Preparation of composite nanofiltration membrane with β-cyclodextrin as aqueous monomer and dye rejection properties

doi:10.11949/0438-1157.20190919

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 13

Fig.1 Schematic diagram of interfacial polymerization

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

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

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

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

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

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

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

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

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

Fig.9 Flux and rejection of different dyes

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

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

References 42

1	Ning X A, Lin M Q, Shen L Z, et al. Levels, composition profiles and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in sludge from ten textile dyeing plants[J]. Environmental Research, 2014, 132: 112- 118.
2	Jhaveri J H, Murthy Z V P. A comprehensive review on anti-fouling nanocomposite membranes for pressure driven membrane separation processes[J]. Desalination, 2016, 379: 137- 154.
3	Park H B, Kamcev J, Robeson L M, et al. Maximizing the right stuff: the trade-off between membrane permeability and selectivity[J]. Science, 2017, 356( 6343): 1138- 1146.
4	蔡卫滨, 夏阳, 王玉军, 等. 白炭黑填充PDMS/PVDF复合膜的纳滤分离性能及传质特性[J]. 化工学报, 2015, 66( 7): 2555- 2564.
	Cai W B, Xia Y, Wang Y J, et al. Nanofiltration performance and mass transfer characteristics of PDMS/PVDF composite membranes filled with white carbon black[J]. CIESC Journal, 2015, 66( 7): 2555- 2564.
5	Hilal N, Al-Zoubi H, Darwish N A, et al. A comprehensive review of nanofiltration membranes: treatment, pretreatment, modelling, and atomic force microscopy[J]. Desalination, 2004, 170( 3): 281- 308.
6	唐元晖, 扈阳, 燕至琴, 等. 高浓度含盐草甘膦溶液的纳滤分离实验研究[J]. 化工学报, 2019, 70( 7): 2574- 2583.
	Tang Y H, Hu Y, Yan Z Q, et al. Experimental study on nanofiltration separation of high concentrated saline glyphosate solution[J]. CIESC Journal, 2019, 70( 7): 2574- 2583.
7	Babu J, Murthy Z V P. Treatment of textile dyes containing wastewaters with PES/PVA thin film composite nanofiltration membranes[J]. Separation and Purification Technology, 2017, ( 183): 66- 72.
8	Pan F S, Guo W X, Su Y L, et al. Direct growth of covalent organic framework nanofiltration membranes on modified porous substrates for dyes separation[J]. Separation and Purification Technology, 2019, ( 215): 582- 589.
9	邱实, 吴礼光, 张林, 等. 纳滤分离机理[J]. 水处理技术, 2009, 35( 1): 20- 24.
	Qiu S, Wu L G, Zhang L, et al. Seperation mechanisms of nanofiltration[J]. Technology of Water Treatment, 2009, 35( 1): 15- 19.
10	黄裕, 张晗, 董秉直, 等. 纳滤膜去除卡马西平的影响因素研究[J]. 环境科学, 2011, 32( 3): 705- 710.
	Huang Y, Zhang H, Dong B Z, et al. Researches on factors affecting the removal of carbamazepine by nanofiltration membranes[J]. Environment Science, 2011, 32( 3): 705- 710.
11	Wang X L, Tsuru T, Nakao S I, et al. The electrostatic and steric-hindrance model for the transport of charged solutes through nanofiltration membranes[J]. Journal of Membrane Science, 1997, 135( 1): 19- 32.
12	Attarde D, Jain M, Gupta S K. Modeling of a forward osmosis and a pressure-retarded osmosis spiral wound module using the Spiegler-Kedem model and experimental validation[J]. Separation and Purification Technology, 2016, 164: 182- 197.
