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.     

Influence of filtration conditions on the performance of nanofiltration and reverse osmosis membranes in dairy wastewater treatment

Filtration performance and fouling of nanofiltration (NF) and reverse osmosis (RO) membranes in the treatment of dairy industry wastewater were investigated. Two series of experiments were performed. The first one involved a NF membrane (TFC-S) for treating the chemical-biological treatment plant effluents. The second one used a RO membrane (TFC-HR) for treating the original effluents from the dairy industry. The permeate flux was higher at higher transmembrane pressures and higher feed flowrates. The curves of permeate flux exhibited a slower increase while the feed flowrate decreased and the pressure increased. Membrane fouling resulted in permeate flux decline with increasing the feed COD concentration. Furthermore, the flux decline due to the COD increase was found higher at higher pressures for both NF and RO membranes.     

Hollow fine fiber vs. flat sheet membranes - a comparison of structures and performance

The reverse osmosis performance of polymeric membranes depends not only on the chemical structure of the polymer but also on the physical structure of the membrane. Percolation theory is used to describe water flux and salt passage as functions of the polymer density, or porosity, of the membrane. Water permeability increases with increasing porosity, or decreasing polymer density in the membrane. Salt passage is controlled primarily by the membrane polymer density in the surface layer on the feed side of the membrane. Experimental data on both hollow fine fiber and flat sheet membranes are consistent with the basic concepts of percolation theory.     

Porous polyethersulfone hollow fiber membrane in gas–liquid contacting processes

Porous polyethersulfone hollow fiber membranes were fabricated via dry–wet phase inversion method with the polymer concentration in the spinning dope either 13 wt% or 15 wt%. The fabricated hollow fiber membranes were characterized by different test methods and the performance of membranes in contactor applications was tested by CO₂ absorption. The mean pore size, effective surface porosity and membrane porosity decreased while the membrane density and Liquid Entry Pressure (LEPw) increased as polymer concentration increased. The CO₂ absorption flux of the fabricated membranes was measured in two cases; i.e. when the absorbent, distilled water, was in the lumen side or in the shell side. The CO₂ flux for the membrane, fabricated from 13 wt% PES solution, was compared with some commercial and in-house made membranes. The former membrane had 111% higher flux than a commercial PTFE membrane.     

A Comparative study of organic fouling in hollow fiber and spiral wound membranes

The occurrence of flux decline in brackish water reverse osmosis (RO) plants due to dissolved organics is a topic of ongoing research. This type of organic fouling has also been found in seawater RO plants. A study was undertaken to compare organic fouling in hollow fiber and spiral wound membranes using a seawater feed that possessed a high concentration of huraic acid. This study was undertaken at an RO plant on Grand Cayman Island, British West Indies. The feed water came from a sea well and possessed a concentration of humic acid that varied between 35 and 60 mg/l.The hollow fiber membrane was operated at a recovery of 25% while the recovery with the spiral wound membrane varied between 5 and 25%. The performance data which included permeate flow, salt rejection, pressure drops across the membrane and analysis of the membranes for organic fouling were undertaken. This study compared the performance data and organic fouling between the hollow fiber and spiral wound meembranes.     

A high flux graphene oxide nanoparticles embedded in PAN nanofiber microfiltration membrane for water treatment applications with improved anti-fouling performance

A high flux and anti-fouling graphene oxide (GO) nanoparticles embedded in polyacrylonitrile (PAN) nanofiber microfiltration membranes (PANGMs) were fabricated through the facile electrospinning method and were characterized by water treatment applications. The synthesized GO nanoparticles and GO nanoparticles embedded in PAN nanofiber membranes were characterized by FESEM, FTIR, and EDS. SEM images showed that the PANGMs possessed randomly overlaid fibers with a network-like highly porous structure similar to the pristine PAN nanofiber membrane, while agglomeration of GO nanoparticles was observed at high GO concentration. The introduction of GO nanoparticles into the PAN polymeric matrix significantly increased the permeation flux of the resulting membrane in both dead-end and cross-flow filtration systems. A high flux recovery ratio of 96.6% and a low irreversible fouling ratio of 3.4% were obtained at 2% (wt.) GO nanoparticles. More importantly, a high flux recovery ratio of GO nanoparticles embedded in PAN nanofiber membrane was retained after 20 repeated cycles of activated sludge suspension filtration. Therefore, it can speculate that the incorporation of GO nanoparticles into the PAN nanofibers could efficiently improve the anti-fouling ability of membranes which had opened up an alternative for the preparation of high flux and anti-fouling microfiltration membranes in practical water treatment applications such as membrane bioreactors.

