含氟MOF与PVDF共混制备高通量油水分离膜

doi:10.19965/j.cnki.iwt.2024-0653

摘要/Abstract

摘要：

将一种全氟烷基聚乙氧基乙酸（FPEOAA）接枝在NH₂-MIL-88B上制备得到含氟MOF（FNM88B），利用FPEOAA内部化学链结构全氟烷基链（—C _n F₂ _n ₊₁—）和聚乙氧基链〔—O—（CH₂—CH₂O） _m —〕所带来的疏油性和亲水性提升MOF的亲水疏油性。将经过FPEOAA改性的FNM88B按照不同比例投加至聚偏氟乙烯（PVDF）中，利用非溶剂致相分离法（NIPs）制备出具有高水通量和高油水分离性能的混合基质膜。结果表明，FNM88B投加质量分数为1%时的共混膜（P/FN-1.0）具有良好的机械强度，拉伸应力（PVDF膜1.27 MPa）提升至2.01 MPa。同时，其纯水通量高达10 526 L/（m²·h⋅MPa），相比PVDF膜〔5 614 L/（m²·h⋅MPa）〕，纯水通量提升了约87.5%。此外，最佳比例改性膜也表现出优异的油水分离性能，截留率达96.9%。

关键词: 金属有机框架, 聚偏氟乙烯, 混合基质膜, 膜改性, 油水分离

Abstract:

In this study,perfluoroalkyl polyethylene oxide acetic acid(FPEOAA) was grafted onto NH₂-MIL-88B to synthesize a fluorine-containing metal-organic framework(FNM88B).The perfluoroalkyl (—C _n F₂ _n ₊₁—) and polyethoxy 〔—O—(CH₂—CH₂O) _m —〕 chains in the FPEOAA structure impart oil-repellent and hydrophilic properties to the MOF, thereby enhancing its hydrophilic-oil-repellent nature. The modified FNM88B, with improved properties, was incorporated into polyvinylidene fluoride (PVDF) at different proportions, and hybrid matrix membranes with high water flux and excellent oil-water separation performance were prepared by non-solvent induced phase separation (NIPS). The results showed that the blend membrane (P/FN-1.0) with 1% FNM88B exhibited excellent mechanical strength, with tensile stress increased from 1.27 MPa for the PVDF membrane to 2.01 MPa. In addition, its pure water flux was found to reach 10 526 L/(m²·h⋅MPa), an increase of approximately 87.5% compared to the PVDF membrane 〔5 614 L/(m²·h⋅MPa)〕. Furthermore, the membrane with the optimal modification ratio also demonstrated excellent oil-water separation performance, with a retention rate of 96.9%.

Key words: metal-organic framework, polyvinylidene fluoride, mixed matrix membrane, membrane modification, oil-water separation

中图分类号:

TQ028.8

徐伦波, 刘钰, 李红林, 沈舒苏, 周晓吉. 含氟MOF与PVDF共混制备高通量油水分离膜[J]. 工业水处理, 2025, 45(8): 83-89.

Lunbo XU, Yu LIU, Honglin LI, Shusu SHEN, Xiaoji ZHOU. Preparation of high-flux oil-water separation membranes by blending fluorine-containing MOF with PVDF[J]. Industrial Water Treatment, 2025, 45(8): 83-89.

https://gyscl.magtechjournal.com/CN/Y2025/V45/I8/83

图/表 10

表1 共混膜铸膜液的组成

Table 1 Composition of casting solutions for mixed matrix membranes

膜编号	PVDF/%	MOF/%	PVP/%	DMAc/%
PVDF	16	0	4	80
P/N-0.1	16	0.1	4	79.9
P/FN-0.1	16	0.1	4	79.9
P/FN-0.5	16	0.5	4	79.5
P/FN-1.0	16	1.0	4	79

图1 NM88B与FNM88B的红外光谱图

Fig.1 FTIR analysis of NM88B and FNM88B

图2 NM88B和FNM88B的SEM

Fig.2 SEM images of NM88B and FNM88B

表2 NM88B与FNM88B的EDS分析

Table 2 EDS analysis of NM88B and FNM88B

元素	原子数分数/%
元素	NM88B	FNM88B
C	44.9	38.5
O	41.1	32.1
F	—	14.6
Fe	14	14.8

图3 PVDF、P/N-0.1、P/FN-0.1、P/FN-0.5和P/FN-1.0的FTIR

Fig.3 FTIR analysis of PVDF，P/N-0.1，P/FN-0.1，P/FN-0.5 and P/FN-1.0

图4 PVDF、P/N-0.1、P/FN-0.1、P/FN-0.5、P/FN-1.0膜上表面和横截面的SEM

Fig.4 SEM images of the surface and cross-section of PVDF，P/N-0.1，P/FN-0.1，P/FN-0.5 and P/FN-1.0 membranes

图5 共混膜的水接触角

Fig.5 Water contact angles of the mixed matrix membranes

表3 共混膜的机械强度

Table 3 Mechanical strength of mixed matrix membranes

膜编号	拉伸应力/MPa
PVDF	1.27±0.033
P/FN-0.1	0.85±0.025
P/FN-0.5	1.68±0.031
P/FN-1.0	2.01±0.041

图6 共混膜的纯水通量

Fig.6 Pure water flux of the mixed matrix membranes

图7 共混膜对油水乳液的分离性能及通量恢复率

Fig.7 Separation performance and flux recovery rate of mixed matrix membranes for oil-water emulsion

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