Improving chlorine resistance of piperazinyl polyamide nanofiltration membranes with in-situ modification of DAT

Abstract

Abstract:

A chlorine-stable DAT was modified on the membrane surface by in-situ modification to improve the chlorine resistance of piperazinyl polyamide nanofiltration membranes. After DAT introduction，the surface of the modified membrane appeared larger and more nodular structure，and the surface of the membrane became rougher and more hydrophilic. Under the conditions of 0.1% DAT and 2 minute assembly，the pure water flux of the modified membrane was as high as 55.9 L/（m²·h），and the rejection order of inorganic salts were Na₂SO₄（96.7%）>MgSO₄（79.5%）>MgCl₂（33.7%）>NaCl（27.3%）. After soaking in different pH sodium hypochlorite solutions，the surface structure of the unmodified membrane was seriously damaged，forming huge polymer particles，blocking the water transfer path，and the water flux decreased by more than 20%，resulting in the deterioration of separation performance. On the other hand，the active chlorine which attacked on the modified membrane was very small，the surface morphology was well preserved，and the water flux increased while maintaining a high salt retention rate，which was very attractive for the construction of chlorine-resistant desalination nanofiltration membranes.

Key words: nanofiltration membranes, in-situ modification, DAT, chlorine resistance

摘要：

为了提高哌嗪基聚酰胺纳滤膜的耐氯性，通过原位改性的方法在膜表面修饰了对氯稳定的3，5-二氨基-1，2，4-三唑（DAT）。DAT引入后，改性膜表面出现了更大、更多的结节结构，膜表面变得更加粗糙和亲水。在DAT质量分数为0.1%、交联时间为2 min的条件下，改性膜的纯水通量高达55.9 L/（m²·h），对无机盐的截留顺序为Na₂SO₄（96.7%）>MgSO₄（79.5%）>MgCl₂（33.7%）>NaCl（27.3%）。经不同pH次氯酸钠溶液浸泡后，未改性膜的表面结构被严重破坏，形成了巨大的聚合物颗粒，堵塞了水的传递路径，水通量下降了20%以上，分离性能恶化。而改性膜受到活性氯攻击很小，表面形貌较完整地保存下来，并且在保持较高盐截留率的同时，其水通量还有所上升，这对于构建耐氯脱盐纳滤膜具有很大的吸引力。

关键词: 纳滤膜, 原位改性, DAT, 耐氯性

CLC Number:

Jaikai HAN, Huazhong JI, Dapeng LIU, Yaoliang HONG. Improving chlorine resistance of piperazinyl polyamide nanofiltration membranes with in-situ modification of DAT[J]. Industrial Water Treatment, 2023, 43(6): 67-73.

韩家凯, 嵇华忠, 刘大朋, 洪耀良. 原位修饰DAT提升哌嗪基聚酰胺纳滤膜耐氯性能研究[J]. 工业水处理, 2023, 43(6): 67-73.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/Y2023/V43/I6/67

Figures/Tables 10

Fig. 1 Schematic diagram of the preparation process of the membrane

Fig. 2 ATR-FTIR spectra （a） and XPS survey spectra （b） of the membranes

Table 1 Elemental composition of the membranes surface

膜	C/%	N/%	O/%	S/%	Cl/%	C/N
PSF	76.31	3.53	14.21	5.95	0.00	21.62
NF-PIP	70.23	12.31	16.92	0.21	0.33	5.71
NF-1	67.65	14.93	16.91	0.20	0.30	4.53
NF-PIP（氯化后）	72.49	11.46	15.06	0.23	0.77	6.33
NF-1（氯化后）	69.30	11.80	18.17	0.21	0.52	5.87

Fig. 3 SEM images of the membranes

Fig. 4 Surface contact angles of the membranes

Fig. 5 Water flux and salt rejection of the composite membranes

Fig. 6 Effects of crosslinking time on the separation performance of membranes

Fig. 7 ATR-FTIR spectra （a） and XPS survey spectra （b） of the composite membranes after chlorination

Fig. 8 Variations of separation performance of NF-PIP and NF-1 membranes after chlorination treatment

