亲水改性PVDF膜材料及其膜生物反应器应用

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

摘要/Abstract

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

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

中图分类号:

TQ028.8

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.

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.

图/表 6

参考文献 34

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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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