Membrane Science and Technology

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Chlorine-resistant fully aromatic polyamide reverse osmosis composite membranes: research progress and future perspectives

Authors： XIE Qingming1, GE Qingchun2

Units： 1. Weifang Intellectual Property Protection Center, Weifang 261105, China；2. College of
Environment and Safety Engineering, Fuzhou University, Fuzhou 350108, China

KeyWords： PA membrane; chlorine-resistant performance; membrane chlorination; membrane technology; membrane fouling

ClassificationCode：TQ028.8

year,volume(issue):pagination： 2026, 46(3):193-204

Abstract：

Polyamide (PA) membranes have been widely applied in water treatment owing to their facile synthesis, excellent chemical resistance, and high separation efficiency. To mitigate biofouling, chlorine-containing disinfectants are commonly added during operation, resulting in the widespread presence of active chlorine in aqueous environments. However, PA membranes are highly susceptible to degradation upon exposure to active chlorine, leading to reduced selectivity and shortened service life. To address this challenge, the development of chlorine-resistant PA membranes has become a major research focus in recent years, and numerous novel chlorine-resistant membranes have been reported. However, few studies have systematically reviewed the research progress based on the chlorination degradation mechanisms of PA membranes. Based on this, this review first elucidates the chlorination degradation pathways and chlorine-resistant mechanisms of PA membranes, followed by a comprehensive discussion of recent design strategies and advances in chlorine-resistant PA membranes. Furthermore, the main challenges in this field are summarized, and potential future research directions are proposed to provide theoretical guidance and reference for the continuous development of high-performance chlorine-resistant PA membranes.

Funds：

福建省自然科学基金面上项目（2021J01629）

AuthorIntro：

第一作者简介：谢清明（1975-），女，山东青州人，高级工程师，硕士，主要从事水处理相关技术研究.*通讯作者,E-mail：qcge2015@fzu.edu.cn