     

Investigating the effect of zirconium-based and titanium-based metal–organic frameworks nanoparticles on the performance of polysulfone hollow fiber mixed matrix membrane for dialysis application

This study aims to investigate polysulfone (PSF) mixed matrix membranes (MMMs) properties containing zirconium-based and titanium-based metal–organic frameworks (MOFs). for hemodialysis application. The nanoparticles were synthesized, and the membranes were produced by the phase inversion method. Membrane characterization conducted by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), field emission Scanning electron microscope (FE-SEM), energy-dispersive x-ray analysis (EDX), transmission electron microscopy (TEM), x-ray diffraction (XRD), and atomic force microscopy (AFM) confirmed the presence of MOF nanoparticles. Also, the evaluation of the specific surface area of nanoparticles was done by BET. The water contact angle reduced from 64.4° to 51.2°, indicating the hydrophilicity improvement, enhancing the pure water flux from 46.8 L/m²h for the pristine membrane to 76.7 L/m2h for the pristine membrane M₄. The total fouling resistance decreased from 30% to 21%, and the bovine serum albumin (BSA) adsorption of modified membranes was lower than that of the pristine membrane. Urea and creatinine were cleared significantly for modified ones, up to 82.6% and 72.1%, respectively, and all membranes showed BSA retention of more than 93%. A comparison between MMMs that contained UIO-66-NH₂ and MIL-125-NH₂ showed that the former had a better effect on the performance. M₄ had better results, indicating high water flux, the lowest fouling resistance, high porosity, lower BSA adsorption, proper clearance for urea and creatinine, and 94.2% BSA retention.     

Removal of dyes by poly(p-phenylene terephthamide)/polyvinylidene fluoride hollow fiber in-situ blend membranes

In order to obtain the compatible poly(p-phenylene terephthalamide) (PPTA)/polyvinylidene fluoride (PVDF) blend membranes, the casting solution was synthesized via the in situ polycondensation process and flat sheet blend membranes were successfully prepared through the immersion precipitation phase inversion method in our previous study. In this study, the polycondensation solution was directly used as the spinning dope to fabricate PPTA/PVDF hollow fiber in-situ blend membrane by the dry-wet spinning technique. Hollow fiber membranes were employed to remove the dyes including Congo red (CR) and methylene blue (MB) from the dyeing liquor. Effects of operation conditions on dye rejection and membrane water flux were investigated. With the increase of operation pressure, feed concentration and feed temperature, dye rejection rates gradually decreased, but the rejection value of CR and MB still remained above 99.5%. On the contrary, the permeation water flux basically increased. During the continuous dye filtration of 300 min, hollow fiber membrane can maintain high dye rejection rates and stable water flux. The combination method of physical backwashing and chemical cleaning can effectively alleviate membrane fouling and recover membrane water flux. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48569.     

Experimental investigation and modeling hybrid nano-porous membrane process for industrial oily wastewater treatment

The aims of this work are to construct a pilot scale purification set-up using membrane process for Tehran Oil Refining Company desalter plant wastewater. The investigation was shown that the high amount of impurities in the feed was the main reason of low permeation flux. The nano-porous membrane-powdered activated carbon (NPM–PAC) was employed to settle this problem. Results demonstrated NPM alone was ineffective in removing TSS, COD, and TOC. In the NPM process the removal of COD and TOC are around 62.5 and 75.1%, respectively, and the steady permeation flux (SPF) is around 78.7 L/(m² h). Optimum PAC dosage, which leads to less deposit layer with high porosity on the membrane surface, could increase permeation flux up to 133.8 L/(m² h), the removal of COD and TOC, 78.1% and 90.4%, respectively, and also decreased steady fouling resistance (SFR) around 46.1%. Hermia's models were employed to investigate mechanism of preventing membrane fouling. After coagulation, the kinetic constants, K_b, K_i, K_s, and K_c, showed lower amounts when NPM filtration used alone. Thus, a NPM–PAC hybrid membrane system has the potential to be an effective method to improve NPM removal efficiency in high percentages as well as to improve membrane fouling and permeation flux in desalter plant.     

