Permeate pressure build-up in shellside-fed hollow fiber pervaporation membranes

Pervaporation of water, ethanol and isopropanol through polydimethylsiloxane hollow fiber membranes was studied, with emphasis on elucidating the significance of permeate pressure build-up inside the fibers when the shell-feed mode of operation was used. The differential form of the Hagen-Poiseuille equation was used to describe the permeate pressure profile, and the theoretical predictions of permeate productivity were confirmed by experimental data. A parametric analysis showed that the dimensions of the hollow fiber (inside and outside diameters, and length) significantly affected the overall pervaporation performance of a hollow fiber membrane module, and the fiber dimensions must be optimized in order to achieve high productivity.     

Hydrophilic hollow fiber membranes for water desalination by the pervaporation method

Hydrophilic ion-exchange membranes based on sulfonated polyethylene hollow fibers were manufactured, and their suitability for a water pervaporation process was studied for possible application in water desalination systems. The effects of the following parameters on the average water flux were determined: membrane properties (diameter (0.4–1.8 mm) and wall thickness (0.05–0.18 mm)); charge density (0.6–1.2 meq g⁻¹); and operating conditions (brine inlet temperature (30–68°C), air sweep velocity (0–6 m s⁻¹), and salt concentration in the feed brine (0–3 M)). A water flux of 0.8–3.3 kg m⁻² h⁻¹ was obtained using this type of hollow fiber with an inlet brine temperature of 25–65°C. It was found that, for our application, the optimal specifications for the ion-exchange hollow fibers were an outside diameter of 1.2 mm, a wall thickness of 0.1 mm, and an ion-charge density of about 1.0 meq g⁻¹. This information is required as basic data for the design of a prototype water desalination system based on a pervaporation system that uses this type of ion-exchange hollow fiber membrane.     

Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes for pervaporation separation of ethanol/water solution

Polysulfone (PSF) hollow fiber membranes were spun by phase‐inversion method from 29 wt % solids of 29 : 65 : 6 PSF/NMP/glycerol and 29 : 64 : 7 PSF/DMAc/glycol using 93.5 : 6.5 NMP/water and 94.5 : 5.5 DMAc/water as bore fluids, respectively, while the external coagulant was water. Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes were prepared after PSF hollow fiber membranes were coated using different PVA aqueous solutions, which were composed of PVA, fatty alcohol polyoxyethylene ether (AEO₉), maleic acid (MAC), and water. Two coating methods (dip coating and vacuum coating) and different heat treatments were discussed. The effects of hollow fiber membrane treatment methods, membrane structures, ethanol solution temperatures, and MAC/PVA ratios on the pervaporation performance of 95 wt % ethanol/water solution were studied. Using the vacuum‐coating method, the suitable MAC/PVA ratio was 0.3 for the preparation of PVA/PSF hollow fiber composite membrane with the sponge‐like membrane structure. Its pervaporation performance was as follows: separation factor (α) was 185 while permeation flux (J) was 30g/m²·h at 50°C. Based on the experimental results, it was found that separation factor (α) of PVA/PSF composite membrane with single finger‐void membrane structure was higher than that with the sponge‐like membrane structure. Therefore, single finger‐void membrane structure as the supported membrane was more suitable than sponge‐like membrane structure for the preparation of PVA/PSF hollow fiber composite membrane. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 247–254, 2005     

Fabrication and structural tuning of novel composite hollow fiber membranes for pervaporation

