纺丝条件对PVDF/PVC中空纤维膜性能的影响

采用干-湿法纺丝工艺制备PVDF/PVC共混中空纤维膜,通过对水通量、孔径、截留率等的测试,研究了挤出速率、芯液流量、干纺程对PVDF/PVC中空纤维膜性能及结构的影响,并进行了详细的理论分析。试验结果表明挤出速率与膜通量存在最大值,芯液流量与膜通量及截留率呈线性关系,干纺程的影响效果跟挤出速率类似。可以通过改变纺丝条件来制备性能不同的中空纤维膜。     

Tailoring the morphology of self-assembled block copolymer hollow fiber membranes

Isoporous asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) hollow fiber membranes were successfully made by a dry-jet wet spinning process. Well-defined nanometer-scale pores around 20–40 nm in diameter were tailored on the top surface of the fiber above a non-ordered macroporous layer by combining block copolymer self-assembly and non-solvent induced phase separation (SNIPS). Uniformity of the surface-assembled pores and fiber cross-section morphology was improved by adjusting the solution concentration, solvent composition as well as some important spinning parameters such as bore fluid flow rate, polymer solution flow rate and air gap distance between the spinneret and the precipitation bath. The formation of the well-organized self-assembled pores is a result of the interplay of fast relaxation of the shear-induced oriented block copolymer chains, the rapid evaporation of the solvent mixture on the outer surface and solvent extraction into the bore liquid on the lumen side, and gravity force during spinning. Structural features of the block copolymer solutions were investigated by small-angle X-ray scattering (SAXS) and rheological properties of the solutions were examined as well. The scattering patterns of the optimal solutions for membrane formation indicate a disordered phase which is very close to the disorder-order transition. The nanostructured surface and cross-section morphology of the membranes were characterized by scanning electron microscopy (SEM). The water flux of the membranes was measured and gas permeation was examined to test the pressure stability of the hollow fibers.     

Preparation of Hollow Fiber Membranes by Nonsolvent Induced Phase Separation along with Hydrogen Gas Formation Using a Single Orifice Spinneret

Traditional nonsolvent induced phase separation (NIPS) process for fabrication of hollow fiber membranes (HFMs) faces challenges, like design and manufacture of spinneret with two concentric orifices to provide parallel and continuous feed of polymer solution and bore fluid at specific rates. These factors limit the use of traditional technique to produce HFMs. Here, a new direct spinning method for fabricating HFMs by feeding a polymer solution, containing a gas producing agent using single orifice spinneret is reported. Polysulfone‐dimethylacetamide solution containing NaBH₄ is extruded through a stainless‐steel needle (single orifice spinneret) into HCl aqueous solution (coagulation bath) at specific rates. Effects of polysulfone concentration, temperature, and pH of coagulant bath on structure and performance of the HFMs are investigated. Synergy between hydrogen from NaBH₄ hydrolysis and NIPS process benefits fabrication of HFMs with good hollow bore structure and high porous wall. The prepared HFMs show good dye separation.     

Transient Analysis of Mass-Transfer Rate in Recovering Metal Ions Using a Microporous Hollow Fiber Membrane and a Water-Soluble Chelating Polymer

ABSTRACT

Microporous hollow fiber membranes were used with a water-soluble chelating) polymer (polyacrylic acid) to recover and concentrate metal ions [copper(H)] from a solution. The polymer (chelator) solution was pumped through the bore of the fibers which was immersed in the metal ions solution. In this process the metal ions diffuse through the fiber porous space into the bore side and react with the chelator passing in the bore of the fiber. The transient change in concentration of metal ions at the outlet of the fiber were measured. The experimental data were well fitted by a one-dimensional convection equation which was derived with relatively simple assumptions and a steady-state theory, and reasonable values for the dispersion coefficient and an overall mass transfer coefficient were obtained.     

