Preparation and characterization of PVDF-glass fiber composite membrane reinforced by interfacial UV-grafting copolymerization

A novel inorganic–organic composite membrane,namely poly(vinylidene fluoride) PVDF-glass fiber(PGF) composite membrane,was prepared and reinforced by interfacial ultraviolet(UV)-grafting copolymerization to improve the interfacial bonding strength between the membrane layer and the glass fiber.The interfacial polymerization between inorganic–organic interfaces is a chemical cross-linking reaction that depends on the functionalized glass fiber with silane coupling(KH570) as the initiator and the polymer solution with acrylamide monomer(AM) as the grafting block.The Fourier transform infrared spectrometer-attenuated total reflectance(FTIR-ATR) spectra and the energy dispersive X-ray(EDX) pictures of the interface between the glass fiber and polymer matrix confirmed that the AM was grafted to the surface of the glass fiber fabric and that the grafting polymer was successfully embedded in the membrane matrix.The formation mechanisms,permeation,and anti-fouling performance of the PGF composite membrane were measured with different amounts of AM in the doping solutions.The results showed that the grafting composite membrane improved the interfacial bonding strength and permeability,and the peeling strength was improved by 32.6% for PGF composite membranes with an AM concentration at 2 wt.%.     

Performances of biological aerated filter employing hollow fiber membrane segments of surface-improved poly （sulfone） as biofilm carriers

Using the surface of poly （sulfone） hollow fiber membrane segments as grafted layer, the hydrophilic acrylamide chain was grafted on by UV-photoinduced grafting polymerization. The gained improvement of surface wettability for the modified membrane was tested by measuring the contact-angle as well as FTIR spectra. Then correlation between the hydrophilic ability of support material and the biofilm adherence ability was demonstrated by comparing the pollutant removal rates from urban wastewater via two identical lab-scale up-flow biological aerated filters, one employed the surface wettability modified poly （sulfone） hollow fiber membrane segment as biofilm carder and the other employed unmodified membrane segment as biofilm carder. The experimental results showed that under the conditions of influent flux 5 L/h, hydraulic retention time 9 h and gas to liquid ratio （G/L） 10： 1, the removal rates of chemical oxygen demand （COD） and ammonium nitrogen （NH4^＋-N） for the modified packing filter and the unmodified packing filter was averaged at 83.64% and 96.25%, respectively, with the former filter being 5%-20% more than the latter. The effluent concentration of COD, NH4^＋-N and turbidity for the modified packing filter was 25.25 mg/L, 2 mg/L and 8 NTU, respectively. Moreover, the ammonium nitrogen removal performance of the filter packing the modified PSF was compared with the other bioreactor packing of an efficient floating medium. The biomass test indicated that the modified membrane matrixes provided better specific adhesion （3310-5653 mg TSS/L support）, which gave a mean of 1000 mg TSS/L more than the unmodified membrane did. In addition, the phenomenon of simultaneous denitrification on the inner surface of the support and nitrification on the outer surface was found in this work.     

高渗透聚砜中空纤维超滤膜制备

介绍了采用独创制膜液三元体系添加剂,以及相应发展的干喷－湿纺制膜工艺条件,研制出具有高透水性能,无大孔缺陷,孔分布狭窄,截留性能优异的聚砜训空纤维超滤膜。膜结构为双排指状孔结构,膜内外表面具有相近的孔分布皮层,可用于内压或外压超滤操作。     

Beijing Tong Ren Tang Company Limited Scientific Research Institute, Beijing 100011, China