A series of polysiloxaneimide (PSI)/polyetherimide (PEI) composite hollow fibers were fabricated by coextrusion and phase inversion. The hydrophobic PSI outer layer was set as the selective layer which was supported by the PEI inner layer. The PSI was synthesized by polycondensation of 3,3′,4,4′‐Biphenyltetracarboxylic Dianhydride (BPDA) with amino siloxane X‐22‐161A and a chain extender, 1,3‐Bis (3‐aminopropyl) ?1,1,3,3‐tertramethyldisiloxane (BATS). It was found that the macroscopic uniformity of PSI layer was dependent on the dope formulation, coagulant composition and dope flow rate: (1) the higher similarity degree of the solvent(s) for different layers in terms of solubility parameters, (2) the utilization of surfactant as a component in the water coagulant, and (3) higher flow rates of the outer layer dopes, led to the formation of more uniform and smoother PSI outer layer. The maximum outer layer thickness was around 2 μm. The bulk of the PEI layers were porous with finger like macrovoids. The outer surface of the inner PEI layer for some batches of the hollow fibers was confirmed to be porous. The original dual‐layer hollow fibers showed poor pervaporation performance. Post treatment was applied to cure the hollow fiber, delivering composite membranes with performance dominated by the coating material of PDMS. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43324.     

Enhanced hydrophilic polysulfone hollow fiber membranes with addition of iron oxide nanoparticles

Membranes are at the heart of hemodialysis treatment functions to remove excess metabolic waste such as urea. However, membranes made up of pure polymers and hydrophilic polymers such as polyvinylpyrrolidone suffer problems of low flux and bio‐incompatibility. Hence, this study aimed to improve polysulfone (PSf ) membrane surface properties by the addition of iron oxide nanoparticles (IONPs ). The membrane surface properties and separation performance of neat PSf membrane and membrane filled with IONPs at a loading of 0.2 wt% were investigated and compared. The membranes were characterized in terms of morphology, pure water permeability (PWP ) and protein rejection using bovine serum albumin (BSA ). A decrease in contact angle value from 66.62° to 46.23° for the PSf /IONPs membrane indicated an increase in surface hydrophilicity that caused positive effects on the PWP and BSA rejection of the membrane. The PWP increased by 40.74% to 57.04 L m^?2 h^?1 bar^?1 when IONPs were incorporated due to the improved interaction with water molecules. Furthermore, the PSf /IONPs membrane rejected 96.43% of BSA as compared to only 91.14% by the neat PSf membrane. Hence, the incorporation of IONPs enhanced the PSf hollow fiber membrane hydrophilicity and consequently improved the separation performance of the membrane for hemodialysis application. © 2017 Society of Chemical Industry     

Nanometric thin skinned dual‐layer hollow fiber membranes for dehydration of isopropanol

A novel sulfonated polyphenylsulfone (sPPSU)/polyphenylsulfone (PPSU)‐based dual‐layer hollow fiber membrane with a nanometric thin skin layer has been designed for biofuel dehydration via pervaporation. The thickness of skin selective layer is in the range of 15–90 nm under different spinning conditions measured by positron annihilation spectroscopy (PAS) coupled with a mono‐energetic positron beam. The effects of outer‐layer dope properties, coagulation temperature, and dope flow rate during spinning were systematically investigated. By tuning these spinning parameters, a high performance sPPSU/PPSU‐based dual‐layer hollow fiber membrane with desirable morphology was successfully obtained. Particularly owing to its nanometric thin skin layer, a high flux of 3.47 kg/m²h with a separation factor of 156 was achieved for dehydration of an 85 wt % isopropanol aqueous solution at 50°C. After post thermal treatment at 150°C for 2 h, the separation factor was dramatically improved to 687 while flux dropped to 2.30 kg/m²h, which make it comparable to the inorganic membranes. In addition, excellent correlations were found among the results from field emission scanning electron microscopy, PAS spectra, and separation performance. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2943–2956, 2013     

PDMS/ZIF-8 coating polymeric hollow fiber substrate for alcohol permselective pervaporation membranes

In order to develop high performance composite membranes for alcohol permselective pervaporation (PV), poly (dimethylsiloxane)/ZIF-8 (PDMS/ZIF-8) coated polymeric hollow fiber membranes were studied in this research. First, PDMS was used for the active layer, and Torlon®, PVDF, Ultem®, and Matrimid® with different porosity were used as support layer for fabrication of hollow fiber composite membranes. The performance of the membranes varied with different hollow fiber substrates was investigated. Pure gas permeance of the hollow fiber was tested to investigate the pore size of all fibers. The effect of support layer on the mass transfer in hydrophobic PV composite membrane was investigated. The results show that proper porosity and pore diameter of the support are demanded to minimize the Knudsen effect. Based on the result, ZIF-8 was introduced to prepare more selective separation layer, in order to improve the PV performance. The PDMS/ZIF-8/Torlon® membrane had a separation factor of 8.9 and a total flux of 847 g·m^-2·h^-1. This hollow fiber PDMS/ZIF-8/Torlon® composite membrane has a great potential in the industrial application.     