Reference：

［1］Saleem H, Zaidi S. Nanoparticles in reverse osmosis membranes for desalination: A state-of-the-art review［J］. Desalination, 2020, 475:114171.
［2］董倩. 高耐氯性聚酰胺反渗透膜的制备研究［D］. 北京: 北京化工大学, 2020.
［3］岳钰倩, 唐元晖, 李春玉, 等. 界面聚合法聚酰胺分离层形成过程的模拟研究进展［J］. 膜科学与技术, 2024, 44(2):177-187.
［4］何璇. 反渗透膜氯化改性及分子模拟研究［D］. 天津: 天津大学, 2022.
［5］嵇华忠, 韩家凯, 钱璟俐, 等. 表面接枝TAPI改善聚酰胺纳滤膜的耐氯性能［J］. 膜科学与技术, 2023, 43(2):87-94.
［6］Kawaguchi T, Tamura H. Chlorine-resistant membrane for reverse osmosis. I. Correlation between chemical structures and chlorine resistance of polyamides［J］. J Appl Polym Sci, 1984, 29:3359-3367．
［7］Gohil J, Suresh A. Chlorine attack on reverse osmosis membranes: Mechanisms and mitigation strategies［J］. J Appl Polym Sci, 2017, 541:108-126.
［8］Huang K, Reber K, Toomey M, et al. Reactivity of the polyamide membrane monomer with free chlorine: reaction kinetics, mechanisms, and the role of chloride［J］. Environ Sci Technol, 2019, 53(14):8167-8176.
［9］Liu C, Wang W, Yang B, et al. Separation, anti-fouling, and chlorine resistance of the polyamide reverse osmosis membrane: From mechanisms to mitigation strategies［J］. Water Res, 2021, 195:116976.
［10］Ingold C. Structure and mechanism in organic chemistry［M］.London: Interscience Publishers, 1953:604-610.
［11］Avlonitis S, Hanbury W, Hodgkiess T. Chlorine degradation of aromatic polyamides［J］. Desalination, 1992, 85(3):321-334.
［12］Glater J, Zachariah M. A mechanistic study of halogen interaction with polyamide RO membranes［J］. ACS Symp Ser, 1985, 281:345-358.
［13］Bieron J, Dinan F. Rearrangement and elimination of the amido group, the chemistry of amides［M］. New York: Wiley Interscience, 1970:263-266.
［14］Orton K, Soper F, Williams G. The chlorination anilides. Part Ⅲ. N-chlorination and C-chlorination as simultaneous side reactions［J］. J Chem Soc, 1928, 998-1005.
［15］Glater J, Hong S, Elimelech M. The search for a chlorine-resistant reverse-osmosis membrane［J］. Desalination, 1994, 95(3):325-345.
［16］Niu K, Huang X, Xiao Y, et al. Terminal conversion of polyamide membranes by homologous monomer vapors for chlorine-resistant desalination［J］. J Membr Sci, 2024, 709:123095.
［17］Zhai X, Meng J, Li R, et al. Hypochlorite treatment on thin film composite RO membrane to improve boron removal performance［J］. Desalination, 2011, 274(1/2/3):136-143.
［18］Kang G, Gao C, Chen W, et al. Study on hypochlorite degradation of aromatic polyamide reverse osmosis membrane［J］. J Membr Sci, 2007, 300(1):165-171.
［19］Ettori A, Gaudichet-Maurin E, Schrotter J, et al. Permeability and chemical analysis of aromatic polyamide based membranes exposed to sodium hypochlorite［J］. J Membr Sci, 2011, 375(1):220-230.
［20］Gu J, Jun B, Kwon Y. Effect of chlorination condition and permeability of chlorine species on the chlorination of a polyamide membrane［J］. Water Res, 2012, 46(16):5389-5400.
［21］Gabelich J, Frankin C, Gerringer W, et al. Enhanced oxidation of polyamide membranes using monochloramine and ferrous iron［J］. J Membr Sci, 2005, 258(1/2):64-70.
［22］Ling R, Shao J, Chen P, et al. Iron catalyzed degradation of an aromatic polyamide reverse osmosis membrane by free chlorine［J］. J Membr Sci, 2019, 577:205-211.
［23］邴绍所, 周勇, 高从堦. 耐氧化芳香PA膜的研究进展［J］. 膜科学与技术, 2016, 36(2):115-121.
［24］柳圳, 赵颂, 王志, 等. 反渗透膜耐氯及氯化修复研究进展［J］. 膜科学与技术, 2019, 39(2):123-134,142.
［25］Li H, Yu P, Li H, et al. The chlorination and chlorine resistance modification of composite polyamide membrane［J］. J Appl Polym Sci, 2015, 132(10):41584.
［26］Zhang T, Zhang K, Li J, et al. Simultaneously enhancing hydrophilicity, chlorine resistance and anti-biofouling of APA-TFC membrane surface by densely grafting quaternary ammonium cations and salicylaldimines［J］. J Membr Sci, 2017, 528:296-302.