Fig. 9 Long-term stability testing of NF-1 membrane

References 26

1	ZHANG Yan， SU Yanlei， PENG Jinming，et al. Composite nanofiltration membranes prepared by interfacial polymerization with natural material tannic acid and trimesoyl chloride［J］. Journal of Membrane Science，2013，429：235-242. doi:10.1016/j.memsci.2012.11.059
2	樊华，王一雯，姜钦亮，等. 高性能疏松纳滤膜的制备研究进展［J］. 工业水处理，2022，42（5）：1-10.
	FAN Hua， WANG Yiwen， JIANG Qinliang，et al. Research progress of preparation of high performance loose nanofiltration membranes［J］. Industrial Water Treatment，2022，42（5）：1-10.
3	LIU Dapeng， CHEN Yongliang， TRAN T T，et al. Facile and rapid assembly of high-performance tannic acid thin-film nanofiltration membranes via Fe³⁺ intermediated regulation and coordination［J］. Separation and Purification Technology，2021，260：118228. doi:10.1016/j.seppur.2020.118228
4	ZHANG Zhao， KANG Guodong， YU Haijun，et al. From reverse osmosis to nanofiltration：Precise control of the pore size and charge of polyamide membranes via interfacial polymerization［J］. Desalination，2019，466：16-23. doi:10.1016/j.desal.2019.05.001
5	CHO K L， HILL A J， CARUSO F，et al. Chlorine resistant glutaraldehyde crosslinked polyelectrolyte multilayer membranes for desalination［J］. Advanced Materials，2015，27（17）：2791-2796. doi:10.1002/adma.201405783
6	LIU Sihua， WU Chunrui， HOU Xiaotong，et al. Understanding the chlorination mechanism and the chlorine-induced separation performance evolution of polypiperazine-amide nanofiltration membrane［J］. Journal of Membrane Science，2019，573：36-45. doi:10.1016/j.memsci.2018.11.071
7	DO V T， TANG C Y， REINHARD M，et al. Degradation of polyamide nanofiltration and reverse osmosis membranes by hypochlorite［J］. Environmental Science & Technology，2012，46（2）：852-859. doi:10.1021/es203090y
8	XUE Jing， JIAO Zhiwei， BI Ran，et al. Chlorine-resistant polyester thin film composite nanofiltration membranes prepared with β-cyclodextrin［J］. Journal of Membrane Science，2019，584：282-289. doi:10.1016/j.memsci.2019.04.077
9	TANG Yongjian， XU Zhenliang， XUE Shuangmei，et al. Improving the chlorine-tolerant ability of polypiperazine-amide nanofiltration membrane by adding NH₂-PEG-NH₂ in the aqueous phase［J］. Journal of Membrane Science，2017，538：9-17. doi:10.1016/j.memsci.2017.05.049
10	ZHU Xuewu， CHENG Xiaoxiang， XING Jiajian，et al. In-situ covalently bonded supramolecular-based protective layer for improving chlorine resistance of thin-film composite nanofiltration membranes［J］. Desalination，2020，474：114197. doi:10.1016/j.desal.2019.114197
11	孙娟，唐红艳，周文进，等. 耐氯聚酰胺复合纳滤膜的制备与性能［J］. 高分子材料科学与工程，2021，37（9）：157-164.
	SUN Juan， TANG Hongyan， ZHOU Wenjin，et al. Preparation and performance of chlorine-resistant polyamide composite nanofiltration membranes［J］. Polymer Materials Science & Engineering，2021，37（9）：157-164.
12	FENG Xiaoquan， LIU Decheng， YE Hu，et al. High-flux polyamide membrane with improved chlorine resistance for efficient dye/salt separation based on a new N-rich amine monomer［J］. Separation and Purification Technology，2021，278：119533. doi:10.1016/j.seppur.2021.119533
13	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.
	WANG Jing. Fabrication of RO/NF membranes with anti-biofouling and chlorine resistance properties［D］. Tianjin：Tianjin University，2016.
