热法增强型PVDF/GO中空纤维膜结构构筑与机理

doi:10.16085/j.issn.1000-6613.2023-1952

摘要/Abstract

摘要：

目前，膜生物反应器（MBR）用中空纤维膜量大，制备过程中使用溶剂易造成二次污染，本文采用绿色稀释剂热致相分离（TIPS）法与纤维增强联用技术制备了大通量、高强度氧化石墨烯（GO）掺杂编织管增强型聚偏氟乙烯（PVDF）中空纤维膜。GO表面具有含丰富氧官能团可明显改善PVDF中空纤维膜渗透通量与亲水性（抗污染性）。结果表明：纤维增强技术可使中空纤维膜断裂强度223.75MPa，随GO含量增加，增强型PVDF中空纤维膜水接触角值从102.04°降低至89.71°，纯水通量从920.74L/(m²·h)增至1417.45L/(m²·h)。经实验用MBR小试装备测试膜活性污泥过滤表明，其截留率大于99.50%，稳定运行后截留率仍大于98%。因此，本文全流程绿色制备的增强型PVDF中空纤维膜对替代目前市场二次污染中空纤维膜可提供科学依据与技术支撑。

关键词: 聚偏氟乙烯, 氧化石墨烯, 中空纤维膜, 热致相分离法与纤维增强联用技术, 绿色稀释剂

Abstract:

Nowadays, membrane bioreactors (MBR) are the common method used to treat wastewater. In this study, a high-flux, high-strength graphene oxide (GO)-doped braided tube reinforced polyvinylidene fluoride (PVDF) hollow fiber membrane was prepared by green diluent thermal induced phase separation (TIPS) method and fiber reinforcement technology. The surface of GO had the function of abundant oxygen, which can significantly improve the permeability flux and hydrophilicity (anti-fouling) of PVDF hollow fiber membranes. The results showed that the tensile strength of the hollow fiber membrane can reach 223.75MPa, and the water contact angle of the reinforced PVDF hollow fiber membrane decreased from 102.04° to 89.71°, and the pure water flux increased from 920.74L/(m²·h) to 1417.45L/(m²·h) with the increase content of GO. Finally, the experimental test of membrane activated sludge filtration with MBR test equipment indicated that the rejection was greater than 99.50% and the stable rejection was greater than 98%. Consequently, the prepared PVDF hollow fiber membrane by the whole process of green preparation exhibited a good guiding role in replacing the secondary polluted hollow fiber membrane in the current market.

Key words: polyvinylidene fluoride (PVDF), graphene oxide (GO), hollow fiber membrane, TIPS-fiber reinforcement technology, green diluent

中图分类号:

R318.08

赵微, 陈凯凯, 金欣, 严海波, 张爽. 热法增强型PVDF/GO中空纤维膜结构构筑与机理[J]. 化工进展, 2024, 43(11): 6344-6355.

ZHAO Wei, CHEN Kaikai, JIN Xin, YAN Haibo, ZHANG Shuang. Preparation of reinforced PVDF/GO hollow fiber membranes with TIPS-reinforced method and performance analysis[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6344-6355.

图/表 18

图1 PET编织管制备流程图及表面形貌

表1 编织管参数

参数	数值
外径/mm	1.8
复丝直径/mm	0.09
线密度/tex	27.78
目数	60
锭数	24
编织角/(°)	48.12
编织节距/mm	0.4
断裂强度/MPa	177.94

图2 纺丝流程

表2 不同GO掺杂量铸膜液

样品	PVDF/%	GO/%	三醋酸甘油酯/%
G1	30	0.1	69.9
G2	30	0.2	69.8
G3	30	0.5	69.5
G4	30	1	69

表3 增强型PVDF/GO中空纤维膜纺丝参数

参数	值
铸膜液温度/°C	175
喷丝头直径/mm	2.1
卷绕速度/r·min^-1	8.23
空气凝固浴/cm	10
凝固浴温度/°C	20±5

图3 爆破压力测试装置

图4 中空纤维膜纯水通量测试装置

图5 PVDF中空纤维膜相分离示意图(a)；PVDF/GO中空纤维膜相分离示意图(b)；PVDF/GO中空纤维膜横截面形貌(c)

图6 增强型PVDF/GO中空纤维膜的表面SEM形貌

图7 增强型PVDF/GO中空纤维膜的红外光谱、XRD和拉曼光谱图

图8 增强型PVDF/GO中空纤维膜DSC曲线和结晶度

图9 TG曲线

图10 增强型PVDF/GO中空纤维膜

图11 增强型PVDF/GO中空纤维膜的水接触角

表4 增强型PVDF/GO中空纤维膜泡点压力与最大孔径

样品	泡点压力/MPa	最大孔径/μm
G1	0.352	0.95
G2	0.301	1.23
G3	0.266	1.56
G4	0.231	1.78

图12 增强型PVDF/GO中空纤维膜

图13 活性污泥过滤实验前后对比

图14 增强型PVDF/GO中空纤维膜在MBR设备中运行的通量和截留率

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