基于β-环糊精的TFC正渗透膜原位构筑及抗污染性能

doi:10.16085/j.issn.1000-6613.2024-2066

摘要/Abstract

摘要：

采用在水相中引入添加剂调控界面聚合过程的方法对聚酰胺薄膜复合材料（TFC）的活性层进行原位改性，以突破渗透性与选择性之间的“trade-off”效应以及提升膜的抗污染性能。首先，通过相转化制备聚砜（PSF）支撑层，在此基础上通过在界面聚合中掺入水相添加剂β-环糊精（β-CD）原位构筑TFC-β-CD改性正渗透膜。β-CD外部存在亲水性羟基基团，可与酰氯基团进行界面聚合产生聚酯结构而被牢固保留在膜中，并且其携带的纳米空腔结构是一种高效传质通道，使其在提升膜水通量的同时保持高截留率。通过扫描电子显微镜（SEM）、傅里叶变换红外光谱（FTIR）和原子力显微镜（AFM）分析了改性前后的膜表面结构、组成和粗糙度，利用错流式实验装置考察了膜的传质性能和结构参数，并探究了膜的抗有机污染性能和膜污染可逆性。结果表明：TFC-β-CD（1.5）改性膜的水接触角由（62.6±1.52）°下降至（44.9±0.52）°，亲水性显著提升，且粗糙度降低。在有机污染实验中，与TFC膜相比，当3种特征污染物的原料液不含Ca²⁺时，TFC-β-CD改性膜的通量恢复率在90%以上，当原料液含Ca²⁺时，TFC-β-CD改性膜的不可逆污染程度较轻，具有较好的抗污染性能。

关键词: 膜, 薄膜复合材料正渗透膜, β-环糊精, 原位改性, 抗污染

Abstract:

The active layer of thin-film composite (TFC) membranes was modified in situ by introducing an additive in the aqueous phase to regulate the interfacial polymerization process in order to break through the "trade-off" effect and improve the anti-pollution performance of the membrane. Initially, the polysulfone (PSF) support layer was prepared via phase inversion. Subsequently, β-cyclodextrin (β-CD) was incorporated into the aqueous phase during interfacial polymerization to construct TFC-β-CD modified forward osmosis membranes. There were hydrophilic hydroxyl groups outside β-CD, which can be interfacial polymerized with acyl chloride groups to produce polyester structure and be firmly retained in the membrane. Moreover, the nanocavity structure carried by β-CD was an efficient mass transfer channel so that it can improve the membrane water flux while maintaining a high retention rate. The surface structure, composition and roughness of the membranes before and after modification were analyzed using scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM). The mass transfer properties and structural parameters of the membranes were examined using a cross-flow experimental setup, and the antifouling performance for organics and fouling reversibility were evaluated. The results indicated that the water contact angle of the TFC-β-CD (1.5) modified membrane decreased from (62.6±1.52)° to (44.9±0.52)°, demonstrating a significant enhancement in hydrophilicity and a reduction in roughness. During the antifouling experiments, compared to the TFC membrane, the flux recovery of the TFC-β-CD modified membrane was above 90% when the feed solution was three model organics respectively with Ca²⁺. When the feed solution contained Ca²⁺, the irreversible fouling of the TFC-β-CD modified membrane was less severe, exhibiting better antifouling properties.

Key words: membranes, thin-film composite forward osmosis membrane, β-cyclodextrin, in-situ modification, antifouling

中图分类号:

TQ028

孙燕, 陈马超, 田娜, 谢晓阳, 李晓玲, 何皎洁, 赵晓红. 基于β-环糊精的TFC正渗透膜原位构筑及抗污染性能[J]. 化工进展, 2025, 44(6): 3671-3682.

SUN Yan, CHEN Machao, TIAN Na, XIE Xiaoyang, LI Xiaoling, HE Jiaojie, ZHAO Xiaohong. Research on in-situ construction of TFC forward osmosis membrane by β-cyclodextrin and its antifouling performance[J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3671-3682.