Robust and high performance pressure retarded osmosis hollow fiber membranes for osmotic power generation

Novel fabrication perspectives have been demonstrated to molecularly construct robust hollow fiber membrane supports for high performance thin‐film composite (TFC) pressure retarded osmosis (PRO) membranes. For the first time, we found that the desirable hollow fiber supports should possess high stretch resistance and acceptable ductility. The microstructure strength of the hollow fiber support may have more weights on overall robustness of the TFC PRO membranes than the apparent cross‐section morphology. Effectively manipulating the kinetics of phase inversion during spinning by maneuvering bore fluid chemistry, and polymer solution composition is a promising method to tailor the strength of hollow fiber supports. Prestabilization of the TFC membranes at elevated lumen pressures can significantly improve their PRO performance. The newly developed TFC PRO hollow fiber membranes exhibit a power density as high as 16.5 W/m² and a very low specific reverse salt flux (J_s/J_w) of 0.015 mol/L at a hydraulic pressure of 15 bar using synthetic seawater brine (1.0 M NaCl) as the draw solution. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1107–1119, 2014     

Highly scalable ZIF‐based mixed‐matrix hollow fiber membranes for advanced hydrocarbon separations

ZIF‐8/6FDA‐DAM, a proven mixed‐matrix material that demonstrated remarkably enhanced C₃H₆/C₃H₈ selectivity in dense film geometry, was extended to scalable hollow fiber geometry in the current work. We successfully formed dual‐layer ZIF‐8/6FDA‐DAM mixed‐matrix hollow fiber membranes with ZIF‐8 nanoparticle loading up to 30 wt % using the conventional dry‐jet/wet‐quench fiber spinning technique. The mixed‐matrix hollow fibers showed significantly enhanced C₃H₆/C₃H₈ selectivity that was consistent with mixed‐matrix dense films. Critical variables controlling successful formation of mixed‐matrix hollow fiber membranes with desirable morphology and attractive transport properties were discussed. Furthermore, the effects of coating materials on selectivity recovery of partially defective fibers were investigated. To our best knowledge, this is the first article reporting successful formation of high‐loading mixed‐matrix hollow fiber membranes with significantly enhanced selectivity for separation of condensable olefin/paraffin mixtures. Therefore, it represents a major step in the research area of advanced mixed‐matrix membranes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2625–2635, 2014     

Effect of polyethylene glycol molecular weights and concentrations on polyethersulfone hollow fiber ultrafiltration membranes

Polyethersulfone (PES) hollow‐fiber membranes were fabricated using poly(ethyleneglycol) (PEG) with different molecular weights (MW = PEG200, PEG600, PEG2000, PEG6000, and PEG10000) and poly(vinyl pyrrolidone) PVP40000 as additives and N‐methyl‐2‐pyrrolidone (NMP) as a solvent. Asymmetric hollow‐fiber membranes were spun by a wet phase‐inversion method from 25 wt % solids of 20 : 5 : 75 (weight ratio) PES/PEG/NMP or 18 : 7 : 75 of PES/(PEG600 + PVP40000)/NMP solutions, whereas both the bore fluid and the external coagulant were water. Effects of PEG molecular weights and PEG600 concentrations in the dope solution on separation properties, morphology, and mechanical properties of PES hollow‐fiber membranes were investigated. The membrane structures of PES hollow‐fiber membranes including cross section, external surface, and internal surface were characterized by scanning electron microscopy and the mechanical properties of PES hollow‐fiber membranes were discussed. Bovine serum albumin (BSA, MW 67,000), chicken egg albumin (CEA, MW 45,000), and lysozyme (MW 14,400) were used for the measurement of rejection. It was found that with an increase of PEG molecular weights from 200 to 10,000 in the dope solution, membrane structures were changed from double‐layer fingerlike structure to voids in the shape of spheres or ellipsoids; moreover, there were crack phenomena on the internal surfaces and external surfaces of PES hollow‐fiber membranes, pure water permeation fluxes increased from 22.0 to 64.0 L m^?2 h^?1 bar^?1, rejections of three protein for PES/PEG hollow‐fiber membranes were not significant, and changes in mechanical properties were decreased. Besides, with a decrease of PEG600 concentrations in the dope solution, permeation flux and elongation at break decreased, whereas the addition of PVP40000 in the dope solution resulted in more smooth surfaces (internal or external) of PES/(PEG600 + PVP40000) hollow‐fiber membranes than those of PES/PEG hollow‐fiber membranes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3398–3407, 2004     

Druckverlustberechnung an konzentrischen porösen Hohlzylinderfiltern anhand dimensionsanalytischer Folgerungen und experimenteller Daten

In practice many geometric shapes of filter mediums are possible which differ from the classical case cross‐flow filtration with hollow fiber membranes. In this paper the influence of the filter medium geometry on the filter medium pressure loss due to porous hollow cylindrical tube with inflow from outside was investigated. An increase in resistance of the filter medium as a function of layer thickness and average curvature was observed. Based on dimensional analyses the obtained data were placed in a meaningful context and an empirical model for the calculation of the pressure loss in curved filter mediums could be derived.     

