Novel antifouling PVDF membrane with hydrophilic modification and its application in membrane bioreactor

doi:10.16085/j.issn.1000-6613.2019-0200

Abstract

Abstract:

Polyvinylidene fluoride (PVDF) is the most commonly used membrane material in membrane bioreactor (MBR) technology. However, PVDF membrane is facing some bottlenecks such as membrane fouling and low permeates flux due to the hydrophobicity of PVDF materials. Therefore, hydrophilic modification of PVDF membrane materials is a hot research topic in recent years. In this review two typical modification methods like membrane coating and grafting of PVDF membrane materials are introduced firstly. Then, with the development of nanotechnology, the hydrophilic modification methods such as the inorganic composite materials including carbon material graphene oxide(GO), inorganic antibacterial material nano silver particles and TiO₂ nanoparticles for functional preparation of PVDF membrane materials are also summarized. With the advantages of straightforward preparation processes, easy to control and broad selectivity of modification materials, MBR systems with new PVDF membranes exhibit great potential in industry, not only for wastewater treatment and re-utilization, but also for the production of bioenergy.

Key words: bioreactors, polyvinylideme fluoride, membrane, hydrophilic modification, nanomaterials

摘要：

膜生物反应器（MBR）技术中最常用的膜材料是聚偏氟乙烯（PVDF），然而由于PVDF膜的疏水性，使其在用于MBR的运行过程中存在易污染、通量低等缺陷，因此对PVDF膜材料进行亲水改性是近年来国内外研究的热点。本文首先介绍了PVDF膜材料典型的表面涂覆改性和表面化学接枝改性这两种亲水改性方法，然后概述了随着纳米科学技术的兴起，采用无机纳米材料如碳材料氧化石墨烯（GO）、无机抑菌材料纳米银粒子及二氧化钛纳米颗粒等进行功能化复合制备PVDF膜材料等亲水改性方法。研究进展表明，新型亲水改性PVDF膜材料不仅在MBR污/废水处理中优势明显，而且在可再生生物能源生产等可持续发展领域极具潜力。

关键词: 生物反应器, 聚偏氟乙烯, 膜, 亲水改性, 纳米材料

CLC Number:

TQ028.8

Wei WU,Chang LI,Xu ZHANG,Lusheng XU,Chengqiang WU,Guoliang ZHANG. Novel antifouling PVDF membrane with hydrophilic modification and its application in membrane bioreactor[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4991-4998.

伍卫,李畅,张旭,许炉生,吴成强,张国亮. 亲水改性PVDF膜材料及其膜生物反应器应用[J]. 化工进展, 2019, 38(11): 4991-4998.