14	SUN Haixiang， CHEN Yuhao， LIU Jiahui，et al. A novel chlorine-resistant polyacrylate nanofiltration membrane constructed from oligomeric phenolic resin［J］. Separation and Purification Technology，2021，262：118300. doi:10.1016/j.seppur.2021.118300
15	王新乐，刘铭辉，于海军，等. 基于BTP/PIP-TMC界面聚合体系制备高通量复合纳滤膜［J］. 膜科学与技术，2022，42（2）：40-46.
	WANG Xinle， LIU Minghui， YU Haijun，et al. Preparation of high throughput composite nanofiltration membranes based on BTP/PIP-TMC interfacial polymerization system［J］. Membrane Science and Technology，2022，42（2）：40-46.
16	ZHU Junyong， HOU Jingwei， YUAN Shushan，et al. MOF-positioned polyamide membranes with a fishnet-like structure for elevated nanofiltration performance［J］. Journal of Materials Chemistry A，2019，7（27）：16313-16322. doi:10.1039/c9ta02299f
17	刘四华. 聚哌嗪酰胺纳滤膜微结构原位调控及氯化机理研究［D］. 天津：天津工业大学，2020. doi:10.1016/j.memsci.2018.11.071
	LIU Sihua. In-situ control of microstructure and chlorination mechanism of piperazine amide nanofiltration membrane［D］. Tianjin：Tianjin Polytechnic University，2020. doi:10.1016/j.memsci.2018.11.071
18	王晓琳，涂丛慧，方彦彦，等. 纳滤膜孔结构、荷电性质、分离机理及动电性质研究进展［J］. 膜科学与技术，2011，31（3）：127-134. doi:10.3969/j.issn.1007-8924.2011.03.019
	WANG Xiaolin， TU Conghui， FANG Yanyan，et al. The researches on the pore structure，charge property，seperation mechanism and electrokinetic phenomena of nanofiltration membranes［J］. Membrane Science and Technology，2011，31（3）：127-134. doi:10.3969/j.issn.1007-8924.2011.03.019
19	SUN Chuangchao， ZHOU Mingyong， YUAN Jiajia，et al. Membranes with negatively-charged nanochannels fabricated from aqueous sulfonated polysulfone nanoparticles for enhancing the rejection of divalent anions［J］. Journal of Membrane Science，2020，602：117692. doi:10.1016/j.memsci.2019.117692
20	李春，贾萌萌，张梦蕾，等. 基于羟丙基-β-环糊精的界面聚合纳滤膜及其性能研究［J］. 膜科学与技术，2021，41（6）：118-125.
	LI Chun， JIA Mengmeng， ZHANG Menglei，et al. The interface polymerized nanofiltration membrane with hydroxypropyl-β-cyclodextrin as aqueous monomer［J］. Membrane Science and Technology，2021，41（6）：118-125.
21	DO V T， TANG C Y， REINHARD M，et al. Effects of chlorine exposure conditions on physiochemical properties and performance of a polyamide membrane：Mechanisms and implications［J］. Environmental Science & Technology，2012，46（24）：13184-13192. doi:10.1021/es302867f
22	LEE J H， CHUNG J Y， CHAN E P，et al. Correlating chlorine-induced changes in mechanical properties to performance in polyamide-based thin film composite membranes［J］. Journal of Membrane Science，2013，433：72-79. doi:10.1016/j.memsci.2013.01.026
23	STOLOV M， FREGER V. Degradation of polyamide membranes exposed to chlorine：An impedance spectroscopy study［J］. Environmental Science & Technology，2019，53（5）：2618-2625. doi:10.1021/acs.est.8b04790
24	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. doi:10.1016/j.desal.2019.114116
25	ZHANG Xiaotai， HUANG Hai， LI Qiang，et al. Facile dual-functionalization of polyamide reverse osmosis membrane by a natural polypeptide to improve the antifouling and chlorine-resistant properties［J］. Journal of Membrane Science，2020，604：118044. doi:10.1016/j.memsci.2020.118044
26	LIU Shasha， LOW Z X， HEGAB H M，et al. Enhancement of desalination performance of thin-film nanocomposite membrane by cellulose nanofibers［J］. Journal of Membrane Science，2019，592：117363. doi:10.1016/j.memsci.2019.117363

