电渗析用季铵化聚氯乙烯均相阴离子交换膜的制备

doi:10.11949/j.issn.0438-1157.20181041

摘要/Abstract

摘要：

以1-甲基咪唑(N-MI)为季铵化试剂一步法对聚氯乙烯(PVC)功能化改性，并制备了均相PVC阴离子交换膜，避免了传统阴离子交换膜制备过程中的氯甲基化步骤。通过对比研究，优化后的PVC-N-MI-5表现出较好的综合性能。离子交换容量和迁移数分别高达2.89 mmol·g^–1和98.4%；吸水率和溶胀率分别为4.24%和0.21%，低于商业JAM-5阴离子交换膜(4.87%和3.33%)；脱盐率、电流效率以及能耗分别为98.38%、55.8%和5.1 kW·h·(kg NaCl)^–1，可与商业JAM-5(93.0%、55.2%和4.6 kW·h·(kg NaCl)^–1)相比较。低廉的原料与简便的制备过程以及相对良好的电渗析应用性能，表明所制备的PVC-N-MI-5具有一定的应用前景。

关键词: 聚氯乙烯, 1-甲基咪唑, 均相阴离子交换膜膜, 电渗析

Abstract:

This work presents the preparation of homogeneous anion exchange membrane (AEM) based on quaternized polyvinyl chloride (PVC) via straight forward quaternization of PVC with 1-methylimidazole (N-MI). In particular, the preparation avoids the use of toxic chloromethylation. The optimized AEM PVC-N-MI-5 shows ion-exchange capacity (IEC) and transport number of 2.89 mmol·g^–1 and 98.4%, respectively. The water uptake and swelling ratio are 4.24% and 0.21%, lower than the commercial AEM JAM-5 (4.87% and 3.33%). The NaCl removal ratio, current efficiency and energy consumption of the as-prepared AEM were 98.38%、55.8% and 5.1 kW·h·(kg NaCl)^－1, respectively, comparable to commerical JAM-5(93.0%, 55.2% and 4.6 kW·h·(kg NaCl)^－1). The cost-effective PVC and relatively good performance are suggestive of the potential electrodialysis application.

Key words: polyvinyl chloride, 1-methylimidazole, homogeneous anion exchange membrane, electrodialysis

中图分类号:

0658. 6⁺8

王超, 潘能修, 鲁丹, 廖俊斌, 沈江南, 高从堦. 电渗析用季铵化聚氯乙烯均相阴离子交换膜的制备[J]. 化工学报, 2019, 70(4): 1620-1627.

Chao WANG, Nengxiu PAN, Dan LU, Junbin LIAO, Jiangnan SHEN, Congjie GAO. Preparation of homogeneous anion exchange membrane based on quaternized PVC for electrodialysis[J]. CIESC Journal, 2019, 70(4): 1620-1627.

图/表 12

图1 1-甲基咪唑改性聚氯乙烯(PVC-N-MI)路线

Fig.1 Modification of PVC with 1-methylimidazole (PVC-N-MI)

图2 离子膜膜面电阻测试装置

Fig.2 Schematic diagram of membrane area resistance measurement setup

图3 电渗析装置

Fig.3 Schematic diagram of continuous-mode ED stack

图4 PVC- N-MI-5阴离子的宏观形态

Fig.4 Photographs of as-prepared PVC-N-MI-5 AEM

图5 PVC和PVC-N-MI离子膜的红外光谱

Fig.5 FTIR spectra of PVC and PVC-N-MI AEMs

图6 PVC-N-MI-5离子膜表面(a)和截面(b)的SEM图

Fig.6 SEM images of PVC-N-MI-5 AEM

图7 PVC-N-MI与JAM-5膜离子交换容量和迁移数

Fig.7 IEC and transport number of PVC-N-MI and JAM-5 AEMs

表1 PVC-N-MI和商业阴膜JAM-5的物化参数

Table 1 Physico-chemical properties of PVC-N-MI and commercial JAM-5 AEM

AEM	IEC/(mmol·g^–1)	Area resistance/(Ω·cm²)	Water uptake/%	Swelling ratio/%	Transport number/%
PVC-N-MI-1	0.98	6784.4	2.22	0.12	65.4
PVC-N-MI-2	1.16	5679.9	2.80	0.14	66.7
PVC-N-MI-3	1.53	79.1	3.19	0.15	97.8
PVC-N-MI-4	2.76	26.4	3.95	0.18	98.2
PVC-N-MI-5	2.89	14.1	4.24	0.21	98.4
JAM-5	3.04	4.5	4.87	3.33	98.8

图8 PVC-N-MI-n离子膜机械强度与断裂伸长率

Fig.8 Mechanical strength change of PVC-N-MI-n

图9 PVC-N-MI-n系列离子膜的极限电流密度曲线

Fig.9 Limit current density curves of PVC-N-MI-n

图10 浓室、淡室电导率(a)和电压(b)随时间变化曲线

Fig.10 Change of conductivity in dilute cell and concentrate cell(a) and change of potential over stack during ED test(b)

图11 PVC-N-MI-n 在电渗析中的脱盐率(a)和电流效率与能耗(b)

Fig.11 Desalination removal ratio(a) and current efficiency and energy consumption (b) of PVC-N-MI-n in ED test

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