图/表 15

表1 支撑层的基本特性[29]

平均孔径/nm	截留分子量/kDa	孔隙率/%	透水性/L·m^-2·Pa^-1·h^-1	接触角/(°)	膜厚度/μm
13.46±0.49	239.57±1.64	72.9±1.0	(275±40)×10^-5	80.5±3.5	50±4

表2 不同浓度β-CD界面聚合反应单体溶液的组成

序号	膜名称	水相				有机相
序号	膜名称	MPD质量分数/%	β-CD质量分数/%	TEA质量分数/%	CSA质量分数/%	TMC质量分数/%
1	TFC	3.4	—	—	—	0.15
2	TFC-β-CD（0.5）	3.4	0.5	1	0.43	0.15
3	TFC-β-CD（1.0）	3.4	1.0	1	0.43	0.15
4	TFC-β-CD（1.5）	3.4	1.5	1	0.43	0.15
5	TFC-β-CD（2.0）	3.4	2.0	1	0.43	0.15

图1 β-CD原位改性TFC FO膜的制备示意图

图2 错流式正渗透装置

表3 传质系数和结构参数测定的运行条件

阶段	运行模式	运行时长	错流速率	原料液（1L）	汲取液（2L）
1	活性层朝向原料液（AL-FS）	1h	8cm/s	去离子水	0.5mol/LNaCl溶液
2					1mol/LNaCl溶液
3					1.5mol/LNaCl溶液
4					2mol/LNaCl溶液

