PEO改性PVDF/SMA膜结构和性能

doi:10.16085/j.issn.1000-6613.2022-0869

化工进展 ›› 2023, Vol. 42 ›› Issue (3): 1515-1526.DOI: 10.16085/j.issn.1000-6613.2022-0869

PEO改性PVDF/SMA膜结构和性能

杨园园¹(), 雷婷¹, 秦青青¹^,², 武晓¹^,³, 李剑¹, 秦舒浩¹^,³(), 李嘉乐⁴, 张兵兵¹, 任露露¹

^1.贵州省材料产业技术研究院，贵州贵阳 550025
^2.中国地质大学（北京）材料科学与工程学院，北京 100083
^3.贵州大学材料与冶金学院，贵州贵阳 550025
^4.贵州理工学院材料与能源工程学院，贵州贵阳 550003

收稿日期:2022-05-10 修回日期:2022-08-17 出版日期:2023-03-15 发布日期:2023-04-10
通讯作者: 秦舒浩
作者简介:杨园园（1987—），女，博士研究生，助理研究员，研究方向为膜分离技术。E-mail：544735956@qq.com。
基金资助:
贵州省省级科技计划（黔科合支撑[2020] 4Y021号，黔科合服企[2021]9号，黔科合支撑[2022]一般211号，黔科合基础[2020] 1Y183号，黔科合支撑[2022]一般057号）;贵阳市科技计划(筑科合同[2021]1-1号)

Structure and properties of PEO modified PVDF/SMA membrane

YANG Yuanyuan¹(), LEI Ting¹, QIN Qingqing¹^,², WU Xiao¹^,³, LI Jian¹, QIN Shuhao¹^,³(), LI Jiale⁴, ZHANG Bingbing¹, REN Lulu¹

^1.Guizhou Material Industry Technology Research Institute, Guiyang 550025, Guizhou, China
^2.School of Materials Science and Engineering, China University of Geosciences, Beijing 100083, China
^3.College of Materials and Metallurgy, Guizhou University, Guiyang 550025, Guizhou, China
^4.School of Materials and Energy Engineering, Guizhou Institute of Technology, Guiyang 550003, Guizhou, China

Received:2022-05-10 Revised:2022-08-17 Online:2023-03-15 Published:2023-04-10
Contact: QIN Shuhao

摘要/Abstract

摘要：

将聚氧化乙烯（PEO）添加到聚偏氟乙烯/苯乙烯马来酸酐树脂（PVDF/SMA）膜体系中，通过非溶剂致相分离法（NIPS）制备了添加不同PEO含量的PVDF/SMA共混膜。其中PEO质量分数为2%的共混超滤膜性能最好，水通量为531.1L/(m²·h)，牛血清蛋白（BSA）截留率为65.8%，水接触角为63.6°，膜剥离强度为0.2756kN/m。接着以PVDF/SMA膜为主要研究对象测试了凝固浴温度对共混超滤膜的纯水通量以及BSA截留率的影响，该实验的结果表明凝固浴温度的改变对膜性能没有产生明显的影响。因此，选择在常温凝固浴温度下测试不同凝固浴成分对共混膜性能的影响。探究了膜在凝固浴成分分别为N,N-二甲基乙酰胺（DMAc）（质量分数为3%、6%、9%）、氯化钠（NaCl）（0.05mol/L、0.1mol/L、0.2mol/L）和乙醇（质量分数为3%、6%、9%）时的膜性能变化，以及对各个组分得到的膜样本进行扫描电子显微镜（SEM）表征。结果表明，随着DMAc含量增加，膜表面的孔在减少，且膜皮层的厚度增加，使得膜的水通量减少而BSA截留率提高。而随着NaCl浓度的升高，共混膜表面的孔结构发生改变，孔数量增多，内部指状孔数量变多变窄，膜通量逐渐增大，BSA截留率降低。同样，随着凝固浴中乙醇含量的增加，膜表面孔数量增加，指状孔变窄孔壁增厚，共混膜的水通量有所提升，BSA截留率降低。总之，存在一个平衡点，采用合适的凝固浴成分和适量的浓度，可以显著提升共混膜部分性能。此外，膜的长期运行稳定性实验结果表明得到的共混膜具有较好的抗污染性和长期运行稳定性，在实际污水处理中具有良好的应用前景。

