Metal coordinated PAN hollow fiber membranes with triaxial cross-linked structure and its self-cleaning performance
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摘要: 为探究一种具有自清洁性能的三维交联结构中空纤维膜(HFM)材料，采用湿法工艺制备了聚丙烯腈(PAN)基中空纤维膜，经不同反应条件对其进行肟化改性，并与金属离子(Fe3+)进行配位制备金属螯合三维交联结构中空纤维膜。对该中空纤维膜的制备工艺、结构组成、表面形貌、亲疏水性能、膜通量和截留率、自清洁性能等进行了表征与测试。结果表明：聚丙烯腈肟化率会随着改性时间、温度和盐酸羟胺浓度的增加而增加；肟化反应导致聚合物非晶结构增加，有利于小分子向纤维材料内部的吸附；铁离子与偕胺肟化中空纤维膜形成的交联网络结构，虽然使其蕴晶结构、亲水性能和膜通量受到一定程度影响，但使其对牛血清白蛋白(BSA)截留率提升至88%。此外，Fe(III)与H2O2形成的Fenton催化体系赋予中空纤维膜较好的抗污自清洁性能，膜通量恢复率达到84.6 %。Abstract: To explore a kind of triaxial cross-linked hollow fiber membrane (HFM) with self-cleaning performance, polyacrylonitrile based HFM prepared by wet processing was chemically modified into amidoximated PAN hollow fiber membranes. Then the active groups were coordinated with metal ions (Fe3+) randomly to achieve metal coordinated amidoximation PAN hollow fiber membranes with triaxial cross-linked structure. Preparation process, structural composition, surface morphology, hydrophilic and hydrophobic properties, membrane flux and retention, self-cleaning performance of the hollow fiber membranes were studied. Results show that the amidoximation rate of the membranes increases with the rise of time, temperature and hydroxylamine hydrochloride concentration during the modification process, and the modification levels would affect the crystallinity of the hollow fiber membranes so as to enhance the adsorption of small molecules into the fiber material. Although the Fe ions on the membranes would impact their crystal structure, hydrophilic property and membrane flux, but the triaxial cross-linked structure would promote the retention performance for bovine serum albumin to 88%. Besides, Fenton catalytic system coupled by Fe(III) and H2O2 endows FePAN-HFM with antifouling and self-cleaning properties and the flux recovery rate reaches to 84.6% significantly.
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Key words:
- polyacrylonitrile /
- hollow fiber membrane /
- self-cleaning /
- metal coordination /
- membrane flux
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图 1 反应条件对AOPAN-中空纤维膜(HFM)改性情况的影响
Figure 1. Effect of reaction conditions on AOPAN-hollow fiber membrane (HFM) anmidoximation
CR—Conversion rate of cyanide group; PAN—Polyacrylonitrile; t—Time; T—Temperature; c—Concentration
图 2 聚丙烯腈(PAN)-HFM在肟化改性(AOPAN-HFM)和Fe配位反应(FePAN-HFM)前后的FTIR图谱(a)和XRD图谱(b)
Figure 2. FTIR spectra (a) and XRD patterns (b) for PAN-HFM, AOPAN-HFM and FePAN-HFM
图 3 PAN-HFM ((a), (b))、AOPAN-HFM ((c), (d))和FePAN-HFM ((e), (f))的SEM图像及FePAN-HFM的EDS能谱(g)
Figure 3. SEM images for PAN-HFM ((a), (b)), AOPAN-HFM ((c), (d)), FePAN-HFM ((e), (f)) and EDS for FePAN-HFM (g)
图 4 PAN-HFM (a)、AOPAN-HFM (b)、FePAN-HFM (c)的静态接触角
Figure 4. Static contact angle for PAN-HFM (a), AOPAN-HFM (b) and FePAN-HFM (c)
图 5 FePAN-HFM自清洁性能在膜分离过程中的表现：中空纤维膜样品在纯水、牛血清白蛋白(BSA)中的通量变化((a), (b))及其截留率(c)
Figure 5. Self-cleaning performance of FePAN-HFM in membrane separation process: Membrane flux variation in pure water, bovine serum albumin (BSA) ((a), (b)) and its retention ratio (c)
FRR—Flux recovery rate; Rr—Reversible ratio; Rir—Irreversibility rate
图 6 Fe离子负载量对FePAN-HFM自清洁性能的影响(a)及其动力学分析(b)
Figure 6. Effect of different Fe ions loading desage on FePAN-HFM self-cleaning performance (a) and its kinetic study (b)
D—Degradation rate
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