Degumming of crude soybean oil by ultrafiltration using polymeric membranes

In this study, the ability of two ultrafiltration polymeric membranes to perform the degumming of a crude soybean oil/hexane mixture is tested. The performance of both membranes is defined in terms of their permeation flux, permeate color, and rejection of phospholipids. One of the membranes was synthesized in our laboratories from polyvinylidenefluoride (PVDF); the other one is a commercially available membrane made of polyimide. The degumming experiments were done in a stirred dead-end ultrafiltration cell pressurized with N₂. Results show that tested membranes are suitable for removing phospholipids from the crude oil/hexane miscella in the range of temperature and transmembrane pressure utilized in this work. Both membranes have high selectivity regarding phospholipids and produce a moderate reduction in permeate color. The PVDF membrane gives permeate fluxes up to threefold larger than those obtained with polyimide membrane at the same operational conditions, making the former more suitable for use at industrial scale.     

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.     

Fouling evaluation on membrane distillation used for reducing solvent in polyphenol rich propolis extract

Membrane distillation (MD) has not been widely studied in the concentrate of phenolic rich solution in comparison to osmotic distillation.In this work,the potential of MD to reduce solvent in the polyphenol rich propolis extract was further investigated.Polyvinylidene fluoride (PVDF) membranes were engineered with the smaller pore size for the less hydrophobic surface in order to avoid wetting,allowing only the solvent vapor to be transferred from the warm feed into the cold permeate.All the membranes exhibited more than 95％ rejection of phenolic and flavonoid compounds.Although the hydrophilic membranes exhibited less fouling,they displayed a lower flux than the hydrophobic membrane due to the hindrance in the wetted pores.The hydrophobic membrane was seriously fouled by the phenolic acid as shown in the Fourier transform infrared spectroscopy spectrum.Pore plugging occurred on these hydrophobic membranes as confirmed in the scanning electron microscope images.     

Desalination by membrane distillation adopting a hydrophilic membrane

Direct contact membrane distillation (MD) by means of composite membranes with a PVA/PEG hydrophilic layeron a hydrophobic PVDF substrate has been developed for desalination. The effects of brine temperature, salt concentration, running time and the addition of ethanol on the flux of composite membranes have been investigated. Results showed that the flux of the composite membrane did not deteriorate by adopting an additional hydrophilic membrane although durability was obviously improved. More than 99% of the separation coefficient in one run was achieved with the conductivity of the produced fresh water in the range of 6-10 μs/cm. The flux of the composite membrane retained 91% flux of substrate at 70°C, being 23.7 kg/h·m². When the brine temperature rose to 70°C, the composite membrane showed a declined concentration polarisation, with a smaller C_mb/C_b (3.89) than that of the substrate (5.79). Although the flux decreased with the increase of brine concentration, it retained 64% flux of pure water at brine solution containing 20% NaCl and was kept almost constant until 25% NaCl. In the continuous running experiments, there was no obvious drop of flux, even after adding 25% ethanol to the brine and running overnight. It is expected that adopting a hydrophilic layer can prohibit the wetting problem that faced traditional MD with hydrophobic membranes.     

Experimental Study and Design of a Submerged Membrane Distillation Bioreactor

A hybrid process incorporating membrane distillation in a submerged membrane bioreactor operated at elevated temperature is developed and experimentally demonstrated in this article. Since organic particles are rejected by an ‘evaporation’ mechanism, the retention time of non‐volatile soluble and small organics in the submerged membrane distillation bioreactor (MDBR) is independent of the hydraulic retention time (mainly water and volatiles). A high permeate quality can be obtained in the one‐step compact process. The submerged MD modules were designed for both flat‐sheet membranes and tubular membrane configurations. The process performance was preliminarily evaluated by the permeate flux stabilities. The module configuration design and air sparging used in the MDBR process were tested. Flux declines were observed for the thin flat‐sheet hydrophobic membranes. Tubular membrane modules provided more stable permeate fluxes probably due to the turbulent condition generated from air sparging injected inside the tubular membrane bundles. The experiments with the submerged tubular MD module gave stable fluxes of approximately 5 L/m² h over 2 weeks at a bioreactor temperature of 56 °C. The total organic carbon in the permeate was consistently lower than 0.7 mg/L for all experiments.     