[1]	Hao XU, Fan ZHANG, Xin YU, Hong CHEN, Gang XUE. Removal of sulfamethoxazole and carbamazepine by Fe-Cu microelectrolysis combined with Fenton process [J]. Industrial Water Treatment, 2025, 45(3): 55-64.
[2]	Fan ZHAO, Qian GONG, Yanhe HAN, Zhi GUO, Hua JI, Xuejiao MA. Study on the treatment of petrochemical industrial wastewater by EGSB-SBR-ozone oxidation combined process [J]. Industrial Water Treatment, 2025, 45(3): 129-136.
[3]	Qiang ZHANG, Yuhua PENG, Jing ZHANG, Jun MA. Hydrothermal alkaline treatment for efficient degradation of per- and polyfluoroalkyl substances [J]. Industrial Water Treatment, 2025, 45(3): 1-9.
[4]	Yuxuan HAN, Zhijiao NI, Hongwei LU. Effects of additives on the degradation of methylene blue using DBD [J]. Industrial Water Treatment, 2025, 45(3): 165-174.
[5]	Xiangyang TANG, Jun WAN, Jianyang SUN, Yan YAN. Study on treatment of high COD fluorine-containing wastewater [J]. Industrial Water Treatment, 2025, 45(3): 193-197.
[6]	Quanfa ZHONG, Lin ZHONG, Guohui XU, Qinghai JIN, Jin YU, Fei XU, Di HE. Unravelling molecular transformation of dissolved organic matter in the full quantization treatment of landfill leachate concentrate [J]. Industrial Water Treatment, 2025, 45(2): 109-117.
[7]	Jingcun LI, Linlin YAN, Chuanjun LI, Libo GUO. Research on the treatment technology of phenolic resin industrial wastewater [J]. Industrial Water Treatment, 2025, 45(2): 193-196.
[8]	Guoqing ZHENG, Yukun HUANG, Yaocong HAN, Xingyong XUE, Yanyue LU, Lihong LAN, Zhennan CHEN. Degradation of Rhodamine B by manganese residue activated peroxymonosulfate [J]. Industrial Water Treatment, 2025, 45(1): 79-86.
[9]	Chaoyun ZHOU, Yulin LING, Wenxue JIANG, Jianhong ZHOU. Preparation of WO₃/rGO/BiOBr and its photocatalytic degradation performance for ciprofloxacin wastewater [J]. Industrial Water Treatment, 2025, 45(1): 73-78.
[10]	Yaqi SHI, Guangyuan MENG, Peng CHEN, Xinwan ZHANG, Tao FU, Zhengwu YANG, Liansheng ZHANG, Lehua ZHANG. Accurate prediction for electro-oxidation regeneration of chromium- containing waste acid based on artificial neural network [J]. Industrial Water Treatment, 2025, 45(1): 131-138.
[11]	Lingli XU, Yuxiang LIU, Jing DONG, Li REN, Wenjun WANG, Ke YUAN. Community structure of highly efficient phenol degrading bacteria and phenol metabolites [J]. Industrial Water Treatment, 2024, 44(9): 85-90.
[12]	Zirui GUO, Hongyan LI, Feng ZHANG, Jiali CUI, Qun YANG, Yun LI. Performance and mechanism of catalytic degradation of benzotriazole in water by Fe₂O₃-CuO/rCG [J]. Industrial Water Treatment, 2024, 44(9): 118-126.
[13]	Kun WEI, Lichang ZHAO, Muyu CHEN, Wantang HUANG, Jiasheng FANG, Shaoyu TANG. Review on treatment technologies and toxicological effects of brominated flame retardants in water environment [J]. Industrial Water Treatment, 2024, 44(9): 9-22.
[14]	Shoubiao LI, Yapin WU, Fengqi XU, Yu GUO, Wei YAN, Bo JIANG. The adverse impacts of produced ClO _x ^- on assessing electrochemical oxidation performance for COD removal and biotoxicity [J]. Industrial Water Treatment, 2024, 44(9): 143-150.
[15]	Lei ZHANG, Jin ZHANG, Xinlong YAN. Synthesis of porous Ni/Co LDHs and its degradation behavior for sulfamethoxazole via peroxymonosulfate activation [J]. Industrial Water Treatment, 2024, 44(8): 162-170.

Please choose a citation manager

Content to export