Poly(vinylidene fluoride) fibrous membranes doped with polyamide 6 for highly efficient separation of a stable oil/water emulsion

Ideal membranes toward separation of stable oil/water emulsions should have surface hydrophilicity and submicron pores in the separating layer. However, electrospun membranes made from poly(vinylidene fluoride) (PVDF) cannot meet these requirements, failing to remove oil droplets from a stable oil/water emulsion. By doping with a certain polyamide 6 solution, surface hydrophilicity, and interconnected pores with submicron size are successfully achieved. As a result, separation of a stable emulsion with an efficiency above 99% is exhibited by the modified PVDF membranes. Moreover, underwater oleophobicity of the modified PVDF membranes imparts them with good antifouling performance. The modified PVDF membranes could have great potentials in practical stable oil/water emulsion separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44980.     

β-SiAlON ceramic membranes modified with SiO2 nanoparticles with high rejection rate in oil-water emulsion separation

Porous ceramic membranes with high mechanical strength are suitable for oil-water emulsion separation. Nonetheless, it is difficult to prepare ceramic membranes with a small pore size and a good antifouling ability. In this work, SiO₂ nanoparticles were used to modify β-SiAlON ceramic membranes, which were successfully utilized to remove small oil droplets from oil-water emulsion. The modified membranes displayed a narrow pore size (the average pore size decreased from 1.05?µm, in the unmodified membrane, to 0.65?µm), and gas and water fluxes which are suitable for oil-water separation. Oil rejection rate was always higher than 90% under various pressures (1.0–2.0?bar) and flow velocities (1.0?3.0?L?min^?1) tested, which is considerably higher (60%) than the rejection rate of the unmodified membrane (which was 39.8%). Moreover, the modified membranes exhibited a good antifouling ability, since flux declined by only 7.0% after three recoveries via a simple ultrasonic treatment, over a total running period of 10?h. Accordingly, the produced membranes can be qualified for further consideration in oily wastewater treatment.     

Zwitterionic monolayer grafted ceramic membrane with an antifouling performance for the efficient oil-water separation

Enormous demands on the separation of oil/water (O/W) emulsions in various industries, such as petrochemical, food and pharmaceutical industries, are looking for high performance and energy-efficient separation methods. Ceramic membranes have been used to deal with O/W emulsions, for its outstanding characteristics of easy-operation, high-flux, and long-term stability. However, membrane fouling is still a challenge in the industrial application of ceramic membranes. Herein, antifouling ceramic membranes were fabricated by grafting zwitterions on the membrane surface via an environment-friendly two-step grafting method, which improves the antifouling property and permeability. Successful grafting of such zwitterion on the ceramic surface was assessed by the combination of FTIR and XPS characterization. More importantly, the hydration can be formed by electrostatic interactions layer on the modified membrane, which was confirmed by TGA characterization. The antifouling performance of prepared zwitterionic ceramic membranes in the separation of O/W emulsions was systematically tested. The results suggested that zwitterion can significantly improve the flux of ceramic ultrafiltration membrane, and can also improve antifouling property dramatically by reducing the irreversible fouling in the separation of O/W emulsions. Therefore, zwitterionic ceramic membranes hold promising potentials as an antifouling, highly efficient and green method in the practical purification of the O/W emulsions.     

Hierarchical amphiphilic high-efficiency oil–water separation membranes from fermentation derived cellulose and recycled polystyrene

A high-efficiency separation of oil and water can be achieved by using specially designed amphiphilic porous membrane. However, the preparation of such membranes often involves complex multistep chemical processes. Herein, we report an amphiphilic composite membrane (polystyrene [PS]/bacterial cellulose [BC] membrane) consisting of hydrophobic recycled PS and hydrophilic BC, fabricated by a facile in situ fermentation process. Not only these membranes exhibit a combination of contrasting wettability but also comprise of a hierarchical network of microfibers and nanofibers, which makes them ideal for oil–water separation. The structural and morphological properties of as-produced BC, recycled PS membrane, and PS/BC composite membrane were studied by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The ability of the membranes to separate oil and water was tested by using an emulsion of hexane-in-water as the feed and the collected filtrates were characterized by optical microscopy and UV–Vis spectroscopy. PS membranes were unable to separate oil and water, while the PS/BC membrane efficiently separated water from the emulsion. PS/BC composite membranes showed a high water recovery of more than 90%, against only 57% recovery shown by BC. Mechanisms of oil–water separation for each membrane are discussed. The reusability of the PS/BC composite membrane was also demonstrated.     