Treatment of wastewater containing oil using phosphorylated silica nanotubes (PSNTs)/polyvinylidene fluoride (PVDF) composite membrane

PVDF membranes are broadly applied in many fields owing to their good physicochemical stability, resistance to oxidation and chlorine. However when treating with wastewater, PVDF membranes are easily contaminated by pollutant, degrading their properties due to the hydrophobicity and poor anti-compaction capabilities, which can result in the decline of flux and lifespan of the membrane and limit their application in large scale. To enhance the integrative capabilities of PVDF membrane, phosphorylated silica nanotubes (PSNTs) were doped to PVDF to prepare a novel PSNTs/PVDF composite membrane through a phase inversion technique. The PSNTs/PVDF composite membranes were exposed to wastewater containing oil, and the effects of doped materials, operating pressure and operating temperature on fluxes were researched. The optimum parameters are: operating pressure is 0.1 MPa, operating temperature 25 °C. Through physical flushing and chemical cleaning, the PSNTs/PVDF membranes could still keep a high permeation flux and long lifetime. Finally, the interaction mechanism between PSNTs and PVDF membrane, the anti-fouling mechanism of PSNTs/PVDF composite membrane were explored and analyzed. The results show that the hydrophilicity, anti-fouling and anti-compaction properties of composite membrane can be obviously enhanced and hence the PSNTs/PVDF composite membrane is desirable in the treatment of wastewater containing oil and sewage.     

Keramische Membranen in der Membrandestillation

TiO₂ membranes were successfully rendered hydrophobic (modified with perfluoroalkyl silanes) and evaluated by liquid entry pressure (LEP) measurements and membrane distillation (MD) tests. It was shown that the LEP is strongly depended on the pore size of the membranes and the feed composition. The obtained permeate fluxes were highest in vacuum MD. None of the membranes showed any sign of wetting during the experiments and salt retentions greater than 99.9 % were recorded and permeate qualities lower than 2 µS cm^?1 were achieved in air gap MD and vacuum MD.     

Fabrication of poly(vinylidene fluoride) membrane via thermally induced phase separation using ionic liquid as green diluent

Ionic liquid(IL), 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6) as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF) membranes via thermally induced phase separation(TIPS). Phase diagram of PVDF/[BMIM]PF6 was measured. The effects of polymer concentration and quenching temperature on the morphologies, properties, and performances of the PVDF membranes were investigated. When the polymer concentration was 15 wt%, the pure water flux of the fabricated membrane was up to nearly 2000 L·m~(-2)·h~(-1), along with adequate mechanical strength. With the increasing of PVDF concentration and quenching temperature, mean pore size and water permeability of the membrane decreased. SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6) presented spherulite structure. And the PVDF membranes were represented as β phase by XRD and FTIR characterization. It provides a new way to prepare PVDF membranes with piezoelectric properties.     

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。     

Formation of multilayer poly(acrylic acid)/poly(vinylidene fluoride) composite membranes for pervaporation

Dual‐ and multilayer composite membranes, consisting of poly(acrylic acid) (PAA) and poly(vinylidene fluoride) (PVDF), were synthesized by the plasma‐induced polymerization technique. The dual‐layer membrane had a dense PAA layer grafted onto a microporous PVDF substrate, whereas in the multilayer membranes, the grafted PAA and the PVDF layers were arranged in an alternating sequence (e.g., PAA/PVDF/PAA and PAA/PVDF/PAA/PVDF/PAA). These membranes were used in a pervaporation process to separate ethanol–water solutions. For the dual‐layer membranes, the results indicated that the separation factor increased and the permeation flux decreased with increasing amounts of grafted PAA. For the case of grafting yield < 0.6 mg/cm², the composite membrane demonstrated poor separation. As the grafting yield reached 0.85 mg/cm², a sharp increase of the separation factor was observed. For the multilayer membranes, the pervaporation performances were very good, with high separation factors (on the order of 100) and reasonable permeation fluxes over a wide ethanol concentration range. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2266–2274, 2004     

铸膜液的粘度和组成对PVDF微孔膜性能的影响

实验采用浸没沉淀相转化的方法制备PVDF微孔膜,考察了聚偏氟乙烯(PVDF)/聚乙二醇(PEG-6000)/二甲基乙酰胺(DMAc)比例的变化,对铸膜液的粘度及膜性能的影响。分析了影响膜过程动力学因素,确定了该体系制膜的理想条件。结果表明,当PVDF质量分数为14%,PEG(6000)质量分数为5%时,制得的平板膜可达较佳性能。     

Controlled pore size, thickness and surface free energy of super-hydrophobic PVDF® and Hyflon®AD membranes

Super-hydrophobic membranes were manufactured by using two per-fluorinated polymers such as PVDF and Hyflon AD. The combination of controlled structure and supra-molecular chemistry made these membranes ideal interfaces to be used in membrane contactors.     

