β-环糊精为水相单体的复合纳滤膜制备及染料截留性能

doi:10.11949/0438-1157.20190919

摘要/Abstract

摘要：

采用β-环糊精(β-CD)作为水相单体，均苯三甲酰氯(TMC)为油相单体，通过界面聚合法制备高通量的β-CD/TMC复合纳滤膜，利用细孔模型和静电排斥-立体位阻模型探究染料分离机理。采用红外光谱仪、场发射电子显微镜、接触角测量仪及Zeta电位分析仪进行分析表征。结果表明，红外光谱中出现了酯基官能团的特征峰；Zeta电位分析表明所制备的复合纳滤膜表面荷负电；SEM图像结构和接触角数值表明β-CD浓度为4.0%时，膜表面出现大量褶皱，膜的亲水性更好，0.2 MPa压力下，纯水通量可达207.81 L·m ^-2·h ^-1，对染料刚果红(CR)、孟加拉玫瑰红(RB)、活性艳红X-3B、亚甲基蓝(MB)的截留率分别为100%、99.05%、97.65%、32.92%；6 h连续运行实验，通量呈现先下降后稳定的趋势，对染料活性艳红X-3B的截留率始终高于97%。

关键词: 膜, 纳滤, 界面聚合, β-环糊精, 分离, 染料

Abstract:

Using β-cyclodextrin (β-CD) as the aqueous phase monomer and trimesyl chloride (TMC) as the oil phase monomer, a high-throughput β-CD/TMC composite nanofiltration membrane was prepared by the interfacial polymerization method. The pore model and electrostatic repulsion-steric hindrance model were used to explore the mechanism of dye separation. Infrared spectrometer, field emission electron microscope, contact angle measuring instrument and Zeta potential analyzer were used for analysis and characterization. The results showed that the peak of ester group which is generated by IP appeared in the FT-IR. Zeta potential analysis indicated that the surface of composite NF membrane was negatively charged. SEM images structure and contact angle values showed that when the concentration of β-CD was 4.0%, a lot of folds appeared on the membrane surface and the membrane was more hydrophilic. At the pressure of 0.2 MPa, the pure water flux can reach 207.81 L·m ^-2·h ^-1, the rejection of the Congo red, the Bengal rose, the reactive brilliant red X-3B and the methylene blue was 100%, 99.05%, 97.65% and 32.92%, respectively. The 6 h operation can effectively reject the dye reactive brilliant red X-3B with rejection higher than 97% flux goes down and then keeps the tendency of stable.

Key words: membrane, nanofiltration, interfacial polymerization, β-cyclodextrin, separation, dye

中图分类号:

TQ 028.8

刘丽雪, 张少峰, 赵长伟, 宝乐尔呼, 俞灵, 王军. β-环糊精为水相单体的复合纳滤膜制备及染料截留性能[J]. 化工学报, 2020, 71(2): 889-898.

Lixue LIU, Shaofeng ZHANG, Changwei ZHAO, Erhu BAOLE, Ling YU, Jun WANG. Preparation of composite nanofiltration membrane with β-cyclodextrin as aqueous monomer and dye rejection properties[J]. CIESC Journal, 2020, 71(2): 889-898.

图/表 13

图1 界面聚合示意图

Fig.1 Schematic diagram of interfacial polymerization

图2 平板膜性能测试装置

Fig.2 Schematic diagram of flat membrane experiment devicea—feed tank；b—feed pump；c—membrane module；d—flow valve；e—flowmeter；f—pressure valve；g—pressure gage

表1 不同类型染料数据

Table 1 Data of different dyes

染料名称	摩尔质量/(g·mol ^-1)	Stokes半径/nm	染料类型	价态	最大吸收波长/nm
Rose bengal(RB)	1017	0.779	非离子型	0	548
reactive red X-3B	616	0.628	非离子型	0	537
Congo red(CR)	696	0.662	阴离子型	-2	498
methylene blue(MB)	319	0.471	阳离子型	+1	664

图3 PES30和β-CD/TMC复合纳滤膜的傅里叶变换红外光谱

Fig.3 FT-IR spectra of PES30 and β-CD/TMC composite NF membrane

图4 β-CD4.0/TMC复合纳滤膜的C 1s XPS谱图

Fig.4 C 1s XPS spectra of β-CD4.0/TMC composite NF membrane

图5 PES30与β-CD/TMC复合纳滤膜的SEM图

Fig. 5 SEM images of PES30 and β-CD/TMC composite NF membrane

图6 PES与β-CD/TMC复合纳滤膜的断面图

Fig.6 SEM cross-section images of PES and β-CD4.0/TMC composite NF membrane

图7 PES30和β-CD/TMC复合纳滤膜通量和截留率

Fig.7 Flux and rejection of PES and β-CD/TMC composite NF membrane

图8 PES30与β-CD/TMC复合纳滤膜表面的接触角

Fig.8 Contact angle of PES30 and β-CD/TMC composite NF membrane

表2 PES与β-CD/TMC复合纳滤膜的Zeta电位

Table 2 Zeta potential of surface of PES and β-CD/TMC composite nanofiltration membrane

Membrane	TMC in organic phase/%(质量)	β-CD in aqueous phase/%(质量)	Zeta potential/mV
PES	0	0	-30.70
β-CD1.0/TMC	0.2	1.0	-34.93
β-CD1.8/TMC	0.2	1.8	-35.36
β-CD3.0/TMC	0.2	3.0	-44.85
β-CD4.0/TMC	0.2	4.0	-53.10
β-CD5.0/TMC	0.2	5.0	-58.83

图9 不同类型染料的通量和截留率

Fig.9 Flux and rejection of different dyes

表3 β-CD为水相单体在本研究和文献中的比较

Table 3 Comparison of β-CD as aqueous monomer in this work and literatures

水相	油相	制膜方法	通量/(L·m ^-2·h ^-1)	截留率/%	压力/MPa	文献
TEOA ^① and β-CD	TMC	IP	26	Na ₂SO ₄ 78	0.6	[ 39]
β-CD	TC ^②	IP	9.6	MO ^③ 91	0.1	[ 36]
β-CD	TMC	IP	5.6	MO 86	0.1	[ 40]
β-CD	TMC	IP	119.2 106.9	CR 100 X-3B 97.6	0.2	this work

图10 β-CD4.0/TMC复合纳滤膜的长周期稳定性实验

Fig.10 Stability properties of β-CD4.0/TMC composite NF membrane

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