［27］Cheng X, Liu Y, Guo Z, et al. Nanofiltration membrane achieving dual resistance to fouling and chlorine for “green” separation of antibiotics［J］. J Membr Sci, 2015, 493:156-166.
［28］Liu M, Chen Z, Yu S, et al. Thin-film composite polyamide reverse osmosis membranes with improved acid stability and chlorine resistance by coating N-isopropylacrylamide-co-acrylamide copolymers［J］. Desalination, 2011, 270:248-257.
［29］黄河清, 辛俊伟, 来仁杰, 等. 聚酰胺薄层复合膜的耐氯改性研究进展［J］. 膜科学与技术, 2023, 43(5):190-201.
［30］Yi Z, Shao F, Yu L, et al. Chemical grafting N-GOQD of polyamide reverse osmosis membrane with improved chlorine resistance, water flux and NaCl rejection［J］. Desalination, 2020, 479:114341.
［31］Kabo M, Keneiloe S, Gebhu N, et al. Antifouling and antibacteria β-cyclodextrin decorated graphene oxide /polyamide thin-film nanocomposite reverse osmosis membranes for desalination applications［J］. Sep Purif Technol, 2022, 278:119594.
［32］Gholami S, Rezvani A, Vatanpour V, et al. Improving the chlorine resistance property of polyamide TFC RO membrane by polyethylene glycol diacrylate (PEGDA) coating［J］. Desalination, 2018, 443:245-255.
［33］Kwon Y, Hong S, Choi H, et al. Surface modification of a polyamide reverse osmosis membrane for chlorine resistance improvement［J］. J Membr Sci, 2012, 415/416:192-198.
［34］Shin D, Kim N, Lee Y. Modification to the polyamide TFC RO membranes for improvement of chlorine-resistance［J］. J Membr Sci, 2011, 376(1/2):302-311.
［35］Zhu X, Cheng X, Xing J, et al. In-situ covalently bonded supramolecular-based protective layer for improving chlorine resistance of thin-film composite nanofiltration membranes［J］. Desalination, 2020, 474(11):114197.
［36］Choi W, Choi J, Bang J, et al. Layer-by-layer assembly of graphene oxide nanosheets on polyamide membranes for durable reverse osmosis applications［J］. ACS Appl Mater Interfaces, 2013, 5(23):12510-12519.
［37］Kim J, Choi Y, Lim M, et al. Reverse osmosis nanocomposite membranes containing graphene oxides coated by tannic acid with chlorine-tolerant and antimicrobial properties［J］. J Membr Sci, 2016, 514:25-34.
［38］Abbaszadeh M, Krizak D, Kundu S. Layer-by-layer assembly of graphene oxide nanoplatelets embedded desalination membranes with improved chlorine resistance［J］. Desalination, 2019, 470:114116.
［39］Gholami S, López J, Rezvani A, et al. Fabrication of thin-film nanocomposite nanofiltration membranes incorporated with aromatic amine-functionalized multiwalled carbon nanotubes. Rejection performance of inorganic pollutants from groundwater with improved acid and chlorine resistance［J］. Chem Eng J, 2020, 384:123348.
［40］Kim H, Lim M, Jung K, et al. High-performance reverse osmosis nanocomposite membranes containing the mixture of carbon nanotubes and graphene oxides［J］. J Mater Chem A, 2015, 3(13):6798-6809.
［41］Wang F, Zheng T, Xiong R, et al. CDs@ZIF-8 modified thin film polyamide nanocomposite membrane for simultaneous enhancement of chlorine-resistance and disinfection byproducts removal in drinking water［J］. ACS Appl Mater Interfaces, 2019, 11(36):33033-33042.
［42］Li H, Shi W, Zhang Y, et al. Improved performance of poly(piperazine amide) composite nanofiltration membranes by adding aluminum hydroxide nanospheres［J］. Sep Purif Technol, 2016, 166:240-251.
［43］Xu R, Wang J, Kanezashi M, et al. Development of robust organosilica membranes for reverse osmosis［J］. Langmuir, 2011, 27(23):13996-13999.
［44］Hu Y, Lu K, Yan F, et al. Enhancing the performance of aromatic polyamide reverse osmosis membrane by surface modification via covalent attachment of polyvinyl alcohol (PVA)［J］. J Membr Sci, 2016, 501: 209-219.
［45］汪婧. 抗生物污染及耐氯化反渗透/纳滤膜研制［D］. 天津: 天津大学, 2016.