关键词: 聚氧化乙烯, 聚偏氟乙烯, 非溶剂致相分离法, 凝固浴

Abstract:

In this study, polyethylene oxide (PEO) was added to poly (vinylidene fluoride)/styrene maleic anhydride copolymer (PVDF/SMA) membrane system, and PVDF/SMA blend membranes with different PEO contents were prepared by nonsolvent induced phase separation (NIPS). The results showed that the blend ultrafiltration membrane with PEO mass fraction of 2% had the best performance. Water flux was 531.1L/(m²·h), BSA rejection rate was 65.8%, water contact angle was 63.6° and the peel strength was 0.2756kN/m. Then, PVDF/SMA membrane was used as the main research object to test the influence of coagulation bath temperature on pure water flux and BSA rejection rate. The results indicated that temperature had no obvious effect on membrane performance. Therefore, the effects of different coagulation bath components on the properties of blend films were tested at room temperature. The changes of membrane properties in coagulation bath with N,N-dimethylacetamide (DMAc) (mass fraction of 3%, 6%, 9%), sodium chloride (0.05mol/L, 0.1mol/L, 0.2mol/L) and ethanol (mass fraction of 3%, 6%, 9%) were investigated, and the membrane samples were characterized by scanning electron microscopy (SEM). The results showed that with the increase of DMAc content, the pores on the membrane surface decreased and the thickness of the cortex increased, resulting in the decrease of water flux and the increase of BSA rejection rate. However, with the increase of NaCl concentration, the number of macropores on the membrane surface increased and the number of finger shaped pores in the membrane became narrower, leading to the gradual increase of membrane flux and the decrease of BSA rejection. Similarly, with the increase of ethanol content in the coagulation bath, the number of pores on the membrane surface increased, the finger like pores narrowed and the pore wall thickened, the water flux of the blend membrane increased, and the BSA rejection decreased. In short, the use of appropriate coagulation bath ingredients and appropriate concentration can significantly improve the partial properties of the blended film. In addition, the experimental results of the long-term operation stability of the membrane showed that the blended membrane had good anti-fouling property and long-term operation stability, and had a good application prospect in practical sewage treatment.

Key words: PEO, PVDF, nonsolvent induced phase separation, coagulation bath

中图分类号:

TQ028.8

杨园园, 雷婷, 秦青青, 武晓, 李剑, 秦舒浩, 李嘉乐, 张兵兵, 任露露. PEO改性PVDF/SMA膜结构和性能[J]. 化工进展, 2023, 42(3): 1515-1526.

YANG Yuanyuan, LEI Ting, QIN Qingqing, WU Xiao, LI Jian, QIN Shuhao, LI Jiale, ZHANG Bingbing, REN Lulu. Structure and properties of PEO modified PVDF/SMA membrane[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1515-1526.

图/表 9

图1 不同PEO含量制备的膜1~膜6的SEM表面图和截面图

表1 共混膜纯水通量、BSA截留率、膜的接触角和剥离强度

膜编号	PEO质量分数/%	SMA质量分数/%	纯水通量/L·m^-2·h^-1	BSA截留率/%	铸膜液黏度/MPa·s	接触角/（°）	剥离强度/kN·m^-1
1	0	2	599.0	50.4	32100	72.5	0.1385
2	0.5	2	508.8	47.3	45400	72.5	0.1478
3	1	2	480.3	67.1	47200	70.6	0.1480
4	1.5	2	370.1	34.6	52800	65.8	0.1705
5	2	2	581.1	65.8	53000	63.6	0.2756
6	2	0	2246.1	59.5	9555	82.9	0.1721

图2 膜5的孔径分布图

图3 温度对共混膜的纯水通量与BSA截留率的影响

图4 不同凝固浴成分对共混膜纯水通量与BSA截留率的影响

图5 在不同凝固浴成分下制备的膜的SEM表面图和截面图

表2 不同凝固浴成分下共混膜的接触角

DMAc质量分数

接触角

/(°)

NaCl浓度

/mol·L^-1

接触角

/(°)

乙醇质量分数

接触角

/(°)

图6 不同凝固浴成分下共混膜的污染指数

图7 共混膜的长期纯水通量和BSA截留率

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PEO改性PVDF/SMA膜结构和性能

Structure and properties of PEO modified PVDF/SMA membrane

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