Effect of polyvinylpyrrolidone molecular weights on morphology,oil/water separation,mechanical and thermal properties of polyetherimide/polyvinylpyrrolidone hollow fiber membranes

We prepared polyetherimide (PEI) hollow fiber membranes using polyvinylpyrrolidones (PVP) with different molecular weights (PVP 10,000, PVP 40,000, and PVP 1,300,000) as additives for oil/water separation. Asymmetric hollow fiber membranes were fabricated by wet phase inversion technique from 25 wt % or 30 wt % solids of 20 : 5 : 75 or 20 : 10 : 70 (weight ratio) PEI/PVP/N‐metyl‐2‐pyrrolidone (NMP) solutions and a 95 : 5 NMP/water solution was used as bore fluid to eliminate resistance on the internal surface. Effects of PVP molecular weights on morphology, oil‐surfactant‐water separation characteristics, mechanical, and thermal properties of PEI/PVP hollow fiber membranes were investigated. It was found that an increase in PVP molecular weight and percentage in PEI/PVP dope solution resulted in the membrane morphology change from the finger‐like structure to the spongy structure. Without sodium hypochlorite posttreatment, hollow fiber membranes with higher PVP molecular weights had a higher rejection but with a lower water flux. For oil‐surfactant‐water emulsion systems (1600 ppm surfactant of sodium dodecylbenzenesulfonate and 2500 ppm oil of n‐decane), experimental results illustrated that the rejection rates for surfactant, total organic carbon, and oil were 76.1 ≈ 79.8%, 91.0 ≈ 93.0%, and more than 99%, respectively. Based on the glass transition temperature values, PVP existed in hollow fiber membranes and resulted in the hydrophilicity of membranes. In addition, using NaOCl as a posttreatment agent for membranes showed a significant improvement in membrane permeability for PVP with a molecular weight of 1300 K, whereas the elongation at break of the treated hollow fiber membranes decreased significantly. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2220–2233, 1999     

Synthesis and morphology of platinum‐coated hollow‐fiber carbon membranes

Hollow‐fiber carbon membranes were prepared and used as support media for a platinum catalyst. The platinum metal was deposited onto the surface of the hollow‐fiber carbon membranes by three different techniques: solution coating with chloroplatinic acid, which is the commonly used technique; vapor deposition, involving the sublimation of the platinum metal; and magnetron sputter coating, the most effective method. The hollow‐fiber carbon membranes coated with a chloroplatinic acid solution were studied with scanning electron microscopy (SEM) and energy‐dispersive X‐ray analysis (EDAX). The platinum coating grew on the surface, unevenly, in the form of small crystals. The percentage of platinum on the surface was too low to be detected by EDAX. The high‐vacuum evaporation coating of the membranes with platinum was also studied with both SEM and EDAX. Again, because of the low percentage of platinum, EDAX did not reveal any platinum on the surfaces of the membranes. The magnetron sputter coating of platinum onto the membranes was performed and studied with SEM. The thickness of the coated platinum could be varied through variations in the coating time. The cavities observed in the micrographs were formed during the coating operations by the presence of dust particles on the membranes. An SEM micrograph of a hollow‐fiber carbon membrane, produced from a polyacrylonitrile‐based precursor, spun with a low amount of dimethyl sulfoxide in the bore fluid, and coated with platinum, showed a skin on the outside and a porous elongated structure inside the skin. The distance between the inner and outer skins contained fingerlike pores of various sizes. The largest pores were found near the inside skin, whereas the smallest pores were next to the outside skin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1051–1058, 2003     

Preparation and membrane performance of poly(ethylene-co-vinyl alcohol) hollow fiber membrane via thermally induced phase separation

Poly(ethylene-co-vinyl alcohol) (EVOH) hollow fiber membranes with ultrafiltration performance were prepared from EVOH/glycerol systems via thermally induced phase separation (TIPS). The diluent glycerol was used as bore liquid to make a lumen of the hollow fiber for the purpose of prevention of the diluent evaporation and the larger pores formation at the inner surface of the hollow fiber. The obtained hollow fiber membranes showed asymmetric structures with skin layer near the outer surface, the larger pores just below the skin layer and the smaller pores near the inner surface. The formation of the larger pores near the outer surface was due to the enhanced pore growth by the water penetration. Some primary factors affecting the structure and performance of the membranes such as ethylene content (EC) in EVOH, cooling water bath temperature and take-up speed were studied extensively. The water permeability can be improved by increasing the water bath temperature and the take-up speed and by decreasing the EC. Both the pore size at the outer surface and the connectivity between the pores have to be considered together to understand the experimental result of the water permeability and the solute rejection.     