13	张菁, 张庆印, 王泽瑞. 纳滤膜的制备技术[J]. 现代化工, 2018, 38( 4): 27- 31+33.
	Zhang J, Zhang Q Y, Wang Z R. Preparation technology of nanofiltration membrane[J]. Modern Chemical Industry, 2018, 38( 4): 27- 31+33.
14	时雅滨, 张学彬, 田明, 等. 纳滤膜的制备及其应用现状[J]. 化工时刊, 2018, 32( 10): 39- 42.
	Shi Y B, Zhang X B, Tian M, et al. Study on the preparation and application of nanofiltration membrane[J]. Chemical Industry Times, 2018, 32( 10): 39- 42.
15	Freitas T V, Sousa E A, Fuzari Jr G C, et al. Different morphologies of polyaniline nanostructures synthesized by interfacial polymerization[J]. Materials Letters, 2018, 224: 42- 45.
16	Hu R R, Zhang R J, He Y J, et al. Graphene oxide-in-polymer nanofiltration membranes with enhanced permeability by interfacial polymerization[J]. Journal of Membrane Science, 2018, 564: 813- 819.
17	Shen L, Hung W S, Zuo J, et al. High-performance thin-film composite polyamide membranes developed with green ultrasound-assisted interfacial polymerization[J]. Journal of Membrane Science, 2019, 570/ 571: 112- 119.
18	张润楠, 李亚飞, 苏延磊, 等. 氨基化氧化石墨烯界面聚合制备超薄复合纳滤膜[J]. 化工学报, 2018, 69( 1): 435- 445.
	Zhang R N, Li Y F, Su Y L, et al. Preparation of thin-film composite nanofiltration membranes with amino-functionalized graphene oxide by interfacial polymerization[J]. CIESC Journal, 2018, 69( 1): 435- 445.
19	Misdan N, Lau W J, Ismail A F, et al. Study on the thin film composite poly (piperazine-amide) nanofiltration membrane: impacts of physicochemical properties of substrate on interfacial polymerization formation[J]. Desalination, 2014, 344: 198- 205.
20	高爱环, 刘金盾, 张浩勤, 等. 聚哌嗪酰胺复合纳滤膜制备及其性能表征[J]. 高校化学工程学报, 2004, 18( 1): 28- 32.
	Gao A H, Liu J D, Zhang H Q, et al. Preparation and characterization of poly-piperazinamide composite nanofiltration membrane[J]. Journal of Chemical Engineering of Chinese Universities, 2004, 18( 1): 28- 32.
21	李洪懿, 翟丁, 周勇, 等. 纳米聚苯胺改性聚哌嗪酰胺纳滤膜的制备[J]. 化工学报, 2015, 66( 1): 142- 148.
	Li H Y, Zhai D, Zhou Y, et al. Polyamide composite NF membrane modified with polyaniline nanoparticles[J]. CIESC Journal, 2015, 66( 1): 142- 148.
22	俞昌朝, 储月霞, 沈江南, 等. 纳米碳管改性聚哌嗪酰胺复合纳滤膜的制备[J]. 高校化学工程学报, 2014, ( 1): 84- 91.
	Yu C C, Chu Y X, Shen J N, et al. Preparation of polypiperazine amide composite nanofiltration membrane modified by carbon nanotubes[J]. Journal of Chemical Engineering of Chinese Universities, 2014, ( 1): 84- 91.
23	Tsuru T, Sasaki S, Kamada T, et al. Multilayered polyamide membranes by spray-assisted 2-step interfacial polymerization for increased performance of trimesoyl chloride (TMC)/ m-phenylenediamine (MPD)-derived polyamide membranes [J]. Journal of Membrane Science, 2013, 446: 504- 512.
24	Yao Z, Guo H, Yang Z, et al. Reactable substrate participating interfacial polymerization for thin film composite membranes with enhanced salt rejection performance[J]. Desalination, 2018, 436: 1- 7.
25	汤蓓蓓, 徐铜文, 武培怡. 界面聚合法制备复合膜[J]. 化学进展, 2007, ( 9): 202- 209.
	Tang B B, Xu T W, Wu P Y. Preparation of thin film composite membrane by interfacial polymerization method[J]. Progress in Chemistry, 2007, ( 9): 202- 209.
26	王进, 赵长伟, 吴珍, 等. 氧化石墨烯/聚哌嗪酰胺复合纳滤膜在染料脱除中的应用研究[J]. 膜科学与技术, 2016, 36( 6): 86- 94.
	Wang J, Zhao C W, Wu Z, et al. Applied research of graphene oxide polypiperazine-amide composite nanofiltration membrane in removal of dye wastewater[J]. Membrane Science and Technology, 2016, 36( 6): 86- 94.