A review of nanoparticle-enhanced membrane distillation membranes: membrane synthesis and applications in water treatment

Membrane distillation (MD) is a thermally driven process that uses low-grade energy to operate and has been extensively explored as an alternative cost-effective and efficient water treatment process compared to conventional membrane processes. MD membranes are synthesized from hydrophobic polymers, e.g. polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or polypropylene (PP), using various methods including phase inversion and electrospinning techniques. Recent literature on MD membranes clearly shows their important role in surface water/wastewater treatment and seawater desalination. Modification of MD membranes with nanoscale materials significantly improves their performance, preventing wetting and fouling. This review presents a critical assessment of the progress on the use of nanomaterials for the modification of MD membranes. The techniques commonly used to synthesize MD membranes, the modifications that have been adopted for the incorporation of nanomaterials onto membranes, and the unique properties these nanomaterials impart on the membranes are discussed. The use of modified membranes in different MD configurations and their application in groundwater, surface water, wastewater, brackish water and seawater treatment is reviewed. Finally, cost implications, commercial viability, environmental sustainability, and future prospects of MD are also discussed to elucidate promising approaches for a future and successful implementation of MD at an industrial scale. © 2019 Society of Chemical Industry     

Preparation and characterization of novel poly(vinylidene fluoride) membranes using self-assembled dibenzylidene sorbitol for membrane distillation

We proposed a method for the preparation of novel poly(vinylidene fluoride) (PVDF) membranes with self-assembled 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS). The vapor-induced phase separation (VIPS) method with a dry/wet process was used to produce DMDBS/PVDF composite membranes. The resulting membranes exhibited the coexistence of PVDF cellular pores and crystalline particles. The DMDBS molecules self-assembled into nanofibril structures, and a large number of nanofibrils were found on the surfaces and in the cross-sections of the prepared membranes. The DMDBS nanofibril networks in the PVDF matrix acted as reinforcing materials that enhance the hardness and stiffness of the membranes. Moreover, because of the entangled DMDBS networks, a greater strain was required to induce sample failure; therefore, the ductility of the membranes increased with increasing amounts of DMDBS. In addition, in a membrane distillation process, our composite membranes exhibited a good permeate flux that was comparable to that of commercial PVDF membranes.     

In‐situ cross‐linked PVDF membranes with enhanced mechanical durability for vacuum membrane distillation

A novel and effective one‐step method has been demonstrated to fabricate cross‐linked polyvinylidene fluoride (PVDF) membranes with better mechanical properties and flux for seawater desalination via vacuum membrane distillation (VMD). This method involves the addition of two functional nonsolvent additives; namely, water and ethylenediamine (EDA), into the polymer casting solution. The former acts as a pore forming agent, while the latter performs as a cross‐linking inducer. The incorporation of water tends to increase membrane flux via increasing porosity and pore size but sacrifices membrane mechanical properties. Conversely, the presence of EDA enhances membrane mechanical properties through in‐situ cross‐linking reaction. Therefore, by synergistically combining the effects of both functional additives, the resultant PVDF membranes have shown good MD performance and mechanical properties simultaneously. The parameters that affect the cross‐link reaction and membrane mechanical properties such as reaction duration and EDA concentration have been systematically studied. The membranes cast from an optimal reaction condition comprising 0.8 wt % EDA and 3‐hour reaction not only shows a 40% enhancement in membrane Young's Modulus compared to the one without EDA but also achieves a good VMD flux of 43.6 L/m²‐h at 60°C. This study may open up a totally new approach to design next‐generation high performance MD membranes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4013–4022, 2016     

相转化法制备PVDF超滤膜及其亲水化改性研究进展

综述了聚偏氟乙烯(PVDF)超滤(UF)膜在相转化制备方法和亲水化改性两方面的最新研究进展。在相转化制备方法中,介绍了聚合物用量、溶剂的选择、添加剂的种类和用量及凝固浴组成和温度对膜结构和性能的影响;在PVDF超滤膜亲水化改性方面,介绍了共混改性、共聚改性、辐照接枝改性、等子体改性等方法的机理、特点和近年来的研究进展,指出了共混改性是今后亲水改性的主要方向。     

Effects of pre-oxidant (KMnO4) on structure and performance of PVDF and PES membranes

The structure and performance of membrane materials are very important to the efficient and stable operation in membrane drinking water purification technology. Potassium permanganate (KMnO₄), which can change the characteristics of organic matters and control membrane surface fouling, has been widely used as pre-oxidant in the front of membrane drinking water process. This study investigates the evolution of membrane surface structure and performance when polyvinylidene fluoride (PVDF) and polyethersulfone (PES) were exposed to 10, 100 and 1000 mg·L^-1 KMnO₄ solution for 6 and 12 d, respectively. The aged membrane physicochemical characteristics such as membrane surface morphology, chemical composition, hydrophilicity, porosity and zeta potential were evaluated by modern analytical and testing instruments. The anti-fouling property of membrane surface was also investigated by the filtration-backwash experiment. The results indicated that the different concentrations and exposure time of KMnO₄ led to a different variation on PVDF and PES membrane surface structure and performance, which could further affect the membrane separation performance and the membrane fouling behaviors. The membrane surface pore size and porosity increased due to the dislodgment and degradation of membrane additive (PVP), which improved membrane permeability and enhanced the adsorption and deposition of pollutants in the membrane pores. With the increase of exposure time, the membrane surface pore size and porosity reduced for the reactions of chain scission and crosslinking on membrane materials, and the backwashing efficiency declined, leading to a more serious irreversible fouling. Compared with PVDF membranes, the formation of sulfonic group for PES membranes increased the negative charge on membrane surface due to the oxidation of KMnO₄. The present study provides some new insights for the regulation of the pre-oxidant dose and the selection of the membrane materials in KMnO₄ pre-oxidation combined with membrane filtration system.     