溶剂对水处理用PVDF微孔膜结构性能影响

利用N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、磷酸三乙酯(TEP)和二甲基亚砜(DMSO)4种溶剂制备PVDF微孔膜,考察溶剂对成膜性能的影响,除了测试膜结构、孔隙率、清水通量等常规指标外,增加膜污染速率指标,研究4种溶剂成膜在实际膜-生物反应器(MBR)内的运行情况,得到4种溶剂成膜结构不同,具有贯穿性指状孔的DMSO溶剂成膜具有最高的孔隙率,高清水通量,并在MBR内表现出最低的污染速率,最适于制备水处理用的PVDF膜;具有海绵状孔的TEP溶剂成膜具有最高的清水通量,高的孔隙率,在MBR内污染速率较低;DMF、DMAc溶剂成膜结构类似,具有不贯穿的指状孔,孔隙率及清水通量均较低,膜污染速率高,不适于水处理MBR用膜。     

Preparation,characterization and performance of cellulose acetate ultrafiltration membranes modified by charged surface modifying macromolecule

A charged surface modifying macromolecule (cSMM) was synthesized, characterized by FT-IR spectroscopy and blended into the casting solution of cellulose acetate (CA) to prepare surface modified UF membranes by phase inversion technique. With an increasing cSMM additive content from 1 to 4 wt%, pure water flux (PWF) and water content (WC) were increases whereas the hydraulic resistance decreases. Surface characteristic study reveals that the surface hydrophilicity increased in cSMM modified CA membranes. The pore size and surface porosity of the 4 wt% cSMM blend CA membranes increases to 41.26 Å and 0.015%, respectively. Similarly, the molecular weight cut-off (MWCO) of the membranes ranged from 20 to 45 kDa, depending on the various compositions of the prepared membranes. Lower flux decline rate (47.2%) and higher flux recovery ratio (FRR) (89.0%), exhibited by 4 wt% cSMM blend membranes demonstrated its fouling resistant characteristic compared to pristine CA membrane.     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m^-1. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m^-2·h^-1 which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

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.     

Poly(vinylidene fluoride) hollow‐fiber membranes containing silver/graphene oxide dope with excellent filtration performance

In this study, an antifouling poly(vinylidene fluoride) (PVDF) hollow‐fiber membrane was fabricated by blending with silver‐loaded graphene oxide via phase inversion through a dry‐jet, wet‐spinning technique. The presence of graphene oxide endowed the blended membrane with a high antifouling ability for organic fouling. The permeation fluxes of the blended membrane was 3.3 and 2.9 times higher than those of a pristine PVDF membrane for filtering feed water containing protein and normal organic matter, respectively. On the other hand, the presence of silver improved the antibiofouling capability of the blended membrane. For the treatment of Escherichia coli suspension, the permeation flux of the blended membranes was 8.2 times as high as that of the pristine PVDF membrane. Additionally, the presented blended membrane improved the hydrophilicity and mechanical strength compared to those of the pristine PVDF membrane, with the water contact angle decreasing from 86.1 to 62.5° and the tensile strength increasing from 1.94 to 2.13 MPa. This study opens an avenue for the fabrication of membranes with high permeabilities and antifouling abilities through the blending of graphene‐based materials for water treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44713.     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m⁻¹. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m⁻²·h⁻¹ which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

用于处理染料废水的PVDF/TPU共混中空纤维膜的制备

采用相转化法制备PVDF／TPU共混中空纤维膜,以PVP为添加剂可以改善成膜性能。通过水通量超滤实验、牛血清白蛋白截留实验、扫描电子显微镜表征膜的表面与截面结构分析得出铸膜液中纤维膜的质量分数为16％,m（PVDF）：m（11Pu）为80：20,添加5％PVP时制备的膜的综合性能最佳。对不同的溶液包括BSA、PVPK30、PEG10000、染料活性艳蓝KN-R进行截留实验分析膜过滤性能。在pH范围为1—14时,膜的水通量及截留率均无明显变化,说明PVDF／TPU共混中空纤维膜具有良好的抗酸、碱性。用清水冲洗10min后,膜污染的恢复率即可达到86．5％,膜的抗污染性能良好。     