Figures/Tables 6

References 34

1	MENGF, ZHANGS, OH Y, et al. Fouling in membrane bioreactors: an updated review[J]. Water Research, 2017, 114: 151-180.
2	WANGG, FANZ, WUD, et al. Anoxic/aerobic granular active carbon assisted MBR integrated with nanofiltration and reverse osmosis for advanced treatment of municipal landfill leachate[J]. Desalination, 2014, 349: 136-144.
3	ZHANGG, QINL, MENGQ, et al. Aerobic SMBR/reverse osmosis system enhanced by Fenton oxidation for advanced treatment of old municipal landfill leachate[J]. Bioresource Technology, 2013, 142: 261-268.
4	QINL, ZHANGG, MENGQ, et al. Enhanced MBR by internal micro-electrolysis for degradation of anthraquinone dye wastewater[J]. Chemical Engineering Journal, 2012, 210: 575-584.
5	QINL, ZHANGG, MENGQ, et al. Enhanced submerged membrane bioreactor combined with biosurfactant rhamnolipids: performance for frying oil degradation and membrane fouling reduction[J]. Bioresource Technology, 2012, 126: 314-320.
6	QINL, ZHANGY, XUZ, et al. Advanced membrane bioreactors systems: new materials and hybrid process design[J]. Bioresource Technology, 2018, 269: 476-488.
7	张松峰, 吴力立. 聚偏氟乙烯膜亲水改性研究进展[J]. 化工进展, 2016, 35(8): 2480-2487.
	ZHANGS F, WUL L. Research progress of hydrophilic modification of polyvinylidene fluoride[J]. Chemical Industry and Engineering Progress, 2016, 35(8): 2480-2487.
8	XUZ, YES, ZHANGG, et al. Antimicrobial polysulfone blended ultrafiltration membranes prepared with Ag/Cu₂O hybrid nanowires[J]. Journal of Membrane Science, 2016, 509: 83-93.
9	ZHANGG, LUS, ZHANGL, et al. Novel polysulfone hybrid ultrafiltration membrane prepared with TiO₂-g-HEMA and its antifouling characteristics[J]. Journal of Membrane Science, 2013, 436: 163-173.
10	LIUF, AWANIS HASHIMN, LIUY, et al. Progress in the production and modification of PVDF membranes[J]. Journal of Membrane Science, 2011, 375(1/2): 1-27.
11	WANGJ, CHENY, CHENY, et al. Fabrication and characterization of superhydrophilic and antibacterial surfaces by silver nanoparticle self-assembly[J]. Colloid and Polymer Science, 2017, 295(11):2191-2196.
12	MAW, RAJABZADEHS, MATSUYAMAH. Preparation of antifouling poly(vinylidene fluoride) membranes via different coating methods using a zwitterionic copolymer[J]. Applied Surface Science, 2015, 357: 1388-1395.
13	XUL, HEY, FENGX, et al. A comprehensive description of the threshold flux during oil/water emulsion filtration to identify sustainable flux regimes for tannic acid (TA) dip-coated poly(vinylidene fluoride) (PVDF) membranes[J]. Journal of Membrane Science, 2018, 563: 43-53.
14	VENAULTA, CHANGY, YANGH, et al. Surface self-assembled zwitterionization of poly(vinylidene fluoride) microfiltration membranes via hydrophobic-driven coating for improved blood compatibility[J]. Journal of Membrane Science, 2014, 454: 253-263.
15	SHENX, YINX, ZHAOY, et al. Improved protein fouling resistance of PVDF membrane grafted with the polyampholyte layers[J]. Colloid and Polymer Science, 2015, 293(4): 1205-1213.
16	QINA, LIX, ZHAOX, et al. Engineering a highly hydrophilic PVDF membrane via binding TiO₂ nanoparticles and a PVA layer onto a membrane surface[J]. ACS Applied Materials Interfaces, 2015, 7: 8427-8436.
17	ZHAOR J, WANGW S, ZHUF F, et al. Surface modification of PVDF membrane by simultaneously using low temperature plasma and ammonium carbonate solution[J]. Desalination Water Treatment, 2015, 56(9): 2276-2283.
18	ZHANGJ, WANGL, ZHANGG, et al. Influence of azo dye-TiO₂ interactions on the filtration performance in a hybrid photocatalysis/ultrafiltration process[J]. Journal of Colloid and Interface Science, 2013, 389:273-283.
19	ZHANGG, ZHOUM, XUZ H. Guanidyl-functionalized graphene/polysulfone mixed matrix ultrafiltration membrane with superior permselective, antifouling and antibacterial properties for water treatment[J]. Journal of Colloid and Interface Science, 2019, 540:295-305.
20	ZHAOC, XUX, CHENJ, et al. Highly effective antifouling performance of PVDF/graphene oxide composite membrane in membrane bioreactor (MBR) system[J]. Desalination, 2014, 340: 59-66.
21	LVJ, ZHANGG, ZHANGH, et al. Graphene oxide-cellulose nanocrystal (GO-CNC) composite functionalized PVDF membrane with improved antifouling performance in MBR: behavior and mechanism[J]. Chemical Engineering Journal, 2018, 352: 765-773.
22	ZHANGJ, WANGZ, LIUM, et al. In-situ modification of PVDF membrane during phase-inversion process using carbon nanosphere sol as coagulation bath for enhancing anti-fouling ability[J]. Journal of Membrane Science, 2017, 526: 272-280.
23	JAVADIM, JAFARAZDEHY, YEGANIR, et al. PVDF membranes embedded with PVP functionalized nanodiamond for pharmaceutical wastewater treatment[J]. Chemical Engineering Research and Design, 2018, 140: 241-250.
24	LIJ, LIUX, LUJ, et al. Anti-bacterial properties of ultrafiltration membrane modified by graphene oxide with nano-silver particles[J]. Journal of Colloid and Interface Science, 2016, 484: 107-115.
25	LIJ, SHAOX, ZHOUQ, et al. The double effects of silver nanoparticles on the PVDF membrane: surface hydrophilicity and antifouling performance[J]. Applied Surface Science, 2013, 265: 663-670.
26	CHENM, ZHANGX, WANGZ, et al. QAC modified PVDF membranes: antibiofouling performance, mechanisms, and effects on microbial communities in an MBR treating municipal wastewater[J]. Water Research, 2017, 120: 256-264.
27	HUW, YINJ, DENGB, et al. Application of nano TiO₂ modified hollow fiber membranes in algal membrane bioreactors for high-density algae cultivation and wastewater polishing[J]. Bioresource Technology, 2015, 193: 135-141.
28	SAFARPOURM, KHATAEEA, VATANPOURV. Effect of reduced graphene oxide/TiO₂ nanocomposite with different molar ratios on the performance of PVDF ultrafiltration membranes[J]. Separation and Purification Technology, 2015, 140: 32-42.
29	HOUF, LIB, XINGM, et al. Surface modification of PVDF hollow fiber membrane and its application in membrane aerated biofilm reactor (MABR) [J]. Bioresource Technology, 2013, 140: 1-9.
30	TAVAKOLMOGHADAMM, MONHAMMADT, HEMMATIM, et al. Surface modification of PVDF membranes by sputtered TiO₂: fouling reduction potential in membrane bioreactors[J]. Desalination Water Treatment, 2014, 57(8): 3328-3338.
31	JINM Y, LIAOY, LOH C H, et al. Preparation of polydimethylsiloxane-polyvinylidene fluoride composite membranes for phenol removal in extractive membrane bioreactor[J]. Industrial Engineer Chemistry Research, 2017, 56: 3436-3445.
32	RAHIMIZ, ZINAYIZADEHA A, ZINADINIS. Milk processing wastewater treatment in a bioreactor followed by an antifouling O-carboxymethyl chitosan modified Fe₃O₄/PVDF ultrafiltration membrane[J]. Journal of Industrial and Engineering Chemistry, 2016, 38: 103-112.
33	FANZ, QINL, ZHENGW, et al. Oscillating membrane photoreactor combined with salt-tolerated chlorella pyrenoidosa for landfill leachates treatment[J]. Bioresource Technology, 2018, 269:134-142.
34	CHONGW, MAHMOUDIE, CHUNGY, et al. Improving performance in algal organic matter filtration using polyvinylidene fluoride-graphene oxide nanohybrid membranes[J]. Algal Research, 2017, 27: 32-42.