Fabrication and characterization of hydrophobic PVDF hollow fiber membranes for desalination through direct contact membrane distillation

The mixture of inorganic salt LiCl and soluble polymer polyethylene glycol (PEG) 1500 as non-solvent additive was introduced to fabricate hydrophobic hollow fiber membrane of polyvinylidene fluoride (PVDF) by phase inversion process, using N,N-dimethylacetamide (DMAc) as solvent and tap water as the coagulation medium. Compared with other three membranes from PVDF/DMAc, PVDF/DMAc/LiCl and PVDF/DMAc/PEG 1500 dope solution, it can be observed obviously by scanning electron microscope (SEM) that the membrane spun from PVDF/DMAc/LiCl/PEG 1500 dope had longer finger-like cavities, ultra-thin skins, narrow pore size distribution and porous network sponge-like structure owing to the synergistic effect of LiCl and PEG 1500. Besides, the membrane also exhibited high porosity and good hydrophobicity. During the desalination process of 3.5 wt% sodium chloride solution through direct contact membrane distillation (DCMD), the permeate flux achieved 40.5 kg/m² h and the rejection of NaCl maintained 99.99% with the feed solution at 81.8 °C and the cold distillate water at 20.0 °C, this performance is comparable or even higher than most of the previous reports. Furthermore, a 200 h continuously desalination experiment showed that the membrane had stable permeate flux and solute rejection, indicating that the as-spun PVDF hollow fiber membrane may be of great potential to be utilized in the DCMD process.     

纳米二氧化硅对PVDF/CA锂离子电池共混膜性能影响的研究

以聚偏氟乙烯(PVDF)与醋酸纤维素(CA)的共混物为基本材料,加入纳米SiO2对其进行共混改性,制备了有机/无机复合锂离子电池隔膜,研究了纳米SiO2添加量对复合膜物理性能与电化学性能的影响。通过万能试验机、接触角仪、扫描电子显微镜(SEM)、热重分析仪(TG)、交流阻抗与电池充放电测试,对复合隔膜及其组装的电池进行表征,结果表明,在PVDF/CA共混基体中加入纳米SiO2可有效提高隔膜的相关性能,其中添加9%纳米SiO 2的复合膜(PCS9)综合性能较优,即吸液率124.97%,离子电导率1.01 mS/cm,拉伸强度27.35 MPa,组装的锂离子半电池在0.2 C/0.2 C下循环充放电50圈后,放电比容量保持良好稳定,达到145.7 mA·h/g左右。     

Effect of salt additive on the formation of microporous poly(vinylidene fluoride) membranes by phase inversion from LiClO4/Water/DMF/PVDF system

The effect of a salt additive, lithium perchlorate, on the morphology and crystal structure of PVDF membranes prepared by wet phase inversion process was studied. The gelation phase boundaries of the quaternary system, LiClO4/water/DMF/PVDF, were determined at 25 °C. It was found that the gelation lines shifted up progressively with increasing salt contents in this system. For a salt-free casting dope, the formed membrane exhibited a typical asymmetric structure characterized by the skin, parallel columnar macrovoids, and cellular pores. WAXD analysis indicated that PVDF crystallized into ‘α’ (type II) structure in this membrane. By contrast, when PVDF was precipitated from high salt-content dopes (e.g. ≥5 wt%), the macrovoids bent and extended towards the bottom region while the original cellular pores evolved into very large voids. The PVDF crystallites became ‘β’ form (type I) in these membranes. Thermal analysis (DSC) of all membranes showed dual melting peaks at low heating rates (≤5 °C/min), suggesting that the crystallites formed in the immersion-precipitation process were imperfect and they underwent re-crystallization during the heating process. Using low voltage SEM at high magnifications (e.g. 100 KX at 0.55 KV) on uncoated samples, the fine structures (10-20 nm) of the PVDF crystallites were observed. And at very high magnifications (225 KX at 0.59 KV), it was observed that the skin region of the membrane prepared from high salt-content dopes actually contained many nano-pores (e.g. 20 nm). This contributes to the high permeation rate and low solute rejection as revealed from the water-flux measurements.