Deacetylated Cellulose Acetate/Polyurethane Composite Nanofiber Membranes with Highly Efficient Oil/Water Separation and Excellent Mechanical Properties

Nowadays, oil pollution has become more serious, which causes great threats both to the ecological environment and human life. In this study, a novel type of multifunctional deacetylated cellulose acetate/polyurethane (d-M_CA:M_TPU) composite nanofiber membranes for oil/water separation are successfully fabricated by electrospinning, which show super-amphiphilicity in air, super-hydrophilicity in oil, and oleophobicity in water. All the d-M_CA:M_TPU composite nanofiber membranes with different mass ratios can be used as water-removing, oil-removing, and emulsion separation substance only by gravity driving force. The highest separation flux for water and oil reaches up to 37 000 and 74 000 L m⁻² h⁻¹, respectively, and all the separation efficiencies are more than 99%. They have outstanding comprehensive mechanics performance, which can be controlled by simply adjusting the mass ratios. They show excellent antifouling and self-cleaning ability, endowing powerful cyclic stability and reusability. Those results show that d-M_CA:M_TPU composite nanofiber membranes have great application prospects in oil/water separation.     

超亲水SiO2修饰膜的构建及其油水乳液分离性能

采用硅溶胶和多巴胺作为修饰剂,通过一步反应在微孔聚丙烯膜(MPPM)表面构建了SiO₂修饰层。利用FTIR、ESEM和EDX对膜进行了表征,发现膜表面SiO₂颗粒分布非常均匀。水/油接触角及纯水通量实验结果表明,修饰膜具有超亲水性及水下超疏油性,透水能力强,水通量大[在0.1 MPa时,水通量高达(5100±500)L·m^-2·h^-1]。油水乳液分离结果表明,修饰膜能有效分离油水乳液,在0.05 MPa时,油水乳液水通量达2830 L·m^-2·h^-1,油截留率达99.8%以上,即使过膜压力增大到0.15 MPa,油截留率也能保持在99%以上,且膜表面的油污可用水清洗除去,展现出很好的应用前景。     

Electrospun nanofibrous polyvinylidene fluoride-co-hexafluoropropylene membranes for oil–water separation

Effective separation of oil from water is of significant importance globally for various applications such as wastewater treatment, oil spill cleanup, and oil purification. Among the numerous approaches for oil removal, membrane separation is considered one of the most promising approaches due to its selectivity and ease of operation. Electrospinning is a promising technique for producing polymeric membranes with tunable structures with interconnected pores, large surface area, and high porosity. In this study, hydrophobic poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibrous membranes were electrospun and used for this purpose. The effects of various parameters (e.g., polymer concentration, applied voltage, tip to collector distance, and feed rate) were investigated to find the optimum electrospinning conditions. Further, the electrospun membranes were characterized according to average fiber diameter, morphology, average pore size, and wettability to identify the combinations most likely to succeed in oil–water filtration. The physical–chemical properties of the membranes (i.e., thickness, areal density, porosity, average pore size, water/oil contact angle, hydrostatic pressure head, and oil filtration flux) were studied based on standard test methods. The separation efficiency of eight electrospun membranes with various pore sizes and average fiber diameters were tested for diesel/water mixtures. A linear relation was found between the initial oil flux and the average pore size of the membranes. The maximum oil filtration flux of about 224 L/m²/h, achieving over 75% oil recovery in 10 min, was obtained for the electrospun membrane with the average pore size of 4.5 μm. The membranes were successfully used for eight consecutive oil–water separation cycles without noticeable loss of flux.     

Superhydrophobic–superoleophilic electrospun nanofibrous membrane modified by the chemical vapor deposition of dimethyl dichlorosilane for efficient oil–water separation

Superhydrophobic and superoleophilic functionalized electrospun poly(vinylidene fluoride) (PVDF) membranes with water repellence, breathability, and oil-sorption and oil–water separation properties were achieved with a combination of an electrospinning technique and the chemical vapor deposition of dichlorodimethyl silane. The samples were laterally characterized by scanning electron microscopy, atomic force microscopy, water contact angle measurement, and Fourier transform infrared spectroscopy. The maximum water contact angle value was 152.0 ± 2.5° for the PVDF nanofibrous membranes with 500 μL of deposited silane (PMS2) obtained under certain conditions. The PMS2 membranes showed 100.0, 93.7, 23.3, 35.0, and 100.0% separation efficiencies for n-hexane, kerosene, crude oil, frying oil, and toluene, respectively. The understudy membrane exhibited reasonable waterproofness and remarkable breathability (water vapor transition rate = 215.21 g/m².h). Moreover, the superhydrophobic and superoleophilic nanofibrous membranes also showed good reusability, stability, moderate water-repellent properties, breathability, antifouling properties, and oil–water separation ability after several cycles. These properties confirmed potential in feasible applications, including protective cloths and in the purification of oil-polluted water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47621.     