改性方法	优点	缺点
表面涂覆改性	工艺最简单，亲水改性效果好	亲水层稳定性不高，容易脱落，稳定性差
表面化学接枝改性	基团利用率较高，改性效果好，亲水稳定好	改性工艺过程复杂、接枝率较低
多功能纳米材料掺杂改性	无需预处理或后处理，容易规模化工业应用	相容性差，纳米材料易团聚

改性方法	优点	缺点
表面涂覆改性	工艺最简单，亲水改性效果好	亲水层稳定性不高，容易脱落，稳定性差
表面化学接枝改性	基团利用率较高，改性效果好，亲水稳定好	改性工艺过程复杂、接枝率较低
多功能纳米材料掺杂改性	无需预处理或后处理，容易规模化工业应用	相容性差，纳米材料易团聚

改性膜	方法	接触角 /(°)	应用	效果	参考文献
GO/PVDF	无机材料掺杂	60.5	市政污水	NH₄⁺-N和COD去除率分别为93.75%、 87.33%	[21]
TiO₂/PVDF	无机材料掺杂	46.0	生物质能源生产	过滤阻力减少49%，藻类生物量6.5 g·m^-2·d^-1	[27]
DOPA/PVDF	表面涂覆	52.0	市政污水	COD、NH₄⁺-N和总氮（TN）去除效率分别保持在90%、98.8%和84.2%以上	[29]
TiO₂/PVDF	表面化学接枝	43.9	工业废水	较低的通量下降，污泥过滤指数（I40）约是原膜的两倍	[30]
PDMS/PVDF	表面涂覆	116.0	工业废水	苯酚的总传质系数比现有的商用PDMS管状膜高4倍以上	[31]
OCMCS-Fe₃O₄/PVDF	无机材料掺杂	—	食品加工废水	COD、TN和磷的去除效率为分别为92％～99%、52%和69%	[32]

改性膜	方法	接触角 /(°)	应用	效果	参考文献
GO/PVDF	无机材料掺杂	60.5	市政污水	NH₄⁺-N和COD去除率分别为93.75%、 87.33%	[21]
TiO₂/PVDF	无机材料掺杂	46.0	生物质能源生产	过滤阻力减少49%，藻类生物量6.5 g·m^-2·d^-1	[27]
DOPA/PVDF	表面涂覆	52.0	市政污水	COD、NH₄⁺-N和总氮（TN）去除效率分别保持在90%、98.8%和84.2%以上	[29]
TiO₂/PVDF	表面化学接枝	43.9	工业废水	较低的通量下降，污泥过滤指数（I40）约是原膜的两倍	[30]
PDMS/PVDF	表面涂覆	116.0	工业废水	苯酚的总传质系数比现有的商用PDMS管状膜高4倍以上	[31]
OCMCS-Fe₃O₄/PVDF	无机材料掺杂	—	食品加工废水	COD、TN和磷的去除效率为分别为92％～99%、52%和69%	[32]

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