By dynamic method under UV irradiation,commercial melt-blown polypropylene(PPMB)filter element was modified with acrylamide(AAm)using benzophenone(BP)as initiator.Attenuated total reflection-Fourier transform infrared spectroscopy and scanning electron microscope verified that polyacrylamide chain was grafted on the fiber surface of PPMB filter element.Elemental content analysis with energy dispersive X-ray of fibers revealed that the polymerization content in the inner part of filter element was relatively higher than that in the outer.Degree of grafting changed with initiator concentration,monomer concentration,reaction temperature and reached 2.6% at the reaction condition:C_(BP)=0.06 mol/L,C_(AAm)=2.0 mol/L,irradiation time:80 min,temperature: 60℃.Relative water flux altered with the hydrophilicity and pore size of filter element.In the antifouling test,the modified filter gave greater flux recovery(approximately 70%)after filtration of the water extract of Liuweidihuang,suggesting that the fouling layer was more easily reversible due to the hydrophilic nature of the modified filter.     

聚离子液体刷接枝改性PVDF膜及其对药物硫酸氢氯吡咯雷分离性能研究

以聚偏氟乙烯(PVDF)超滤膜为底膜,通过浸渍法使多巴胺(DOPA)在膜表面形成聚多巴胺(PDOPA)层,然后由化学反应固定溴代卤化物,并通过原子转移自由基聚合(ATRP)反应在膜表面接枝聚离子液体刷(PBIVm-Br),以制备聚离子液体刷改性PVDF膜,即PVDF-g-PBIVm-Br膜.结果表明,改性PVDF膜的接触角下降至60°以下且显示出良好的荷正电性.改性膜的药物通量和截留率均大于未改性PVDF膜,分离10 mg·L~(-1)的硫酸氢氯吡咯雷时,改性膜(M4)的药物通量可达27.62 L·m~(-2)·h~(-1),截留率为89.03%,通量恢复率为95.32%.经过60 h分离实验后,膜M4对硫酸氢氯吡咯雷溶液的分离通量维持在18.05 L·m~(-2)·h~(-1),截留率从89.03%上升到92.19%.以上结果表明,聚离子液体刷改性膜在荷正电有机污染物的分离方面具有一定的应用前景.     

中空纤维复合膜用于回收有机溶剂蒸气的研究

采用新的制膜工艺制备聚二甲基硅氧烷-聚砜中空纤维复合膜.该复合膜对有机溶剂蒸气具有适宜的渗透速度,且对有机溶剂蒸气和空气的分离系数较大.用该复合膜组装φ10×500mm中空纤维膜分离器,以正己烷(C_6)和氮气(N_2)的混合气做分离器性能实验.混合气从中空纤维膜内管进气,考察了压力、进气中C_6的浓度、驰放气流速等操作条件对C_6的渗透速率、驰放气及渗透气中C_6的浓度以及C_6同N_2的分离系数的影响.实验结果表明,进料浓度对分离效果有重要影响;中空纤维复合膜用于从含溶剂蒸气浓度高的废气中回收有机溶剂是可行的.     

Modifying glass fiber surface with grafting acrylamide by UV-grafting copolymerization for preparation of glass fiber reinforced PVDF composite membrane

Experimental design and response surface methodology(RSM) were used to optimize the modification of conditions for glass surface grafting with acrylamide(AM) monomer for preparation of a glass fiber reinforced poly(vinylidene fluoride)(PVDF) composite membrane(GFRP-CM). The factors considered for experimental design were the UV(ultraviolet)-irradiation time, the concentrations of the initiator and solvent, and the kinds and concentrations of the silane coupling agent. The optimum operating conditions determined were UV-irradiation time of 25 min, an initiator concentration of 0–0.25 wt.%,solvent of N-Dimethylacetamide(DMAC), and silane coupling agent KH570 with a concentration of 7 wt.%. The obtained optimal parameters were located in the valid region and the experimental confirmation tests conducted showed good accordance between predicted and experimental values. Under these optimal conditions, the water absorption of the grafted modified glass fiber was improved from 13.6% to 23%; the tensile strength was enhanced and the peeling strength of the glass fiber reinforced PVDF composite membrane was improved by 23.7% and 32.6% with an AM concentration at 1 wt.% and 2 wt.%. The surface composition and microstructure of AM grafted glass fiber were studied via several techniques including Field Emission Scanning Electron Microscopy(FESEM), Fourier transform infrared spectroscopy-attenuated total reflectance(FTIR-ATR) and energy dispersive X-ray spectroscopy(EDX). The analysis of the EDX and FTIR-ATR results confirmed that the AM was grafted to the glass fiber successfully by detecting and proving the existence of nitrogen atoms in the GFRP-CM.     