Investigation on the effect of spinning conditions on the properties of hollow fiber membrane for hemodialysis application

Polyethersulfone (PES) hollow fiber membranes were fabricated via the dry‐wet phase inversion spinning technique, aiming to produce an asymmetric, micro porous ultrafiltration hollow‐fiber specifically for hemodialysis membrane. The objective of this study is to investigate the effect of spinning conditions on the morphological and permeation properties of the fabricated membrane. Among the parameters that were studied in this work are air gap distance, dope extrusion rate, bore fluid flow rate, and the take‐up speed. The contact angle was measured to determine the hydrophilicity of the fibers. Membrane with sufficient hydrophilicity properties is desired for hemodialysis application to avoid fouling and increase its biocompatibility. The influences of the hollow fiber's morphology (i.e., diameter and wall thickness) on the performance of the membranes were evaluated by pure water flux and BSA rejection. The experimental results showed that the dope extrusion rate to bore fluid flow rate ratio should be maintained at 1:1 ratio to produce a perfectly rounded asymmetric hollow fiber membrane. Moreover, the flux of the hollow fiber spun at higher air gap distance had better flux than the one spun at lower air gap distance. Furthermore, spinning asymmetric hollow fiber membranes at high air gap distance helps to produce a thin and porous skin layer, leading to a better flux but a relatively low percentage of rejection for BSA separation. Findings from this study would serve as primary data which will be a useful guide for fabricating a high performance hemodialysis hollow fiber membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43633.     

新型中空纤维陶瓷膜的制备方法

新型中空纤维陶瓷膜由于具有装填密度大、单位体积膜有效分离面积大、膜壁薄、渗透通量高和节省原料、易于实现分离设备小型化等独特优点而受到广泛关注,在用于多孔和致密陶瓷分离膜、固体氧化物燃料电池、微通道反应器、催化剂载体等方面都有着潜在的应用前景。本文在概括中空纤维陶瓷膜特点的基础上,综述了中空纤维陶瓷膜的制备方法及研究进展,着重分析比较了不同制备方法的优缺点。将相转化法应用于中空纤维陶瓷膜的制备,可实现通过一步成型制造具有自支撑非对称结构的复合陶瓷膜,有利于提高膜的渗透通量,简化膜制备工艺和显著降低制造成本。     

热致相分离法iPP中空纤维微空膜结构与性能--稀释剂的作用

Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.     

Hydrogen separation at elevated temperatures using metallic nickel hollow fiber membranes

Nickel is a cheaper metallic material compared to palladium membranes for H₂ separation. In this work, metallic Ni hollow fiber membranes were fabricated by a combined phase inversion and atmospheric sintering method. The morphology and membrane thickness of the hollow fibers was tuned by varying the spinning parameters like bore liquid flow rate and air gap distance. H₂ permeation through the Ni hollow fibers with N₂ as the sweep gas was measured under various operating conditions. A rigorous model considering temperature profiles was developed to fit the experimental data. The results show that the hydrogen permeation flux can be well described by using the Sieverts’ equation, implying that the membrane bulk diffusion is still the rate‐limiting step. The hydrogen separation rate in the Ni hollow fiber module can be improved by 4–8% when switching the co‐current flow to the countercurrent flow operation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3026–3034, 2017     

PEEKWC ultrafiltration hollow‐fiber membranes: Preparation,morphology, and transport properties

A series of hollow‐fiber membranes was produced by the dry–wet spinning method from PEEKWC, a modified poly(ether ether ketone) with good mechanical, thermal, and chemical resistance. The fibers were prepared under different spinning conditions, varying the following spinning parameters: polymer concentration in the spinning solution, height of the air gap, and bore fluid composition. The effect of these parameters on the water permeability, the rejection of macromolecules (using dextrane with an average molecular weight of 68,800 g/mol), and the morphology of the membranes was studied. The results were also correlated to the viscosity of the spinning solution and to the ternary polymer/solvent/nonsolvent phase diagram. The morphology of the cross section and internal and external surfaces of the hollow fibers were analyzed using scanning electron microscopy (SEM). All membranes were shown to have a fingerlike void structure and a skin layer, depending on the spinning conditions, varying from (apparently) dense to porous. Pore size measurements by the bubble‐point method showed maximum pore sizes ranging from 0.3 to 2 μm. Permeability varied from 300 to 1000 L/(h^?1 m^?2 bar) and rejection to the dextrane from 10 to 78%. The viscosity of polymer solutions was in the range of 0.2 to 3.5 Pa s. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 841–853, 2004     

