Polyethersulfone ultrafiltration membrane with low molecular weight cut off

doi:10.11949/j.issn.0438-1157.20181192

Abstract

Abstract:

The PES ultrafiltration base membranes were prepared with PES, DMAc and TMA through the method of immersion precipitation phase inversion. Then PVA solution was coated on the base membranes surface and crosslinked by heating to obtain low molecular weight cut-off ultrafiltration membranes. The experimental results showed that with the increase of PVA concentration, the molecular weight cut-off first decreased and then increased; as the heat treatment temperature increased, the water flux decreased and the molecular weight cut-off decreased. When the PVA mass fraction is 0.1% and heat-treated at 80°C for 10 min, the molecular weight cut-off of the membrane was 900. The pure water flux was 6.10 L/(m²·h) . The cross-linking structure of PVA and TMA was confirmed by infrared spectroscopy analyzer.

Key words: membrane, ultrafiltration, phase inversion, polyvinyl alcohol, filtration

摘要：

以聚醚砜(PES)为原料，均苯三甲酸(TMA)为添加剂，采用浸没沉淀相转化法制备聚醚砜超滤基膜，之后将聚乙烯醇(PVA)溶液涂覆在膜表面，经加热交联得到低截留分子量超滤膜。实验结果表明，随着聚乙烯醇浓度升高，截留分子量先减小再增加；随着热处理温度的升高，水通量减少，截留分子量减小。聚乙烯醇质量浓度为0.1%，80℃加热10 min，膜的截留分子量为900，纯水通量为6.10 L/(m²·h)。红外光谱分析证实PVA与TMA反应生成了交联结构。

关键词: 膜, 超滤, 相转化, 聚乙烯醇, 过滤

CLC Number:

TQ 028.8

Hao XU, Kaifeng GU, Yunhao LI, Yong ZHOU, Congjie GAO. Polyethersulfone ultrafiltration membrane with low molecular weight cut off[J]. CIESC Journal, 2019, 70(5): 1999-2006.

许浩, 顾凯锋, 李韵浩, 周勇, 高从堦. 低截留分子量聚醚砜超滤膜[J]. 化工学报, 2019, 70(5): 1999-2006.