吸附Cu~(2+)接枝纤维的制备与表征

以漂白蔗渣浆纤维素为基体,二乙烯三胺为单体,硝酸铈铵为引发剂,制备胺基接枝纤维,制备高效重金属吸附剂。研究了单体用量、引发剂用量、温度、时间等反应因素对胺基接枝纤维制备的影响。采用红外光谱、X射线衍射和扫描电镜分析表征胺基接枝纤维的结构。结果表明:绝干蔗渣纤维:单体二乙烯三胺=1:1(质量比),硝酸铈铵的用量为25%,温度为70℃,时间为2 h时可以获得较高的吸附量,其吸附量可以达到12.8 mg/g。通过红外光谱和扫描电镜分析手段,对接枝纤维的结构进行表征。     

纳米二氧化硅改性聚酰胺复合膜及其抗污染性能

采用经3-氨基丙基三甲氧基硅烷（APTMS）修饰的纳米二氧化硅（SiNPs）,对正渗透聚酰胺复合膜（TFC）进行抗污染改性.在静电吸附作用下,APTMS-SiNPs可通过表面涂覆的方式接枝在带负电的TFC表面,以提高膜的亲水性和抗污染效能.改性后,大量纳米材料成功接枝在膜表面,膜表面的接触角降低了54%,而膜电位和表面粗糙度无明显变化.采用海藻酸钠作为代表污染物,对原膜和改性膜的动态污染行为进行探究,通过监测污染阶段的通量变化和膜表面滤饼层含量,发现改性膜在膜污染后期表现出优良的抗污染性能,最终通量衰减降低了28%,膜表面滤饼层含量减少了35%.改性膜的抗污染性能主要归因于APTMS-SiNPs带来的膜表面亲水性的大幅提高.     

吐温20吸附改性聚乙烯膜改善MBR抗污染性能

通过物理吸附Tween20对聚乙烯中空纤维微孔膜(polyethylene hollow fiber microporous membranes,PEHFMM)进行表面改性。衰减全反射傅立叶变换红外光谱(attenuated total reflection Fourier transform infrared spectroscopy,FT-IR/ATR)和场发射扫描电子显微镜(field emission scanning electron microscopy,FE-SEM)观察结果表明:吐温20有效地吸附到了PEHFMM上。采用停滴法测定水接触角(contact angle,CA)以表征膜表面的亲水性。数据显示:30℃时随着吸附量的增加膜的水接触角先降后升并出现最低值;40℃吸附时水接触角则单值下降直至稳定。为建立吸附量与膜生物反应器(membrane bioreactor,MBR)中膜污染作用之间的关系,使用人工污水进行了活性污泥过滤实验。结果发现:吐温20吸附量大约是100～200μmol/g时可以明显地提高膜在MBR中的抗污染能力。     

纳米聚丙烯-丙烯酸酯改性材料的制备及其吸油性能研究

以纳米聚丙烯(nano-polypropylene,PP)为基体,丙烯酸丁酯为单体,采用紫外辐射方法制备高吸油性复合材料(butyl acrylate grafted nano-polypropylene,BAPP)。试验确定的最佳制备条件为:辐照时间1 h,单体浓度33.3%,光敏剂浓度0.2%,并通过傅里叶变换红外光谱仪对改性前后样品的结构进行了表征,结果表明丙烯酸丁酯被成功接枝到纳米聚丙烯纤维上。考察了接枝率、吸附时间、吸附温度和pH值等对改性纳米聚丙烯材料吸油性能的影响,改性纳米聚丙烯对机油的吸附符合二级动力学模型。实验数据显示,常温下纳米聚丙烯和改性材料对原油的吸油量分别为35.5 g/g和28.5 g/g,改性后的材料吸油性能明显改善。温度对改性纳米聚丙烯纤维的吸油率有明显影响,与油品种类及粘度有关系,随着pH值的升高,改性纳米聚丙烯纤维对机油的吸油率迅速增加。     