An oil-contamination-resistant PVP/PAN electrospinning membrane for high-efficient oil–water mixture and emulsion separation

Oil–water separation is an urgent issue due to the frequently occurred oil leakages and increasing discharge of oily wastewater. The pollutional and wastewater can not only damage the environment, but endanger human health. Owing to the small particle size of the oil contamination, it is still a challenge for the separation of oil–water emulsion. In this study, we developed a facile strategy to prepare a hydrophilic polyvinylpyrrolidone/polyacrylonitrile (PVP/PAN) nanofibrous membrane for oil–water mixture and emulsion separation. The lowest water contact angle on the membrane surface can achieve 16.7°, thus the membranes can effectively resist the oil contamination on them. Moreover, the membrane can efficiently separate oil–water mixtures and emulsion by gravity. In addition, it can separate oil–water mixtures in harsh conditions (pH = 1 and 14). Membranes prepared in this work would hold a great potential in the practical use of water treatment and environmental industry.     

纳米银在水处理膜中的应用进展

水处理膜是具有选择性分离功能的材料,利用水处理膜的选择性分离可实现污水的不同组分的分离、纯化、浓缩。基于纳米银的独特性质,将其引入水处理膜可使纳米银复合膜具有较强的抗生物污染能力。本文综述了近年来将纳米银引入应用较广泛的微滤膜、超滤膜和纳滤膜以及反渗透膜这些水处理膜中以改善膜的抗污染性能的研究进展。此外,指出了提高纳米银水处理复合膜抗菌的持续性以及开发环境友好型的复合膜是未来的发展方向。     

Biofouling alleviation and flux enhancement of electrospun PAN microfiltration membranes by embedding of para‐aminobenzoate alumoxane nanoparticles

Membrane bioreactor (MBR) as a hybrid technology for wastewater treatment is becoming more popular for wastewater treatment. However, membrane fouling has hindered the widespread application of MBRs. Many efforts have been done for fouling mitigation. In this study, high flux and antifouling microfiltration membranes with unique surface structure, high surface porosity, and permeability were prepared by electrospinning technique. Initially, the optimum thickness of electrospun polyacrylonitrile (PAN) membranes was determined and then, electrospun PAN membrane at optimum thickness were prepared by embedding para‐aminobenzoate alumoxane (PABA) nanoparticles at different concentrations. The effect of PABA nanoparticles on membrane performance was investigated. To investigate the characterization of the prepared membranes Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, energy dispersive X‐ray spectroscopy, and water contact angle measurement were employed. The flux recovery ratio results revealed that the antifouling properties of the electrospun PAN membrane were enhanced by modification. The 3 wt % electrospun PABA embedded PAN had the best permeability, hydrophilicity, and antifouling properties among the fabricated membranes and showed remarkable reusability during filtration. The results obtained suggested that the high flux and antifouling electrospun PAN membranes embedded PABA nanoparticles could be used as MBR membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45738.     

疏水性油水分离膜及其过程研究进展

油水分离是治理含油废水和含水油液的重要工业过程。本文概括了疏水性油水分离膜的类型与制备方法,包括常规分离膜和高度疏水/超亲油分离膜。前者为常规微滤、超滤及纳滤过程用膜;后者由构筑高度疏水（水滴接触角≥120°）表面方法得到,形式有金属网膜、纤维膜、滤纸、复合膜及不对称膜,其为制备耐污染的疏水性油水分离膜提供了新思路。指出了疏水性膜用于油水分离的过程原理及应用现状：含油废水除油中,疏水性膜可实现O/W乳液的破乳、粗粒化油滴、滤除油滴及吸附油分子几方面的功能;含水油液除水中,膜被用来截留水滴,可直接得到净化的油品。最后,指出了其过程规模化应用前尚需解决的重要问题,特别是高度疏水/超亲油分离膜的制备、相关过程研究的深入及其规模化试验等方面需着力加强。     