Interfacial resistance of dual-layer asymmetric hollow fiber pervaporation membranes formed by co-extrusion

Interface is critical for dual-layer membranes fabricated by co-extrusion and dry-jet wet spinning. In this work, for the first time, the importance of interface structure in overall membrane transport property was revealed by using Polysulfone (outer layer)/Matrimid (inner) dual-layer hollow fibers as a demonstration system. Due to the dope formulations of the two layers, dense skins came into formation at the shell side of Matrimid inner layer facing the interface. The Matrimid inner layer obtained from the dual-layer hollow fiber with the thinnest Polysulfone outer layer exhibited a flux around 1.0 × 10⁻³ kg/m²-s and a separation factor of ~800 in tert-butanol dehydration (feed flow rate 30 L/h, temperature 80 °C, permeate pressure 2 mbar, the same for the other tests). An estimation based on resistance model clearly indicated the dominance of Matrimid inner layer in the overall mass transfer of corresponding dual-layer membrane. As for hollow fibers with the thickest Polysulfone outer layer, the bulk substrate comprising the interfacial dense skin of Matrimid inner layer also displayed significant resistance and appreciable selectivity. Conclusively, the function of interface should not be ignored. The rule for the evolution of interface structure requires further exploration for fully understanding and utilizing the composite membrane by co-extrusion and phase inversion approach.     

Characterization and comparative evaluation of polysulfone and polypropylene hollow fiber membranes for blood oxygenators

Blood oxygenators are used to saturate oxygen levels and remove carbon dioxide from the body during cardiopulmonary bypass. Although the natural lung is hydrophilic, commercially used oxygenator materials are hydrophobic. Surface hydrophobicity weakens blood compatibility, as long-term contact with the blood environment may lead to different degrees of blood activity. Polysulfone may be considered an alternative hydrophilic material in the design of oxygenators. Therefore, it may be directed toward developing hydrophilic membranes. This study aims to investigate the feasibility of achieving blood gas transfer with a polysulfone-based microporous hollow fiber membrane and compare it with the commercially available polypropylene membranes. Structural differences in the membrane morphology, surface hydrophilicity, tortuosity, mass transfer rate, and material properties under different operation conditions of temperature and flow rates are reported. The polysulfone membrane has a water contact angle of 81.3°, whereas a commercial polypropylene membrane is 94.5°. The mass transfer resistances (s/m) for the polysulfone and polypropylene membranes are calculated to be 4.8 × 10⁴ and 1.5 × 10⁴ at 25°C, respectively. The module made of polysulfone was placed in the cardiopulmonary bypass circuit in parallel with the commercial oxygenator, and pH, pO₂, pCO₂ levels, and metabolic activity were measured in blood samples.     

Pore size control technique in the spinning of polysulfone hollow fiber ultrafiltration membranes

Conditions for finger-like void formation in polysulfone (PS) ultrafiltration membranes were studied empirically. It was found that both the “mixability parameter” which was obtained in separate titration experiments and the viscosity of coagulants could be used to predict membrane morphology. It was also found that finger-like void layers appeared under the conditions which dope had concentrations quite apart from the phase separation area and which coagulant had both a low mixability parameter and low viscosity.

These factors proved to play a very important role in controlling the pore size of membranes. The results of this study were applied to obtaining pore size variations of PS hollow fiber membranes.     