超滤法处理含原油污水的研究

本文论述了用聚砜中空纤维超滤膜处理含原油污水的研究,讨论了料液循环速度、操作温度、操作压力和料液浓度对膜传输性能的影响。设计了直径为10.2cm(4英寸)的中空纤维组件和相应的超滤设备,考察了透水速度随操作时间的变化,选用合适的膜清洗工艺,膜透水速度可保持为60L/m~2·h(40℃,1kg/cm~2压力)。工业化实验证明,用中空纤维膜处理含原油污水是成功的,透过液含油量低于10mg/L。该法亦适用于其它种类含油污水的处理。     

城市污水二级出水超滤膜污染与膜特性的研究

以城市污水二级出水为过滤介质,考察了PVA、PVP、PMMA等与PVDF的二元及三元共混超滤膜的过滤污染行为.结果表明,共混优化了PVDF超滤膜的结构参数,添加剂PVP、PVA可有效改善膜的亲水化程度,提高膜渗透通量.超滤膜的亲水性和结构特性对膜抗污染性能影响较大;堵孔阻力是二级出水过滤膜污染不可逆的主要原因.亲水性较强的超滤膜,二级出水过滤初期易因浓差极化而导致滤饼层污染,造成一定的通量衰减,但易清洗恢复,不可逆污染指数(rir)为0,抗污染性能好.致密的超滤膜表面有利于防止二级出水中的中低分子量污染物进入膜内部,而断面通透大孔和疏松海绵层结构的超滤膜,能减少二级出水中的污染物在膜中沉积形成堵孔阻力.膜表面多孔,内部大孔发育不充分,易形成堵孔污染,通量衰减大且不易清洗恢复,膜污染不可逆.     

纳米氧化物粒子对PVDF中空纤维膜结构与性能的影响

采用相转化法制备纳米氧化物/聚偏氟乙烯复合中空纤维膜,讨论了纳米氧化钛和氧化铝粒子对PVDF膜结构和性能的影响.应用牛血清白蛋白截留实验、扫描电子显微镜、傅立叶红外光谱分别对不同膜的分离性能、微观结构和晶相组成进行了分析.结果表明,复合膜的性能与纯PVDF膜相比有显著地改善,其中纯PVDF膜、Al₂O₃/PVDF和TiO₂/PVDF复合膜对牛血清白蛋白的截留率分别为3.27%、67.20%和86.67%,复合膜的水通量则较纯PVDF膜分别提高2.3倍和2.6倍.氮气吸附实验测定的孔径分布进一步表明复合膜的孔径分布变窄,孔径变小.     

碳纳米管改性PVDF中空纤维超滤膜处理二级出水抗污染性能研究

采用碳纳米管改性PVDF中空纤维超滤膜以缓解膜污染.考察了CNTs的乙醇分散液浓度、CNTs尺寸和负载量对改性中空纤维膜的抗污染性能和改性膜内表面CNTs层稳定性的影响,分析了该改性膜对二级出水DOC、UV254的去除效果,并对改性膜出水的荧光特性进行了表征.结果表明,选用体积分数为50%的乙醇分散液、外径为30~50 nm碳纳米管、负载量为3 g·m-2时,制备的改性中空纤维膜CNTs层稳定,抗污染能力显著提高.与未改性膜相比,改性膜对二级出水DOC和UV254的去除率分别提高了37%和56%;且对二级出水中的腐殖类和蛋白质类物质去除能力明显增强.     