具有动态属性的聚轮烷在膜领域应用进展

聚轮烷独特的超分子结构和动态属性引起科学家极大的关注，其在膜领域也具有重要应用潜力，国内外已有系列报道。本文介绍了分子机器的发展、膜分离技术、聚轮烷的概念和制备方法、聚轮烷改性膜的种类和性质，综述了聚轮烷在膜领域的应用进展，特别是其在抗污染膜、吸附功能膜、离子传导膜、油水分离膜构建及性能提升等方面的研究进展，总结了聚轮烷的动态结构在膜及膜分离过程中的功能作用，分析了聚轮烷改性膜的分离性能和分离机理，结果说明了具有自移动结构的聚轮烷超分子功能体在改善膜性能方面（如提高膜的亲水性、通量、抗污染性能、吸附性能、传导性能、力学性能等）具有独特优势。本文最后对聚轮烷改性膜的发展前景及未来趋势进行了分析。     

聚丙烯微孔膜的表面矿化修饰及其亲水性能

为了改善聚丙烯微孔膜(MPPM)的表面亲水性,通过组合多巴胺氧化聚合和交替浸渍矿化修饰技术,在MPPM表面构建了均匀的CaCO₃矿物层,实现了利用CaCO₃矿物对膜表面进行亲水化修饰的目的。采用FTIR、XPS、ESEM、EDX和水接触角对矿化膜表面进行了相应的表征。考察了溶液浓度、浸渍循环次数及聚多巴胺涂覆率等对CaCO₃矿化率的影响。结果证实,CaCO₃矿物均匀地负载在MPPM表面,膜的亲水性因CaCO₃固有的润湿性而明显改善。纯水通量测试结果表明,矿化膜具有强的水渗透能力,纯水通量大(高达6450 L·m^-2·h^-1),渗透阻力小,施加0.01 MPa的外压,水即可透过膜。油水乳液分离研究发现,矿化膜能有效地分离一定范围的油水乳液,水通量大(> 1800 L·m^-2·h^-1),且膜容易用水清洗,展现出理想的油水乳液分离应用前景。     

Ag3PO4改性PVDF超滤膜的结构与性能

将不同量Ag₃PO₄均匀地分散在聚偏氟乙烯(PVDF)铸膜液中, 利用相转化法制备了改性PVDF膜, 通过扫描电镜(SEM)、接触角测定、过滤实验和污染性测试等研究了其微结构、分离性和耐污染性等, 并考察了膜污染后的清洗效果。结果表明, 添加Ag₃PO₄ 的PVDF膜具有不同的微结构与性能, 当添加1% 的Ag₃PO₄时, 膜皮层变薄、微孔数增多, 并呈现出最优化的水通量、亲水性、力学性、抗污染能力和截留率等。采用太阳光-水清洗能使改性膜的通量恢复率达到85%以上。     

Facile ZIF‐8 functionalized hierarchical micronanofiber membrane for high‐efficiency separation of water‐in‐oil emulsions

The efficient separation and recovery of oil from water‐in‐oil emulsion poses a great challenge because of the rapid development of the petrochemical industry throughout the world. In this study, a facile method to develop a ZIF‐8 functionalized hierarchical micronanofiber membrane for high‐efficiency oil/water separation was investigated. The electrospun PVDF/ZnO membrane was made, on which ZIF‐8 crystal seeds were then created with the revitalizing step and expanded in the growth step, and finally functionalized hierarchical micronanofiber PVDF‐g‐ZIF‐8 membrane was obtained. Results showed that oleophilic ZIF‐8 crystals on the surface of PVDF membrane dramatically increased the wettability of oil and tuned PVDF membrane from olephobicity to oleophilicity. The hydrophobic/lipophilic PVDF‐g‐ZIF‐8 membrane with a water contact angle up to 158° and a toluene contact angle down to 0° provides its separation efficiency for water‐in‐oil emulsion of 92.93% in an environmentally friendly and energy‐saving manner. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46462.     