Preparation and performance of braid‐reinforced poly(vinyl chloride) hollow fiber membranes

A novel braid‐reinforced (BR) poly(vinyl chloride) (PVC) hollow fiber membrane was fabricated via dry‐wet spinning process. The mixtures of PVC polymer solutions were uniformly coated on the tubular braid which contained polyester (PET) and polyacrylonitrile (PAN) fibers. The influences of braid composition on structure and performance of BR PVC hollow fiber membranes were investigated. The results showed that the prepared BR PVC hollow fiber membranes were composed of two layers which contained separation layer and tubular braid supported layer when the PET and PET/PAN hybrid tubular braids were used as the reinforcement. But the sandwich structure appeared when the PAN tubular braid was used as the reinforcement, which revealed outer separation layer, tubular braid supported layer and the inner polymer layer. The BR PVC hollow fiber membranes that prepared by PET/PAN hybrid tubular braid had favorable interfacial bonding state compared with the membrane prepared by pure PET or PAN tubular braid. The pure water flux of the BR PVC hollow fiber membranes that prepared by the PET/PAN hybrid tubular braid were lower than that prepared by pure PET or PAN tubular braid, but the rejection of Bovine serum albumin was opposite. The tensile strength of prepared BR PVC hollow fiber membrane was higher than 50 MPa. Both of the tensile strength and elongation at break decreased with the increase of the PAN filaments in the PET/PAN hybrid tubular braid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45068.     

Preparation of a heterogeneous hollow‐fiber affinity membrane modified with a mercapto chelating resin

A high‐quality, heterogeneous hollow‐fiber affinity membranes modified with mercapto was prepared through phase separation with blends of a chelating resin and polysulfone as membrane materials, poly(ethylene glycol) as an additive, N,N‐dimethylacetamide as a solvent, and water as an extraction solvent. The effects of the blending ratio and chelating resin grain size on the structure of the hollow‐fiber affinity membrane were studied. The effects of the composition of the spin‐cast solution and process parameters of dry–wet spinning on the structure of the heterogeneous hollow‐fiber affinity membrane were investigated. The pore size, porosity, and water flux of the hollow‐fiber affinity membrane all decreased with an increase in the additive content, bore liquid, and dry‐spinning distance. With an increase in the extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow‐fiber affinity membrane all increased, but the pore size and water flux of the hollow‐fiber affinity membrane decreased. It was also found that the effects of the internal coagulant composition and external coagulant composition on the structure of the heterogeneous hollow‐fiber affinity membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of the heterogeneous hollow‐fiber affinity membrane and decrease the pore size, porosity, and water flux of the heterogeneous hollow‐fiber affinity membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the heterogeneous hollow‐fiber affinity membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Enhancing oxygen permeation via multiple types of oxygen transport paths in hepta‐bore perovskite hollow fibers

The multiple types of efficient oxygen transport paths were demonstrated in high‐mechanical‐strength hepta‐bore Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ hollow fiber membranes. These types of paths play a prominent role in enhancing oxygen permeation fluxes (17.6 mL min^?1 cm^?2 at 1223 K) which greatly transcend the performance of state‐of‐the‐art Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ hollow fiber membranes, showing a good commercialization prospect. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4273–4277, 2017     

Two‐dimensional simulation of hollow fiber membrane fabricated by phase inversion method

In the steady fabricating process, two‐dimensional hollow fiber membrane near the spinneret was numerically simulated using the finite element method (FEM). The unknown positions of free surface and moving interface were calculated simultaneously by the velocity and pressure fields. The effects of seven relevant parameters, i.e., inertia term, gravity term, dope flow rate, bore flow rate, dope viscosity, tensile force, end velocity and non‐Newtonian on the velocity and diameter profile were studied. On the basis of the simulated results, the inertia term in hollow fiber‐spinning process was safely neglected in low speed, while the effect of gravity was not be neglected. Besides, the outer diameter of the fibers increased with an increase of dope flow rate and bore flow rate; Large tensile force or large end velocity could cause large deformation in the air gap; larger viscous dope solution tended to make less deformation in the air gap. It was found that an increase of the dope flow rate at small dope flow rate resulted in an increase of the inner diameter, while at large dope flow rate, it decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2067–2074, 2006