附加电场对中空纤维膜污染的减缓作用

通过对新型附加电场的中空纤维膜组件的实验室研究,探讨了电场对缓解微滤膜污染的作用.在恒定流量下过滤含有20mg/L腐殖酸的原水,无电压时,跨膜压力从0.0200MPa上升到0.0300MPa耗时2h,而施加60V电压时该时间段延长至10h.研究表明,原水中的腐殖酸在电场中发生电泳迁移,减少了向膜表面的移动,其对膜的污染被减缓;同时腐殖酸在电场中发生凝聚现象,沉积在膜表面形成疏松的滤饼层,是跨膜压力增加缓慢的另一原因.     

β-环糊精/醋酸纤维素纳米纤维的制备及对染料废水的处理

制备了不同β-环糊精(β-CD)含量的醋酸纤维素(CA)纳米纤维膜,并对纤维膜的结构形貌、尺寸分布、孔隙率、比表面积以及纤维膜的力学性能进行表征分析。随后研究了不同β-CD含量、初始浓度、吸附时间下,纳米纤维膜对甲基红染料的截留性能和吸附性能。结果表明:过量(≥30%)的β-环糊精会使纳米纤维产生珠节,纤维的形貌和力学性能变差;吸附试验表明,β-CD的加入提高了CA纳米纤维膜对染料的吸附,MR吸附率可达93.48%,最大平衡吸附量可达181.74 mg/g,比纯CA纳米纤维膜提高了将近40%;此外,染料的截留实验表明,纳米纤维膜对染料的截留效果较差,最大截留率为50.35%。     

膜萃取处理水溶液中镉、锌离子的工艺

以P204+正庚烷为萃取剂,将中空纤维膜萃取技术用于处理水溶液中镉离子、锌离子.研究了两相流速、初始浓度及溶液pH等因素对传质系数和萃取率的影响,计算了膜萃取器的传质单元高度(HTU)_w,同时还研究了萃取剂的再生问题.实验结果表明,在低浓度下(＜500 mg/L),平衡分配系数较大,传质阻力主要是在水相;在初始浓度较高时(＜2000mg/L),由于分配系数较小,三项传质阻力均不可忽略;在初始浓度很高时(＞2000mg/L),传质由有机相和膜相阻力控制.实验还表明通过膜器串联可以实现萃取剂的再生.对于稀溶液(＜200mg/L),中空纤维膜萃取可以使水溶液中金属离子浓度减小2个数量级,通过计算,中空纤维膜萃取器(HTU)_w在15～30cm之间,大大低于传统的萃取塔.     

膜分离法处理加油站油气的研究

针对加油站收油和发油过程中产生的油气污染,分别采用玻璃态油气截留型PEEK中空纤维膜组件和橡胶态油气渗透型GMT板框式膜组件,在自行设计建造的膜分离设备上,对比考察了2种膜组件和整个膜系统对油气污染治理和回收的效果.结果表明,2种膜系统对VOCs/空气混合气有很好的净化能力,尾气能够达标排放;在富油气返回油罐的模拟加油站实际运行情况的循环实验条件下,尾气也低于25 g·m-3的国标.     

无机添加剂对PVDF/PMMA/TPU中空纤维共混膜结构与性能的影响

采用相转化法制备纳米氧化物PVDF/PMMA/TPU共混中空纤维膜。测定共混膜的纯水接触角和黏度、并经扫描电子显微镜、共混膜的超滤实验和拉伸实验分别对不同添加剂膜的亲水性能、微观结构、超滤性能和机械性能进行了分析。结果表明,纳米氧化物的加入使膜的性能有明显的改善,其中无氧化物、添加SiO2、TiO2、Al2O3的PVDF/PMMA/TPU复合膜对牛血清白蛋白的截留率分别为28.7%、65.8%7、1.4%和79.6%,同时添加无机氧化物的膜水通量也较未添加无机氧化物的膜有所提高;而且无机氧化物的加入还能改善膜的亲水性能和机械性能。