图3 PSF支撑层、TFC膜和不同β-CD浓度下TFC-β-CD膜表面的SEM图像及PSF支撑层、TFC膜和TFC-β-CD（1.5）的SEM断面图像

图4 TFC膜和不同β-CD浓度下TFC-β-CD膜表面的AFM图像及粗糙度数值

图5 TFC膜和TFC-β-CD（1.5）膜表面的红外光谱图

图6 TFC膜和不同β-CD浓度下TFC-β-CD膜表面的水接触角

图7 TFC膜和不同β-CD浓度下TFC-β-CD膜的水通量、反向盐通量及盐水比

图8 TFC膜和不同β-CD浓度下TFC-β-CD膜的传质系数和结构参数

图9 未添加Ca2+情况下不同有机物存在时TFC膜和TFC-β-CD膜的水通量衰减曲线

图10 添加Ca2+情况下不同有机物存在时TFC膜和TFC-β-CD膜的水通量衰减曲线

图11 未添加Ca2+情况下TFC膜和TFC-β-CD膜清洗前后的水通量恢复率

图12 添加Ca2+情况下TFC膜和TFC-β-CD膜清洗前后的水通量恢复率

参考文献 42

[1]	DSILVA WINFRED RUFUSS D, KAPOOR V, ARULVEL S, et al. Advances in forward osmosis (FO) technology for enhanced efficiency and output: A critical review[J]. Journal of Cleaner Production, 2022, 356: 131769.
[2]	THARAYIL Jeevan Mathew, CHINNAIYAN Prakash, JOHN Daphne Mary, et al. Environmental sustainability of FO membrane separation applications—Bibliometric analysis and state-of-the-art review[J]. Results in Engineering, 2024, 21: 101677.
[3]	CHANG ZHEN Hong, Jing Yao SUM, LAU Woei Jye, et al. Current state-of-the-art of non-reverse osmosis-like forward osmosis technology[J]. Journal of Membrane Science, 2024, 711: 123209.
[4]	WANG Jianlong, LIU Xiaojing. Forward osmosis technology for water treatment: Recent advances and future perspectives[J]. Journal of Cleaner Production, 2021, 280: 124354.
[5]	ABOUNAHIA Nada, IBRAR Ibrar, KAZWINI Tayma, et al. Desalination by the forward osmosis: Advancement and challenges[J]. Science of the Total Environment, 2023, 886: 163901.
[6]	JAFARINEJAD Shahryar. Forward osmosis membrane technology for nutrient removal/recovery from wastewater: Recent advances, proposed designs, and future directions[J]. Chemosphere, 2021, 263: 128116.
[7]	朱腾义, 曹再植. 正渗透-膜蒸馏耦合工艺在高难度废水处理中的应用研究进展[J]. 化工进展, 2021, 40(11): 5894-5906.
	ZHU Tengyi, CAO Zaizhi. Application research progress of forward osmosis-membrane distillation coupling process in the treatment of highly difficult wastewater[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 5894-5906.
[8]	RAHMAN Sumaita Nawar, SALEEM Haleema, ZAIDI Syed Javaid. Progress in membranes for pressure retarded osmosis application[J]. Desalination, 2023, 549: 116347.
[9]	BLANDIN Gaetan, FERRARI Federico, LESAGE Geoffroy, et al. Forward osmosis as concentration process: Review of opportunities and challenges[J]. Membranes, 2020, 10(10): 284.
[10]	Keng Siang GOH, CHEN Yunfeng, Daniel Yee Fan NG, et al. Organic solvent forward osmosis membranes for pharmaceutical concentration[J]. Journal of Membrane Science, 2022, 642: 119965.
[11]	ZHU Linwei, DING Chun, ZHU Tengyang, et al. A review on the forward osmosis applications and fouling control strategies for wastewater treatment[J]. Frontiers of Chemical Science and Engineering, 2022, 16(5): 661-680.
[12]	FARAHBAKHSH Javad, GOLGOLI Mitra, KHIADANI Mehdi, et al. Recent advances in surface tailoring of thin film forward osmosis membranes: A review[J]. Chemosphere, 2024, 346: 140493.
[13]	IBRAHEEM Bakr M, AANI Saif AL, ALSARAYREH Alanood A, et al. Forward osmosis membrane: Review of fabrication, modification, challenges and potential[J]. Membranes, 2023, 13(4): 379.
[14]	TIAN Miao, MA Tao, Kunli GOH, et al. Forward osmosis membranes: The significant roles of selective layer[J]. Membranes, 2022, 12(10): 955.
[15]	KAHRIZI Mohammad, GONZALES Ralph Rolly, KONG Lingxue, et al. Significant roles of substrate properties in forward osmosis membrane performance: A review[J]. Desalination, 2022, 528: 115615.
[16]	赵珍珍, 郑喜, 王雪琪, 等. 聚酰胺复合膜微孔支撑基底的研究进展[J]. 化工进展, 2023, 42(4): 1917-1933.
	ZHAO Zhenzhen, ZHENG Xi, WANG Xueqi, et al. Research progress on microporous supporting substrate of polyamide composite membrane[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1917-1933.
[17]	张赛晖, 李校阳, 高慧, 等. 制备聚酰胺复合膜中界面聚合反应添加剂研究进展[J]. 化工进展, 2022, 41(9): 4884-4894.
	ZHANG Saihui, LI Xiaoyang, GAO Hui, et al. Recent progress in additives in interfacial polymerization for the preparation of polyamide composite membrane[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4884-4894.
[18]	KANAGARAJ Palsamy, SHANMUGARAJA Masilamani, RANA Dipak, et al. Development of high performance thin-film (nano) composite membranes for forward osmosis desalination applications—A review [J]. Materials Science and Engineering: B, 2024, 299: 116966.
[19]	JAIN Harshita, GARG Manoj Chandra. Fabrication of polymeric nanocomposite forward osmosis membranes for water desalination—A review[J]. Environmental Technology & Innovation, 2021, 23: 101561.
[20]	LI Xu, WANG Zhi, HAN Xianglei, et al. Regulating the interfacial polymerization process toward high-performance polyamide thin-film composite reverse osmosis and nanofiltration membranes: A review[J]. Journal of Membrane Science, 2021, 640: 119765.
[21]	LIAO Zhipeng, ZHU Junyong, LI Xin, et al. Regulating composition and structure of nanofillers in thin film nanocomposite (TFN) membranes for enhanced separation performance: A critical review[J]. Separation and Purification Technology, 2021, 266: 118567.