［46］Lu J, Yang B, Lu D, et al. Secondary interfacial reaction of p-aminodiphenylamine enables polyamide reverse osmosis membrane with enhanced and regenerative chlorine resistance［J］. J Membr Sci, 2023, 688:1221.
［47］Wang J, Li S, Guan Y, et al. Novel RO membranes fabricated by grafting sulfonamide group: Improving water permeability, fouling resistance and chlorine resistant performance［J］. J Membr Sci, 2022, 641:119919.
［48］Zhang X, Choi P, Khanzada N, et al. Highly permeable chlorine-resistant forward osmosis membrane by grafting novel sulfonamide monomers［J］. Desalination, 2023, 564:116754.
［49］Verbeke R, Gómez V, Vankelecom F. Chlorine-resistance of reverse osmosis (RO) polyamide membranes［J］. Prog Polym Sci, 2017, 72:1-15.
［50］Meng Q, Ge Q. Enhancing chlorine resistance and water permeability during forward osmosis separation using superhydrophilic materials with conjugated systems［J］. ACS Appl Mater Interfaces, 2020, 12:35393-35402.
［51］Yan W, Wang Z, Zhao S, et al. Combining co-solvent-optimized interfacial polymerization and protective coating-controlled chlorination for highly permeable reverse osmosis membranes with high rejection［J］. J Membr Sci, 2019, 572:61-72.
［52］La Y, Sooriyakumaran R, Miller C, et al. Novel thin film composite membrane containing ionizable hydrophobes:pH-dependent reverse osmosis behavior and improved chlorine resistance［J］. J Mater Chem, 2010, 20(22):4615-4620.
［53］柳圳. 利用N,N′-亚甲基双丙烯酰胺制备耐氯RO膜及修复氯化RO膜［D］. 天津: 天津大学, 2019.
［54］Wang X, Li Q, Zhang J, et al. Novel thin-film reverse osmosis membrane with MXene Ti3C2Tx embedded in polyamide to enhance the water flux,anti-fouling and chlorine resistance for water desalination［J］. J Membr Sci, 2020, 603:118036.
［55］杨碧野. 聚酰胺反渗透复合膜耐氯性能的可再生改性研究［D］. 杭州: 浙江大学, 2020.
［56］Chen Y, Zhang T, Chai D, et al. Enhancing the NaCl/Na2SO4 separation selectivity and chlorine resistance of nanofiltration membranes by incorporating novel designed starch nanoparticles［J］. Appl Surf Sci, 2022, 604:154417.
［57］Xue S, Ji C, Xu Z, et al. Chlorine resistant TFN nanofiltration membrane incorporated with octadecylamine-grafted GO and fluorine-containing monomer［J］. J Membr Sci, 2018, 545:185-195.
［58］Kim Y, Lee S, Kim D, et al. Preparation and characterization of thermally crosslinked chlorine resistant thin film composite polyamide membranes for reverse osmosis［J］. Desalination, 2010, 250(2):865-867.
［59］Magnus P, Slater M. Studies on the hydrocarboxylation of N-acetylimines, enamines and allylamines［J］. Tetrahedron Lett, 1987, 28(25):2829-2832.
［60］Zhang J, Hai Y, Zuo Y, et al. Novel diamine-modified composite nanofiltration membranes with chlorine resistance using monomers of 1,2,4,5-benzene tetracarbonyl chloride and m-phenylenediamine［J］. J Mater Chem A, 2015, 3(16):8816-8824.
［61］Pan Z, Geng G, Yu S, et al. Highly selective and chlorine-resistant polyamide reverse osmosis membranes for advanced water treatment via Fenton-assisted aromatic amine surface engineering［J］. Water Res, 2025, 289:124828.
［62］Liu M, Wu J, Ma B, et al. Selective layer reconstruction of deteriorated polyamide membrane by surface chemical deposition for desalination performance restoration and simultaneous antifouling and anti chlorine［J］. Desalination, 2023, 547:116224.
［63］Zhang X, Zhang C, Lin Z, et al. Chlorine-resistant and dual anti-biofouling reverse osmosis membranes with zwitterionic and quaternary ammonium copolymers via mussel-inspired one-step codeposition［J］. Sep Purif Technol, 2025, 359(P2):130615.
［64］Wang J, Hao S, Qi P, et al. Superior chlorine-resistance of hyperbranched polyglycerol (hPG) grafted polyamide reverse osmosis membrane and its chlorine-resistant mechanism［J］. J Membr Sci, 2024, 709:123092.

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