27	许中煌, 雷萍萍, 洪昱斌, 等. 氧化石墨烯/碱式硫酸铝掺杂聚醚砜/聚酰胺复合纳滤膜的制备及其性能[J]. 化工学报, 2018, 69( 9): 4066- 4074.
	Xu Z H, Lei P P, Hong Y B, et al. Preparation and performance of graphene oxide/basic aluminum sulfate doped polyethersulfone/polyamide composite nanofiltration membrane[J]. CIESC Journal, 2018, 69( 9): 4066- 4074.
28	Chua M L, Xiao Y C, Chung T S. Modifying the molecular structure and gas separation performance of thermally labile polyimide-based membranes for enhanced natural gas purification[J]. Chemical Engineering Science, 2013, 104: 1056- 1064.
29	Askari M, Yang T, Chung T S. Natural gas purification and olefin/paraffin separation using cross-linkable dual-layer hollow fiber membranes comprising β-cyclodextrin[J]. Journal of Membrane Science, 2012, 423/ 424: 392- 403.
30	Kusumocahyo S P, Sumaru K, Kanamori T, et al. Synthesis and characterization of an ultrathin polyion complex membrane containing β-cyclodextrin for separation of organic isomers[J]. Journal of Membrane Science, 2004, 230( 1/2): 171- 174.
31	Wang Y, Chung T S, Wang H, et al. Butanol isomer separation using polyamide-imide/CD mixed matrix membranes via pervaporation [J]. Chemical Engineering Science, 2009, 64( 24): 5198- 5209.
32	Morin-Crini N, WintertonP, Fourmentin S, et al. Water-insoluble β-cyclodextrin–epichlorohydrin polymers for removal of pollutants from aqueous solutions by sorption processes using batch studies: a review of inclusion mechanisms[J]. Progress in Polymer Science, 2018, 78: 1- 23
33	Wang Y, Chung T S, Wang H. Polyamide–imide membranes with surface immobilized cyclodextrin for butanol isomer separation via pervaporation [J]. AIChE Journal, 2011, 57( 6): 1470- 1484.
34	Alsbaiee A, Smith B J, Xiao L, et al. Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer[J]. Nature, 2015, 529: 190.
35	Adams F V, Nxumalo E N, Krause R W M, et al. Preparation and characterization of polysulfone/β-cyclodextrin polyurethane composite nanofiltration membranes[J]. Journal of Membrane Science, 2012, 405/ 406: 291- 299.
36	Villalobos L F, Huang T F, Peinemann K V. Cyclodextrin films with fast solvent transport and shape-selective permeability[J]. Advanced Materials, 2017, 29( 26): 1606641.
37	Yu Z Y, Pan Y, He Y, et al. Preparation of a novel anti-fouling β-cyclodextrin-PVDF membrane[J]. RSC Advances, 2015, 5( 63): 51364- 51370.
38	Deng J, Liu X, Zhang S, et al. Versatile and rapid post functionalization from cyclodextrin modified host polymeric membrane substrate[J]. Langmuir, 2015, 31( 35): 9665- 9674.
39	Wu H Q, Tang B B, Wu P Y. Preparation and characterization of anti-fouling β-cyclodextrin/polyester thin film nanofiltration composite membrane[J]. Journal of Membrane Science, 2013, 428: 301- 308.
40	Liu J, Hua D, Zhang Y, et al. Precise molecular sieving architectures with Janus pathways for both polar and nonpolar molecules[J]. Advanced Materials, 2018, 30( 11): 1705933.
41	Tang Y J, Shen B J, Huang B Q, et al. High permselectivity thin-film composite nanofiltration membranes with 3D microstructure fabricated by incorporation of beta cyclodextrin[J]. Separation and Purification Technology, 2019, 227: 115718.
42	张显球, 张林生, 吕锡武, 等. 纳滤分离中性溶质的截留分子量参数细孔模型[J]. 化工学报, 2007, 58( 8): 2033- 2037.
	Zhang X Q, Zhang L S, Lyu X W, et al. Steric-hindrance pore model for separation of uncharged solutes by nanofiltration with molecular weight cut-off as parameters[J]. Journal of Chemical Industry and Engineering(China), 2007, 58( 8): 2033- 2037.