[22]	HAY Man Saung Hnin Soe, Phyo Darli MAW, LOFTSSON Thorsteinn, et al. A current overview of cyclodextrin-based nanocarriers for enhanced antifungal delivery[J]. Pharmaceuticals, 2022, 15(12): 1447.
[23]	孙燕, 冯倩颖, 谢晓阳, 等. 基于环糊精构筑薄膜复合膜的研究进展[J]. 化工进展, 2024, 43(8): 4464-4476.
	SUN Yan, FENG Qianying, XIE Xiaoyang, et al. Research progress on the cyclodextrin-based thin film composite membranes[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4464-4476.
[24]	ZHU Bo, SHAO Ruiqi, LI Nan, et al. Progress of cyclodextrin based-membranes in water treatment: Special 3D bowl-like structure to achieve excellent separation[J]. Chemical Engineering Journal, 2022, 449: 137013.
[25]	TANG Yongjian, SHEN Bingjie, HUANG Benqing, 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.
[26]	YU Zongxue, PAN Yang, HE Yi, et al. Preparation of a novel anti-fouling β-cyclodextrin-PVDF membrane[J]. RSC Advances, 2015, 5(63): 51364-51370.
[27]	YASSARI Mehrasa, SHAKERI Alireza. Nature based forward osmosis membranes: A novel approach for improved anti-fouling properties of thin film composite membranes[J]. Chemical Engineering Research and Design, 2022, 184: 137-151.
[28]	JEON Sungkwon, PARK Chan Hyung, SHIN Seung Su, et al. Fabrication and structural tailoring of reverse osmosis membranes using β-cyclodextrin-cored star polymers[J]. Journal of Membrane Science, 2020, 611: 118415.
[29]	郝秀娟. Ca²⁺原位改性对TFC正渗透膜污染的控制效能与机理研究[D]. 哈尔滨: 哈尔滨工业大学, 2020.
	HAO Xiujuan. Research on controlling efficiency and mechanism of tfc forward osmosis membrane fouling by Ca²⁺ in-situ modification[D]. Harbin: Harbin Institute of Technology, 2020.
[30]	刘婷丽. 相转化法制备聚合物滤膜的大数据研究[D]. 合肥: 中国科学技术大学, 2022.
	LIU Tingli. A big data study of polymeric filtration membranes prepared by phase inversion method[D]. Hefei: University of Science and Technology of China, 2022.
[31]	TIRAFERRI Alberto, Ngai Yin YIP, STRAUB Anthony P, et al. A method for the simultaneous determination of transport and structural parameters of forward osmosis membranes[J]. Journal of Membrane Science, 2013, 444: 523-538.
[32]	WU Xing, FANG Fang, ZHANG Bifeng, et al. Biogenic silver nanoparticles-modified forward osmosis membranes with mitigated internal concentration polarization and enhanced antibacterial properties[J]. NPJ Clean Water, 2022, 5: 41.
[33]	ZHAO Haiyang, QIU Shi, WU Liguang, et al. Improving the performance of polyamide reverse osmosis membrane by incorporation of modified multi-walled carbon nanotubes[J]. Journal of Membrane Science, 2014, 450: 249-256.
[34]	TANG Chuyang Y, KWON Young-Nam, LECKIE James O. Effect of membrane chemistry and coating layer on physiochemical properties of thin film composite polyamide RO and NF membranes[J]. Desalination, 2009, 242(1/2/3): 149-167.
[35]	REN Dan, Jet Ing Ngie YEO, LIU Tianyin, et al. Time-dependent FTIR microscopy for mechanism investigations and kinetic measurements in interfacial polymerisation: A microporous polymer film study[J]. Polymer Chemistry, 2019, 10(22): 2769-2773.
[36]	JIANG Zhiwei, KARAN Santanu, LIVINGSTON Andrew G. Water transport through ultrathin polyamide nanofilms used for reverse osmosis[J]. Advanced Materials, 2018, 30(15): e1705973.
[37]	PENG Shaoyin, WANG Zhenbei, QI Fei, et al. Novel insights into the interaction reactive components and synergistic fouling mechanisms of ultrafiltration by natural organic matter fractions and Kaolin[J]. Environmental Research, 2022, 212: 113285.
[38]	ESFAHANI Milad Rabbani, AKTIJ Sadegh Aghapour, DABAGHIAN Zoheir, et al. Nanocomposite membranes for water separation and purification: Fabrication, modification, and applications[J]. Separation and Purification Technology, 2019, 213: 465-499.
[39]	HAO Xiujuan, GAO Shanshan, TIAN Jiayu, et al. Calcium-carboxyl intrabridging during interfacial polymerization: A novel strategy to improve antifouling performance of thin film composite membranes[J]. Environmental Science & Technology, 2019, 53(8): 4371-4379.
[40]	GHORBANI Farnaz, SHAKERI Alireza, VAFAEI Mohammad ALI, et al. Polyoxometalate-cored supramolecular star polymers as a novel crosslinker for graphene oxide-based forward osmosis membranes: Anti-fouling, super hydrophilic and high water permeable[J]. Separation and Purification Technology, 2021, 267:118578.
[41]	BAGHERZADEH Mojtaba, BAYRAMI Arshad, SHEKARI Zahra, et al. High-performance thin-film nanocomposite (TFN) forward osmosis (FO) membranes incorporated with porous hydrophobic-core/hydrophilic-shell nanoparticles[J]. Desalination, 2021, 515: 115181.
[42]	EGHBALAZAR Tala, SHAKERI Alireza. High-Performance thin-film nanocomposite forward osmosis membranes modified with poly(dopamine) coated UiO₆₆-(COOH)₂ [J]. Separation and Purification Technology, 2021, 277: 119438.