.27$	[35]
	ENF	0.1 mol·L^-1 Li⁺/Mg²⁺	10	CSO	11.3/1.62	$J L i + = 57.9$	[36]
	NQS	0.1 mol·L^-1 Na⁺/Mg²⁺	14	CSO	1.6/1.55	$J N a + = 29.6$	[37]
	MCPM	0.1 mol·L^-1 Na⁺/Mg²⁺	14	CSO	3.3/1.7	$J N a + = 42.7$	[28]
	MCMX	0.1 mol·L^-1 Na⁺/Mg²⁺	5	CIMS	35.13/—	$J N a + = 15.0$	[38]
	PDA-mil	0.34/0.021 mol·L^-1 Na⁺/Mg²⁺	恒压-20 V	—	3.3/—	$J N a + = 220.0$	[39]
	Modified SPPO	0.46/0.052 mol·L^-1Na⁺/Mg²⁺	20	CSO	15.5/2.58	$J N a + = 165.0$	[40]
一/多价阴离子交换膜	MAEM	0.1 mol·L^-1 Cl^-/SO $4 2 -$	20	ACS	52.44/—	$J C l - = 79.0$	[41]
	PAES	0.05 mol·L^-1 Cl^-/SO $4 2 -$	5	ACS	12.5/5.27	$J C l - = 37.0$	[29]
	S-rGO	0.05 mol·L^-1 Cl^-/SO $4 2 -$	5	—	2.25/—	—	[30]

图3 选择电渗析浓缩氯化钠示意图

Fig.3 Schematic diagram of concentration of NaCl by selective electrodialysis

图4 选择电渗析回收废酸示意图

Fig.4 Schematic diagram of recovery of waste acid by selective electrodialysis

图5 选择电渗析盐湖提锂示意图

Fig.5 Schematic diagram of recovery of Li+ from salt lake by selective electrodialysis

图6 非对称选择性电渗析分盐原理示意图

Fig.6 Schematic diagram of the principle of asymmetric selective electrodialysis for salt separation

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