Ozone Cleaning of Fouled Poly(Vinylidene) Fluoride/Carbon Nanotube Membranes

This research demonstrates for the first time that ozone is an effective cleaning agent for polyvinylidene fluoride (PVDF) membranes fouled by natural organic matter (NOM). Bare PVDF membranes as well as PVDF impregnated with CNTs (pristine (CNTs–P) and oxidized (CNTs–O)) at 0.3% mass membranes were used. Three different methods were investigated for cleaning the fouled membranes including; A: 10-min cleaning by pure water, B: 5-min water followed by 5-min ozonated water, and C: 10-min fully ozonated water. It was found that the application of fully ozonated water for 10 min was very effective to reinstate the flux to almost its original value of unfouled membrane. The CNTs–P/PVDF membrane exhibited the highest fouling with a total fouling ratio of 81%, while for the bare PVDF and the CNTs–O/PVDF membranes, the fouling ratios were 76% and 74%, respectively. The full ozonated water cleaning method gave the highest removal of fouling leaving the lowest irreversible fouling on the membrane as compared to the other cleaning methods. On the other hand, the highest removal of NOM fouling was obtained for CNTs–O/PVDF membranes indicating that fouling on CNTs–O/PVDF membrane was less bound than the other membranes. Contact angle measurements of the fouled membranes showed that all membranes exhibited increased contact angles due to the NOM deposition but after cleaning, particularly with ozonated water, the membrane contact angles returned to almost their original values. FTIR analysis of the membranes corroborated the results obtained.     

Preparation and performance of the novel PVDF ultrafiltration membranes blending with PVA modified SiO2 hydrophilic nanoparticles

In this study, PVA‐SiO₂ was synthesized by modifying silica (SiO₂) with polyvinyl alcohol (PVA), then a novel polyvinylidene fluoride (PVDF) ultrafiltration (UF) membrane was prepared by incorporating the prepared PVA‐SiO₂ into membrane matrix using the non‐solvent induced phase separation (NIPS) method. The effects of PVA‐SiO₂ particle on the properties of the PVDF membrane were systematically studied by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT‐IR), surface pore size, porosity, and water contact angle. The results indicated that with the addition of PVA‐SiO₂ particles in the PVDF UF membranes, membrane mean pore size increased from 80.06 to 126.00 nm, porosity improved from 77.4% to 89.1%, and water contact angle decreased from 75.61° to 63.10°. Furthermore, ultrafiltration experiments were conducted in terms of pure water flux, bovine serum albumin (BSA) rejection, and anti‐fouling performance. It indicated that with the addition of PVA‐SiO₂ particles, pure water flux increased from 70 to 126 L/m² h, BSA rejection increased from 67% to 86%, flux recovery ratio increased from 60% to 96%, total fouling ratio decreased from 50% to 18.7%, and irreversible fouling ratio decreased from 40% to 4%. Membrane anti‐fouling property was improved, and it can be expected that this work may provide some references to the improvement of the anti‐fouling performance of the PVDF ultrafiltration membrane. POLYM. ENG. SCI., 59:E412–E421, 2019. © 2018 Society of Plastics Engineers     

基于小孔径PVDF内衬膜A/O-MBR膜污染分析

为研究膜生物反应器膜污染问题,在缺氧-好氧一体式膜生物反应器中,对模拟生活污水的处理效果进行考察,考察了4种不同孔径聚偏氟乙烯(PVDF)内衬膜对膜污染的影响规律。结果表明,基于小孔径PVDF膜的MBR工艺对模拟生活污水中COD、NH3-N的去除率分别达到96%、90%,出水浊度在0.35 NTU以下;在操作条件固定的情况下,随着膜孔径增加,临界通量逐渐降低;孔径越小,跨膜压差上升越缓慢,膜污染较轻。膜污染模型分析结果显示:无论何种孔径的膜,在MBR系统中,滤饼层和凝胶层污染所占的比例都最大(>80%),因此,在使用过程中减缓滤饼层及凝胶层的形成至关重要。     

PSF/ER合金膜的膜材料对膜性能的影响

介绍了 PSF与 ER共混对合金膜的成膜性能和力学性能的影响。二者共混改善了 PSF的亲水性 ,提高了 PSF膜的耐污染性 ,并且合金膜获得比 PSF膜高的渗透通量。 PSF/ER合金膜中ER占 30 %时 ,可以得到一个满意的水通量 ,同时湿强度、成膜性能和耐污染性能也较好。