不同侧链BPPO阴离子交换膜的制备及其抗污染性能

doi:10.11949/0438-1157.20200821

摘要/Abstract

摘要：

采用含有不同碳链长度的4-乙基吡啶、3-丁基吡啶与3-己基吡啶，通过亲核取代反应分别对溴化聚苯醚（BPPO）进行季铵化，制得三种阴离子交换膜（QBPPO-1、QBPPO-2、QBPPO-3）并对其电化学性能、脱盐性能以及抗污染性能进行了研究。实验结果表明随着吡啶环上烷基碳链的增长，制得的离子交换膜的离子交换容量呈现下降趋势，由1.92 mmol/g降至1.34 mmol/g，而膜面电阻逐渐增加，由2.99 Ω·cm²增加到10.59 Ω·cm²；在电渗析实验中，与商业日本Fuji阴离子交换膜相比，本实验制备的三种离子交换膜均呈现出较高的脱盐率；在污染实验中，随着高分子骨架侧链碳链的增长，离子交换膜在污染实验中的的转折时间逐渐变短，抗污染能力下降；计算模拟结果表明疏水作用在有机污染物（十二烷基苯磺酸钠）与离子交换膜内高分子骨架侧链的亲和相互作用中占有重要地位。

关键词: 溴化聚苯醚, 阴离子交换膜, 电渗析, 抗污染

Abstract:

Three kinds of anion-exchange membranes were prepared based on polyphenyl bromide (BPPO) modified by pyridine derivatives with different side chain lengths (4-ethylpyridine, 3-butyl pyridine and 3-hexylpyridine). With the increasing of the alkyl carbon chain length on the pyridine ring, the ion exchange capacity decreased from 1.92 mmol/g to 1.34 mmol/g and the membrane resistance was increased from 2.99 Ω·cm² to 10.59 Ω·cm². Compared with the desalination rate of commercial Fuji AEM, the three kinds of prepared AEMs all showed much higher desalination rate during electrodialysis experiment. The result of fouling experiment showed the transition-time of the membrane was more shortened with longer side-chains on the polymer backbone. The calculation and simulation results showed that the hydrophobic interaction played an important role in the affinity interaction between organic pollutants (sodium dodecylbenzene sulfonate) and the side chains of the polymer backbone of the ion exchange membrane.

Key words: BPPO, anion-exchange membrane, electrodialysis, anti-fouling

中图分类号:

0658.

刘元伟, 董晨初, 廖俊斌, 王超, 陈权, 沈江南. 不同侧链BPPO阴离子交换膜的制备及其抗污染性能[J]. 化工学报, 2021, 72(3): 1732-1741.

LIU Yuanwei, DONG Chenchu, LIAO Junbin, WANG Chao, CHEN Quan, SHEN Jiangnan. Anti-fouling properties and preparation of anion-exchange membranes based on BPPO modified by different side chain lengths[J]. CIESC Journal, 2021, 72(3): 1732-1741.

图/表 15

图1 QBPPO离子交换膜制备示意图

Fig.1 Synthesis rout of QBPPO anion-exchange membrane

图2 离子交换膜电渗析测试装置示意图

Fig.2 Experimental setup for ED experiments

图3 离子交换膜抗污染测试装置示意图

Fig.3 Experimental setup for anti-fouling experiments

图4 三种离子交换膜的红外光谱表征a—QBPPO-1; b—QBPPO-2; c—QBPPO-3

Fig.4 FTIR spectra of membranes

图5 三种不同阴离子交换膜的扫描电镜图与EDS能谱分析

Fig.5 SEM images and EDS analysis of three different membranes

图6 三种不同离子交换膜XPS谱图a—QBPPO-1; b—QBPPO-2; c—QBPPO-3

Fig.6 XPS spectra of three different membranes

图7 离子交换膜吸水率与离子交换容量

Fig.7 Wc and IEC of ion-exchange membrane

图8 离子交换膜面电阻与接触角

Fig.8 R and water contact angle of ion-exchange membrane

图9 不同离子交换膜的C-V曲线a—QBPPO-1; b—QBPPO-2; c—QBPPO-3

Fig.9 C-V curves of different ion-exchange membranes

图10 电渗析实验中淡室电导率随时间的变化

Fig.10 The change of electrical conductivity of the dilute solution along with time

表1 电渗析脱盐率、电流密度与能耗测试结果

Table 1 Removal rate, current efficiency and energy consumption in ED test after 3 h

膜	脱盐率/%	电流效率/%	能耗/(kW·h/kg)
QBPPO-1	61.60	49.08	2.20
QBPPO-2	60.16	47.48	2.26
QBPPO-3	55.53	47.26	2.28
Fuji film	59.28	41.79	2.38

图11 不同离子交换膜跨膜压差-时间变化曲线a—QBPPO-3; b—QBPPO-2; c—QBPPO-1; d—Fuji film

Fig.11 The potential across the membrane elapse with the time

表2 不同离子交换膜污染实验转折时间测试结果

Table 2 Transtion time of different membranes in fouling test

膜	转折时间/min
Fuji film	100.5
QBPPO-1	702.4
QBPPO-2	30.7
QBPPO-3	20.1

图12 SDBS与不同侧链形成的复合物的稳定构型

Fig.12 The stable structures of complexs formed by SDBS and different side-chains

表3 不同侧链与SDBS形成的复合物的ADCH原子电荷

Table 3 ADCH atomic charges of complexes formed by different side chains and SDBS

Complex	ADCH (side chain)			ADCH(SDBS)
Complex	Pyridine group	Methyl group	Alkyl chain	Sulfonic group	Phenyl group	Alkyl chain
QBPPO-1	0.662	0.122	0.216	-0.921	-0.161	0.082
QBPPO-2	0.637	0.242	0.121	-0.912	-0.164	0.076
QBPPO-3	0.617	0.273	0.120	-0.911	-0.173	0.083

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