Figures/Tables 10

References 34

1	Dasgupta J , Sikder J , Chakraborty S , et al . Re20181192tion of textile effluents by membrane based treatment techniques: a state of the art review[J]. Journal of Environmental Management, 2015, 147: 55-72.
2	Vincent-Vela M C , Álvarez-Blanco S , Lora-García J , et al . Application of several pretreatment technologies to a wastewater effluent of a petrochemical industry finally treated with reverse osmosis[J]. Desalination and Water Treatment, 2015, 55(13): 3653-3661.
3	李庭, 熊华, 陈望华, 等 . 香蕉汁生产过程中褐变控制和超滤工艺的研究[J]. 食品研究与开发, 2008, 29(11): 100-103.
	Li T , Xiong H , Chen W H , et al . Study on browning control and ultrafiltration process in banana juice production [J]. Food Research and Development, 2008, 29(11): 100-103.
4	汪锰, 王湛, 李政雄 . 膜材料及其制备[M]. 北京: 化学工业出版社, 2003: 175-214.
	Wang M , Wang Z , Li Z X . Membrane Materials and Their Preparation[M]. Beijing: Chemical Industry Press, 2003: 175-214.
5	Arthanareeswaran G , Latha C S , Mohan D , et al . Studies on cellulose acetate/low cyclic dimmer polysulfone blend ultrafiltration membranes and their applications[J]. Separation Science and Technology, 2006, 41(13): 2895-2912.
6	Rana D , Scheier B , Narbaitz R M , et al . Comparison of cellulose acetate (CA) membrane and novel CA membranes containing surface modifying macromolecules to remove pharmaceutical and personal care product micropollutants from drinking water[J]. Journal of Membrane Science, 2012, 409: 346-354.
7	Zhao Y F , Zhu L P , Yi Z , et al . Improving the hydrophilicity and fouling-resistance of polysulfone ultrafiltration membranes via surface zwitterionicalization 20181192ted by polysulfone-based triblock copolymer additive[J]. Journal of Membrane Science, 2013, 440: 40-47.
8	Breitbach L , Hinke E , Staude E . Heterogeneous functionalizing of polysulfone membranes[J]. Die Angewandte Makromolekulare Chemie: Applied Macromolecular Chemistry and Physics, 1991, 184(1): 183-196.
9	Ahmad A L , Abdulkarim A A , Ooi B S , et al . Recent development in additives modifications of polyethersulfone membrane for flux enhancement[J]. Chemical Engineering Journal, 2013, 223: 246-267.
10	Chang H H , Chen S C , Lin D J , et al . The effect of Tween-20 additive on the morphology and performance of PVDF membranes[J]. Journal of Membrane Science, 2014, 466: 302-312.
11	Pezeshk N , Narbaitz R M . More fouling resistant modified PVDF ultrafiltration membranes for water treatment[J]. Desalination, 2012, 287: 247-254.
12	Mondal M , De S . Characterization and antifouling properties of polyethylene glycol doped PAN-CAP blend membrane[J]. RSC Advances, 2015, 5(49): 38948-38963.
13	邬智勇 . 原位聚合型阻燃尼龙6的制备、性能及应用研究[D]. 长沙: 湖南大学, 2011.
	Wu Z Y . Preparation, properties and application of flame retardant polyamide 6 by in-situ ploymerization[D]. Changsha: Hunan University, 2011.
14	Yuan G , Xu Z , Wei Y . Characterization of PVDF-PFSA hollow fiber UF blend membrane with low-molecular weight cut-off [J]. Separation Science and Technology, 2009, 69(2): 141-148.
15	董声雄, 龚琦 . 聚偏氟乙烯/聚醋酸乙烯酯共混小截留分子量超滤膜[J]. 化工学报, 2002, 53(11): 1212-1214.
	Dong S X , Gong Q . PVDF/PVAc blend ultrafiltration membrane with small molecular mass cut-off[J]. Journal of Chemical Industry and Engineering(China), 2002, 53 (11): 1212-1214.
16	Hosseini S M , Gholami A , Madaeni S S , et al . Fabrication of (polyvinyl chloride/cellulose acetate) electrodialysis heterogeneous cation exchange membrane: characterization and performance in desalination process[J]. Desalination, 2012, 306: 51-59.
17	Anis S F , Lalia B S , Hashaikeh R . Controlling swelling behavior of poly (vinyl) alcohol via networked cellulose and its application as a reverse osmosis membrane [J]. Desalination, 2014, 336: 138-145.
18	高嵩, 张守海, 杨大令, 等 . 低截留分子量PPES超滤膜的制备[J]. 功能高分子学报, 2008, 21(3): 317-321.
	Gao S , Zhang S H , Yang D L , et al . Preparation of ploy(phthalazinone ether sulfone) ultrafiltration membranes with low molecular weight cut-off[J]. Journal of Functional Polymer, 2008, 21(3): 317-321.
19	Han R , Zhang S , Liu C , et al . Effect of NaA zeolite particle addition on poly (phthalazinone ether sulfone ketone) composite ultrafiltration (UF) membrane performance[J]. Journal of Membrane Science, 2009, 345(1/2): 5-12.
20	See-Toh Y H , Silva M , Livingston A . Controlling molecular weight cut-off curves for highly solvent stable organic solvent nanofiltration (OSN) membranes[J]. Journal of Membrane Science, 2008, 324(1/2): 220-232.
21	Peng F , Jiang Z , Hoek E M V . Tuning the molecular structure, separation performance and interfacial properties of poly (vinyl alcohol)–polysulfone interfacial composite membranes[J]. Journal of Membrane Science, 2011, 368(1/2): 26-33.
22	Peng F , Huang X , Jawor A , et al . Transport, structural, and interfacial properties of poly (vinyl alcohol)-polysulfone composite nanofiltration membranes[J]. Journal of Membrane Science, 2010, 353(1/2): 169-176.
23	史凤娇 . 低截留分子量超滤膜对有机微污染物的截留效能与机制研究[D]. 哈尔滨: 哈尔滨工程大学, 2014.
	Shi F J . Rejection effet and mechanism of micro-organic pollutants by ultrafiltration with low molecular weight cut-off [D]. Harbin: Harbin Engineering University, 2014.
24	王姣, 张守海, 杨大令, 等 . 非溶剂添加剂对杂萘联苯聚醚砜超滤膜结构和性能的影响[J]. 膜科学与技术, 2008, 28(3): 50-53.
	Wang J , Zhang S H , Yang D L , et al . Effect of nonsolvent additives on configuration and performance of poly (phthalazinone ether sulfone) ultrafiltration membrane[J].Membrane Science and Technology, 2008, 28(3): 50-53.
25	陶杰 . 界面聚合制备小孔径复合超滤膜及其性能研究[D]. 杭州: 浙江理工大学, 2011.
	Tao J . Preparation and properties of small-pore composite ultrafiltration membranes by interfacial polymerization [D]. Hangzhou: Zhejiang University of Technology, 2011.
26	Wang K , Matsuura T , Chung T , et al . The effects of flow angle and shear rate within the spinneret on the separation performance of poly (ethersulfone) (PES) ultrafiltration hollow fiber membranes[J]. Journal of Membrane Science, 2004, 240(1/2): 67-79.
27	吴宗策, 郭玉阳, 梁松苗, 等 . 高性能聚醚砜/聚乙烯醇复合超滤膜的研究[J]. 水处理技术, 2016, (2): 51-55.
	Wu Z C , Guo Y Y , Liang S M , et al . Study on high performance PES/PVA composite ultrafiltration membrane [J]. Technology of Water Treatment, 2016, (2): 51-55.
28	Bolto B , Tran T , Hoang M , et al . Crosslinked poly (vinyl alcohol) membranes[J]. Progress in Polymer Science, 2009, 34(9): 969-981.
29	Petersen R J . Composite reverse osmosis and nanofiltration membranes[J]. Journal of Membrane Science, 1993, 83(1): 81-150.
30	Dai W S , Barbari T A . Hydrogel membranes with mesh size asymmetry based on the gradient crosslinking of poly (vinyl alcohol)[J]. Journal of Membrane Science, 1999, 156(1): 67-79.
31	Yong S K , Hyo J K , Un Y K . Asymmetric membrane formation via immersion precipitation method(Ⅰ): Kinetic effect[J]. Journal of Membrane Science, 1991, 60(2/3): 219-232.
32	冷云飞, 潘凯, 原涛, 等 . 聚砜超滤膜的表面化学改性[J]. 北京化工大学学报(自然科学版), 2009, 36(3): 65-70.
	Leng Y F , Pan K , Yuan T , et al . Surface chemical modification of a polysulfone membrane[J]. Journal of Beijing University of Chemical Technology (Natural Science Edition), 2009, 36(3): 65-70.
33	赵劲彤, 张学俊, 邸玉静 . 柠檬酸改性聚乙烯醇制备可生物降解膜的研究[J]. 塑料助剂, 2009, (6): 28-33.
	Zhao J T , Zhang X J , Di Y J . Study on the preparation of biodegradable film by citric acid modified polyvinyl alcohol [J]. Plastic Additives, 2009, (6): 28-33.
34	Guo M , Wang S , Gu K , et al . Gradient cross-linked structure: towards superior PVA nanofiltration membrane performance[J]. Journal of Membrane Science, 2019, 569: 83-90.

