KMnO4溶液pH调控对PVDF膜物化性能和污染行为影响

doi:10.11949/0438-1157.20191278

摘要/Abstract

摘要：

膜材料形貌结构和物化性能对膜过滤系统的安全和稳定至关重要。以聚偏氟乙烯(PVDF)改性中空纤维膜为研究对象，考察了预氧化剂高锰酸钾(KMnO₄)在pH分别为5、7、9条件下对膜材料表面形貌、亲疏水性、机械强度、纯水通量及膜污染行为的影响。结果表明，在不同pH条件下，KMnO₄对PVDF膜表面的改性层及分离层造成了破坏，导致了膜表面不同的形貌结构、化学成分、亲疏水性及抗污染性的演变。酸性条件下，由于高锰酸钾的氧化性，PVDF膜材料的CC遭到破坏，同时引入羟基(OH)，继续氧化生成了醛类和酮类化合物；而在碱性条件下，膜表面发生了脱氟化氢反应，生成了羰基(CO)。膜污染实验表明，膜分离界面的物化性质变化严重影响了膜污染行为。此研究为预氧化膜过滤工艺中pH的变化对PVDF膜材料形貌结构和性能的影响提供了数据参考。

关键词: 膜, 氧化, 超滤, 膜性能, 高锰酸钾, 预氧化, pH, 膜污染

Abstract:

The morphological structure and physicochemical properties of membrane materials are critical to the safety and stability of membrane filtration systems. The polyvinylidene fluoride (PVDF) modified hollow fiber membrane was used to investigate the effect of KMnO₄ on the surface morphology, hydrophobicity, mechanical strength, pure water flux and membrane fouling behavior at pH 5, 7 and 9, respectively. The results indicate that KMnO₄ destroys the modified and separated layers on the surface of PVDF membrane under different pH conditions, which leads to the evolution of different morphological structure, chemical composition, hydrophobicity and antipollution. Under acidic conditions, due to the oxidation of potassium permanganate, the CC of the PVDF membrane material is destroyed, and the hydroxyl group (OH) is introduced, then the aldehyde and ketone compounds are further oxidized. However, in the alkaline condition, the dehydrofluorination reaction took place on the membrane surface, resulting in the formation of carbonyl (CO). Membrane fouling experiments indicate that the change of physicochemical properties of membrane separation interface seriously affected the membrane fouling behavior. With the decrease of pH of KMnO₄ solution and the increase of contact time, the irreversible fouling of membrane surface became more and more serious. This study provides data references for the effect of pH changes on the morphology and properties of PVDF membrane materials in the pre-oxidation membrane filtration process.

Key words: membranes, oxidation, ultrafiltration, membrane property, potassium permanganate, pre-oxidation, pH, membrane fouling

中图分类号:

X 506

赵学辉, 李晓乐, 刘洋, 胡岩, 许青, 张宏伟. KMnO₄溶液pH调控对PVDF膜物化性能和污染行为影响[J]. 化工学报, 2020, 71(5): 2401-2412.

Xuehui ZHAO, Xiaole LI, Yang LIU, Yan HU, Qing XU, Hongwei ZHANG. Effect of pH control of KMnO₄ solution on physicochemical properties and fouling behavior of PVDF membrane[J]. CIESC Journal, 2020, 71(5): 2401-2412.

图/表 12

表1 PVDF膜参数

Table 1 Parameters of PVDF membrane

Characteristic	Value
outer diameter/mm	1.30
inner diameter/mm	0.70
contact angle/(°)	80.40
elongation/%	102.60
tensile strength/MPa	7.30
average pore size/μm	0.01

图1 PVDF中空纤维膜电镜图

Fig.1 SEM image of PVDF hollow fiber membrane

图2 通量测试及膜污染评价装置图

Fig.2 Schematic diagram of experimental setup1, 9—nitrogen; 2, 10—pneumatic setter; 3, 11—pressure gage; 4—feed water tank; 5—membrane module; 6—permeate tank and balance; 7—computer; 8—drain; 12—backwash water tank; 13—backwash water tank and balance

图3 高锰酸钾溶液浸泡30 d后膜的SEM图

Fig.3 SEM image of membrane surface after 30 d of immersing in potassium permanganate solution

图4 高锰酸钾溶液浸泡90 d后膜的SEM图

Fig.4 SEM image of membrane surface after 90 d of immersing in potassium permanganate solution

图5 不同pH条件下高锰酸钾溶液浸泡的膜表面ATR-FTIR谱图

Fig.5 ATR-FTIR spectra of PVDF membranes immersing in potassium permanganate solution at different pH

图6 不同pH的KMnO4浸泡后膜表面接触角的变化

Fig.6 Change of contact angle immersing in potassium permanganate solution at different pH

图7 不同pH条件高锰酸钾浸泡后膜纯水通量随跨膜压差的变化

Fig.7 Variations of pure water flux as a function of TMP immersing in potassium permanganate solution at different pH

图8 不同pH的KMnO4处理90 d后膜伸长率的变化

Fig.8 Change of elongation after 90 d immersing in potassium permanganate solution at different pH

图9 不同pH高锰酸钾溶液对PVDF膜通量影响

Fig.9 Change of J/J0 immersing in potassium permanganate solution at different pH

图10 不同pH高锰酸钾对PVDF膜表面可逆污染的影响

Fig.10 Change of reversible fouling immersing in potassium permanganate solution at different pH

图11 不同pH高锰酸钾对PVDF膜不可逆污染的影响

Fig.11 Change of irreversible fouling immersing in potassium permanganate solution at different pH

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KMnO₄溶液pH调控对PVDF膜物化性能和污染行为影响

Effect of pH control of KMnO₄ solution on physicochemical properties and fouling behavior of PVDF membrane

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