Separation of oil/water emulsions using nano MgO anchored hybrid ultrafiltration membranes for environmental abatement

This work focuses on utilizing the dual role of sulfonated polyphenyl sulfone (SPPSU) as both an anchoring agent and an interlayer modifying agent in the preparation of nano MgO/SPPSU/PPSU membranes for oil removal from water. These asymmetric membranes were prepared using the phase inversion technique. The dispersed nano MgO was observed in the membrane matrix as seen by scanning electron microscope and energy dispersive X‐ray analysis. The reduction in contact angle value establishes the increases in hydrophilicity. An increase in SPPSU (wt %) loosens the nano MgO/SPPSU/PPSU membrane packing as exhibited by the increase of d‐spacing by X‐ray diffraction analysis. The antifouling properties were tested using humic acid, as a model foulant. Further, in castor oil/water emulsion separation, it was found that the membrane with 25 wt % anchored moiety SPPSU/nano MgO produced a greater flux recovery ratio of 94.9% (±0.3) without compromising the oil rejection of 99% (±0.4) and better oleophobic surfaces for oil. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42848.     

Amphiphilic poly(ether sulfone) membranes for oil/water separation: Effect of sequence structure of the modifier

Oil‐contaminated wastewater threatens our environment and health thus novel membrane materials with low or nonfouling properties are an immediate need for oily wastewater treatment in a cost‐effective and environmentally friendly manner. In this study, three types of amphiphilic random, gradient, and block copolymers with similar molecular weights and chemical compositions, based on poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate (TFOA), were synthesized by the reversible addition‐fragmentation chain transfer (RAFT) method. The amphiphilic Poly(ether sulfone) membranes were then fabricated by blending with these copolymers via a facile coupled process of nonsolvent induced phase separation and surface segregation. Accompanying the phase inversion process of polymer matrix, the hydrophilic and hydrophobic segments in the amphiphilic modifiers would migrate and immobilize onto the membrane surfaces. This surface segregation process leaded to a chemical heterogeneous membrane surface comprising both hydrophilic PEGMA and low surface energy PTFOA brushes, which was confirmed by X‐ray photoelectron spectroscopy (XPS) and surface wettability analyses. Oil‐in‐water emulsion filtration test of the membranes displayed a lower permeate flux decline and a higher flux recovery (as high as 99.8%), establishing their considerably elevated antifouling properties. Additionally, cyclic oil/water separation and long‐term underwater immersion tests demonstrated that the as‐prepared membranes modified by these amphiphilic additives possessed excellent antifouling stabilities. © 2016 American Institute of Chemical Engineers AIChE J, 63: 739–750, 2017     

PMIA@PVDF同轴电纺纤维膜的制备及其油水分离性能研究

以聚间苯二甲酰间苯二胺(PMIA)为芯、聚偏氟乙烯(PVDF)为壳,使用22-17G同轴静电纺丝针头制备不同纺丝液芯壳流速比的PMIA@PVDF同轴电纺纤维膜,对纤维膜的芯壳结构、力学性能、热性能及油水分离性能进行了表征。结果表明:在纺丝液芯壳流速比为35时,PMIA@PVDF同轴电纺纤维膜具有理想的表面形貌和芯壳结构,具有较好的力学性能和热性能,且具有最佳疏水性和油水分离性能;纤维膜的纤维直径分布较为均匀,很少出现不规则的细丝,有比较分明的分层结构,PVDF包裹PMIA比较均匀;纤维膜的拉伸强度为10.42 MPa,断裂伸长率为38.76%;纤维膜在250℃有轻微的质量损失,最终质量保持率高于纯PVDF电纺纤维膜;纤维膜的水接触角达145.7°,对油水混合物(二氯甲烷-水、三氯甲烷-水)的分离流量都在1900 L/(m²·h)之上、分离效率均达99%以上。     

Fabrication of magnetically responsive anti-fouling and easy-cleaning nanofiber membrane and its application for efficient oil-water emulsion separation

The magnetically responsive anti-fouling nanofiber membrane (MRANM) was fabricated for efficient oil-water emulsion separation,which could be cleaned using oscillating magnetic field.MRANM was pre-pared by grafting superparamagnetic Fe3O4 nanoparticles onto the surface of electrospun polyacryloni-trile nanofiber membrane (PANM).Compared with PANM,the water contact angle of MRANM decreased from 104° to 0°,indicating that the hydrophilicity of the membrane was significantly improved.For the emulsions of hexadecane,octane and rapeseed oil,the separation efficiency was 98.04％,96.59％ and 92.67％,respectively.After the treatments in oscillating magnetic field,the separation efficiency kept above 95％ after 8 times recycling,which indicated that the MRANM had good regenera-bility and reusability.The as-fabricated membrane with magnetic responsiveness facilitated an effective method for solving the membrane fouling problem during practical applications of separation high vis-cosity oil-water emulsion.