[1]	Yanpeng WU, Xiaoyu LI, Qiaoyang ZHONG. Experimental analysis on filtration performance of electrospun nanofibers with amphiphobic membrane of oily fine particles [J]. CIESC Journal, 2023, 74(S1): 259-264.
[2]	Yaxin ZHAO, Xueqin ZHANG, Rongzhu WANG, Guo SUN, Shanjing YAO, Dongqiang LIN. Removal of monoclonal antibody aggregates with ion exchange chromatography by flow-through mode [J]. CIESC Journal, 2023, 74(9): 3879-3887.
[3]	Yitong LI, Hang GUO, Hao CHEN, Fang YE. Study on operating conditions of proton exchange membrane fuel cells with non-uniform catalyst distributions [J]. CIESC Journal, 2023, 74(9): 3831-3840.
[4]	Shuang LIU, Linzhou ZHANG, Zhiming XU, Suoqi ZHAO. Study on molecular level composition correlation of viscosity of residual oil and its components [J]. CIESC Journal, 2023, 74(8): 3226-3241.
[5]	Yali HU, Junyong HU, Suxia MA, Yukun SUN, Xueyi TAN, Jiaxin HUANG, Fengyuan YANG. Development of novel working fluid and study on electrochemical characteristics of reverse electrodialysis heat engine [J]. CIESC Journal, 2023, 74(8): 3513-3521.
[6]	Lei XING, Chunyu MIAO, Minghu JIANG, Lixin ZHAO, Xinya LI. Optimal design and performance analysis of downhole micro gas-liquid hydrocyclone [J]. CIESC Journal, 2023, 74(8): 3394-3406.
[7]	Jiayi ZHANG, Jiali HE, Jiangpeng XIE, Jian WANG, Yu ZHAO, Dongqiang ZHANG. Research progress of pervaporation technology for N-methylpyrrolidone recovery in lithium battery production [J]. CIESC Journal, 2023, 74(8): 3203-3215.
[8]	Ruihang ZHANG, Pan CAO, Feng YANG, Kun LI, Peng XIAO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Analysis of key parameters affecting product purity of natural gas ethane recovery process via ZIF-8 nanofluid [J]. CIESC Journal, 2023, 74(8): 3386-3393.
[9]	Zhaolun WEN, Peirui LI, Zhonglin ZHANG, Xiao DU, Qiwang HOU, Yegang LIU, Xiaogang HAO, Guoqing GUAN. Design and optimization of cryogenic air separation process with dividing wall column based on self-heat regeneration [J]. CIESC Journal, 2023, 74(7): 2988-2998.
[10]	Yuanliang ZHANG, Xinqi LUAN, Weige SU, Changhao LI, Zhongxing ZHAO, Liqin ZHOU, Jianmin CHEN, Yan HUANG, Zhenxia ZHAO. Study on selective extraction of nicotine by ionic liquids composite extractant and DFT calculation [J]. CIESC Journal, 2023, 74(7): 2947-2956.
[11]	Jinming GAO, Yujiao GUO, Chenglin E, Chunxi LU. Study on the separation characteristics of a downstream gas-liquid vortex separator in a closed hood [J]. CIESC Journal, 2023, 74(7): 2957-2966.
[12]	Zhaoguang CHEN, Yuxiang JIA, Meng WANG. Modeling neutralization dialysis desalination driven by low concentration waste acid and its validation [J]. CIESC Journal, 2023, 74(6): 2486-2494.
[13]	Kuikui HAN, Xianglong TAN, Jinzhi LI, Ting YANG, Chun ZHANG, Yongfen ZHANG, Hongquan LIU, Zhongwei YU, Xuehong GU. Four-channel hollow fiber MFI zeolite membrane for the separation of xylene isomers [J]. CIESC Journal, 2023, 74(6): 2468-2476.
[14]	Xingchi ZHU, Zhiyuan GUO, Zhiyong JI, Jing WANG, Panpan ZHANG, Jie LIU, Yingying ZHAO, Junsheng YUAN. Simulation and optimization of selective electrodialysis magnesium and lithium separation process [J]. CIESC Journal, 2023, 74(6): 2477-2485.
[15]	Hao GU, Fujian ZHANG, Zhen LIU, Wenxuan ZHOU, Peng ZHANG, Zhongqiang ZHANG. Desalination performance and mechanism of porous graphene membrane in temporal dimension under mechanical-electrical coupling [J]. CIESC Journal, 2023, 74(5): 2067-2074.