Mass transfer simulation on pervaporation dehydration of ethanol through hollow fiber NaA zeolite membranes

A multi‐layer series‐resistance mass transfer model was developed to simulate mass transfer behaviors of water/ethanol mixture through hollow fiber NaA zeolite membranes. The mass transfer through zeolite layer was described by Maxwell‐Stefan mechanism based on adsorption and diffusion parameters obtained from molecular simulation. The mass transfer through asymmetric hollow fiber support was described by dusty gas model involving Knudsen diffusion and viscous flow. It was found that the sponge‐like layer of support besides of zeolite layer made an important contribution to overall membrane transfer resistance while the finger‐like layer had less effect. When permeate pressure shifted from 0.2 to 7.5 kPa, the mass transfer resistance contribution of sponge‐like layer varied from 27.1 to 17.8%. Effects of microstructure parameters of support on mass transfer through membrane were investigated extensively. Large pore size and thin thickness for sponge‐like layer of support were beneficial to improve water permeation flux. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2468–2478, 2016     

Composite hollow fiber membranes

Composite polysulfone hollow fibers consisting of a polysulfone porous substrate coated with crosslinked polyethyleneimine (PEI) or furan resin are reported. These composite hollow fibers are analogous to the flat-sheet composite membranes known as NS-100 and NS-200. The surface structure of the porous substrate was rigorously studied before and after coating. Scanning electron microscope observations and reverse osmosis transport studies showed that the support fiber must have surface pore diameters of less than 0.2 μm to obtain a durable composite hollow fiber membrane. The curing process would normally follow in situ condensation of the PEI or the cationic polymerization of the furfuryl alcohol. However, since both the dense layer and surface of the porous substrate contract when exposed to the curing temperature (110–150°C), it was found to be profitable to cure the hollow fiber before applying the coating. When tested in a reverse osmosis rig, PEI/TDI-coated polysulfone hollow fiber bundles displayed 98% salt rejection and a flux of 5–7 gfd for a feed solution of 10,000 ppm NaCl at a hydraulic pressure of 400 psi. A new method of depositing furan resin on the polysulfone hollow fiber is described. The furfuryl alcohol is instantaneously polymerized by exposing the alcohol-soaked fiber to a 60% solution of concentrated sulfuric acid. It has been demonstrated that in such a polymerization procedure a dense, semipermeable layer is formed on top of the porous substrate; the resulting composite hollow fiber membrane yields salt rejections higher than 98% when tested under the above reverse osmosis conditions.     

Morphology and performance of polysulfone hollow fiber membrane

Polysulfone hollow fiber membranes were prepared via the dry-wet spinning process from dope solutions comprised of polysulfone, n-methyl-2-pyrrolidone, polyvinyl-2-pyrrolidone, and dodecylbenzene sulfonic acid, sodium salt. Morphology and performance of the membranes were affected by the compositions of coagulant and dope solution. Pore size and the water flux of the membrane increased by the addition of dodecylbenzene sulfonic acid, sodium salt to water in the coagulation bath, due to the changes of physicochemical properties of the outer coagulant. Addition of dodecylbenzene sulfonic acid, sodium salt to the dope solution also increased the pore size. The absence of polyvinyl-2-pyrrolidone, the pore forming agent, in the dope solution resulted in a remarkable decrease of pore size of the membrane. The distance between the spinneret and coagulation bath affected the membrane structure and performance. The membranes prepared in this study were suitable for hemofiltration in terms of molecular weight cut-off characteristics. © 1993 John Wiley & Sons, Inc.     

Modeling investigation of geometric size effect on pervaporation dehydration through scaled-up hollow fiber NaA zeolite membranes

A mass transfer model in consideration of multi-layer resistances through NaA zeolite membrane and lumen pressure drop in the permeate sidewas developed to describe pervaporation dehydration through scaled-up hollowfiber supported NaA zeolitemembrane. Itwas found that the transfer resistance in the lumen of the permeate side is strongly related with geometric size of hollow fiber zeolite membrane,which could not be neglected. The effect of geometric size on pervaporation dehydration could bemore significant under higher vacuumpressure in the permeate side. The transfer resistance in the lumen increaseswith the hollowfiber length but decreaseswith lumen diameter. The geometric structure could be optimized in terms of the ratio of lumen diameter to membrane length. A critical value of dI/L (Rc) to achieve high permeation flux was empirically correlated with extraction pressure in the permeate side. Typically, for a hollow fiber supported NaA zeolite membrane with length of 0.40 m, the lumen diameter should be larger than 2.0 mm under the extraction pressure of 1500 Pa.     