PES基膜	PES/%(mass)	TMA%(mass)	DMAc%(mass)
P1	15	0	85
P2	15	1	84
P3	15	2	83
P4	15	3	82
P5	15	4	81

PES基膜	PES/%(mass)	TMA%(mass)	DMAc%(mass)
P1	15	0	85
P2	15	1	84
P3	15	2	83
P4	15	3	82
P5	15	4	81

PES基膜	水通量/(L/(m²·h))	接触角/(°)	表面孔径/nm
P1	116.02±40	75.05±3	11.2
P2	149.53±30	55.36±1	14.9
P3	412.63±50	53.85±3	13.5
P4	624.9±150	64.45±1	15.2
P5	726.83±70	60.38±1	18.4

PES基膜	水通量/(L/(m²·h))	接触角/(°)	表面孔径/nm
P1	116.02±40	75.05±3	11.2
P2	149.53±30	55.36±1	14.9
P3	412.63±50	53.85±3	13.5
P4	624.9±150	64.45±1	15.2
P5	726.83±70	60.38±1	18.4

TMA concent/%(mass)	元素含量/%(atom)
TMA concent/%(mass)	C(理论/实际)	O(理论/实际)	S(理论/实际)	O/C(理论/实际)
0	75/72.79	18.75/20.27	7.25/6.94	0.25/0.278
1	69.66/69.73	26.31/25.96	4.03/4.31	0.379/0.372
2	67.13/70.76	29.91/25.49	2.96/3.75	0.446/0.360
3	65.65/70.55	32.00/25.29	2.35/4.15	0.487/0.358