中空纤维式渗透汽化膜内流动的CFD模拟

采用计算流体动力学(CFD)数值模拟软件研究了入口速度和管径对中空纤维式渗透汽化膜内流动特征及分离性能的影响.结果表明,膜通道内压降和壁面剪切应力与入口速度呈正相关,与管径呈反相关;分离性能随着入口速度的增大,呈现先增大后减小的趋势;管径越小,分离性能越高.     

中空纤维渗透汽化复合膜及组件研究进展

中空纤维渗透汽化膜组件具有器件小型化及成本较低等方面的优势,其工业应用潜力巨大。本文介绍了中空纤维渗透汽化复合膜及组件的研究进展,阐述了膜材料、成膜方法以及组件结构参数等对组件渗透汽化性能的影响,并对中空纤维渗透汽化膜组件的中试研究进行了总结。通过组件放大及中试研究发现,中空纤维渗透汽化膜组件的装填密度、长度以及抽吸方式均会影响其下游侧的真空度,从而影响其渗透汽化性能。膜材料的分子设计、组件的结构参数优化以及耐溶剂耐高温封装将是中空纤维渗透汽化膜组件未来工业放大过程中的关键环节。     

Thermo-responsive mixed-matrix hollow fiber membranes

Up to date, preparation of thermo-responsive mixed-matrix membranes (MMM) has only be described as small scale flat membranes or multi-step processes for hollow fiber membranes. In this work, the development of thermo-responsive MMM hollow fibers composed of polyethersulfone as membrane polymer and poly(N-isopropylacrylamide) (PNIPAM) microgel particles via the wet spinning process is presented. PNIPAM particles are synthesized with (NP-S, z_{avg 20°C} = 105 nm) and without (NP-L, z_{avg 20°C} = 250 nm) sodium dodecyl sulfate and their thermo-responsive behavior is characterized by dynamic light scattering. Particle size (NP-S, NP-L), particle content (10%, 15%) and the extrusion pressure in the wet spinning process (1.0–3.0 bar) are investigated as experimental parameters. Reversible thermo-responsive behavior of the hollow fibers is demonstrated by water permeability measurements at different temperatures (20 and 50°C). The largest switching factors (R) are observed for the hollow fibers containing NP-L. For 15% NP-L and 1 bar extrusion pressure, water permeances between 0.5 and 6.0 L m⁻² h⁻¹ bar⁻¹ are observed, corresponding to R = 12 and a dextran (500 kDa) rejection of 91% at 25°C.     

Iron oxide nanoparticles improved biocompatibility and removal of middle molecule uremic toxin of polysulfone hollow fiber membranes

Middle molecule uremic toxins constitute to a quarter of uremic toxins present in human blood. In a condition where these uremic toxins accumulate in bloodstream due to renal failure, blood purification process using a high performance membrane is required. Here, we develop biocompatible mixed matrix membranes (MMMs) made up of polysulfone (PSf) and iron oxide nanoparticles (Fe₂O₃ NPs) with the focus to remove middle molecule uremic toxin effectively. The MMMs were evaluated in terms of their biocompatibility and separation performance. At higher Fe₂O₃ NPs loading, the MMM displayed a huge reduction of protein adsorption and platelet adhesion while maintaining normal blood coagulation time and acceptable complement activation. The optimized MMM exhibited high permeability (110.47 L m⁻² h⁻¹ bar⁻¹), protein retention (99.9%) and demonstrated excellent clearance of urea (82%) and lysozyme (46.7%). The PSf/Fe₂O₃ MMM is proven to have promising attributes for hemodialysis application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48234.