Fabrication of ZIF-8 membranes on dual-layer ZnO-PES/PES organic hollow fibers by in-situ crystallization

Compared to inorganic supports, polymeric supports can offer additional benefits, e.g., easier processing and cheaper. However, the organic surface has weak adhesion to the zeolitic imidazolate frameworks(ZIFs) membrane layer, which usually requires complex surface modification or seeding. Herein, we demonstrate that a dual-layer asymmetric polymer support prepared by a simple spinning process is a good candidate for the preparation of ZIF-8 membrane. The inner layer of the support is an organic hollow fiber(PES) with finger-like pores, and the outer layer is a ZnO-PES composite layer with finger-like pores also. The ZnO-PES composite layer is expected to contain uniform ZnO crystals in the polymer matrix, i.e., the ZnO particles in the skin layer of the support are not easy to fall off. Under the induction of ZnO particles in the outer layers, continuous ZIF-8 membranes can be prepared by single in-situ crystallization, showing good adhesion to the supports. The obtained ZIF-8 membranes show a H_(2) permeance of 8.7 × 10^(-8)mol·m^(-2)·s^(-1)·Pa^(-1) with a H_(2)/N_(2) ideal separation selectivity of 18.0. The design and preparation of this dual-layer polymer support is expected to promote the large-scale application of MOF membranes on polymer supports.

Effect of polytetrafluoroethylene hollow fiber microstructure on formaldehyde carbonylation performance in membrane contactor

Membrane contactor is regarded as a promising method for reaction and process intensification. The feasibility of formaldehyde carbonylation to synthesize glycolic acid using polytetrafluoroethylene(PTFE)membrane contactor has been proved in our previous study. In this paper, the effect of membrane microstructure on process performance was further investigated. Three porous PTFE hollow fibers with different pore sizes and one polydimethylsiloxane(PDMS)/PTFE composite membrane with dense layer were fabricated for comparison. The physical and chemical properties of four membranes, including chemical composition, morphology, contact angle, liquid entry pressure, thermodynamic analysis and gas permeability, were systemically characterized. Experiments of formaldehyde carbonylation under different reaction conditions were conducted. The results indicated that the yield of glycolic acid increased with decreasing pore size for porous membranes, which was due to the improvement of wetting behavior. The dense layer of PDMS in composite hollow fiber could effectively prevent the solvent from entering membrane pores, thus the membrane exhibited the best performance. At reaction temperature of 120℃ and operation pressure of 3.0 MPa, the yield of glycolic acid was always higher than 90% as the mass ratio of trioxane and phosphotungstic acid increased from 0.2:1 to 0.8:1. The highest turnover frequency was up to 26.37 mol·g^(-1)·h^(-1). This study provided a reference for the understanding and optimization of membrane contactors for the synthesis of glycolic acid using solvent with low surface tension.

Performances of biological aerated filter employing hollow fiber membrane segments of surface-improved poly(sulfone) as biofilm carriers

Using the surface of poly （sulfone） hollow fiber membrane segments as grafted layer, the hydrophilic acrylamide chain was grafted on by UV-photoinduced grafting polymerization. The gained improvement of surface wettability for the modified membrane was tested by measuring the contact-angle as well as FTIR spectra. Then correlation between the hydrophilic ability of support material and the biofilm adherence ability was demonstrated by comparing the pollutant removal rates from urban wastewater via two identical lab-scale up-flow biological aerated filters, one employed the surface wettability modified poly （sulfone） hollow fiber membrane segment as biofilm carder and the other employed unmodified membrane segment as biofilm carder. The experimental results showed that under the conditions of influent flux 5 L/h, hydraulic retention time 9 h and gas to liquid ratio （G/L） 10： 1, the removal rates of chemical oxygen demand （COD） and ammonium nitrogen （NH4^＋-N） for the modified packing filter and the unmodified packing filter was averaged at 83.64% and 96.25%, respectively, with the former filter being 5%-20% more than the latter. The effluent concentration of COD, NH4^＋-N and turbidity for the modified packing filter was 25.25 mg/L, 2 mg/L and 8 NTU, respectively. Moreover, the ammonium nitrogen removal performance of the filter packing the modified PSF was compared with the other bioreactor packing of an efficient floating medium. The biomass test indicated that the modified membrane matrixes provided better specific adhesion （3310-5653 mg TSS/L support）, which gave a mean of 1000 mg TSS/L more than the unmodified membrane did. In addition, the phenomenon of simultaneous denitrification on the inner surface of the support and nitrification on the outer surface was found in this work.

STRUCTURE AND PROPERTIES OF COMPOSITE POLYURETHANE HOLLOW FIBER MEMBRANES

Composite polyurethane(PU)-SiO_2 hollow fiber membranes were successfully prepared via optimizing thetechnique of dry-jet wet spinning,and their pressure-responsibilities were confirmed by the relationships of pure water flux-transmembrane pressure(PWF-TP)for the first time.The origin for this phenomenon was analyzed on the basis of membranestructure and material characteristics.The effects of SiO_2 content on the structure and properties of membrane wereinvestigated.The experimental results indicated that SiO_2 in membrane created a great many interfacial micro-voids andplayed an important role in pressure-responsibility,PWF and rejection of membrane:with the increase of SiO_2 content,theability of membrane recovery weakened,PWF increased,and rejection decreased slightly.

Two-dimensional MXene hollow fiber membrane for divalent ions exclusion from water

Two-dimensional material membranes with fast transport channels and versatile chemical functionality are promising for molecular separation.Herein,for the first time,we reported design and engineering of two-dimensional Ti_(3)C_(2)Tx MXene(called transition metal carbides and nitrides)membranes supported on asymmetric polymeric hollow fiber substrate for water desalination.The membrane morphology,physicochemical properties and ions exclusion performance were systematically investigated.The results demonstrated that surface hydrophilicity and electrostatic repulsion and size sieving effect of interlayer channels synergistically endowed the MXene hollow fiber membrane with fast water permeation and efficient rejection of divalent ions during nanofiltration process.

Gas-initiation under UV and liquid-grafting polymerization on the surface of polysulfone hollow fiber ultrafiltration membrane by dynamic method

Using the inner-surface of polysulfone hollow fiber ultrafiltration membranes as grafted layer, the method of gas-initiation and liquid-polymerization has been studied, which aimed to adjust the diameter of the pores in the membranes. The degree of polymerization varied with the changes of the parameters, such as irradiation time, monomer concentration, temperature and time of polymerization and so on. The results indicated that using benzophenone(BP) which is in a gaseous condition as photo-initiator, acrylamide as graft monomer, the polyacrylamide chain was grafted on the surface of membranes. After the surface membrane being modified, the water flux and retention altered,and thus it can be seen that the diameter of the pores in the membrane was altered. These experiments contribute to finding a new way to produce the hollow fiber membrane with the small pore size and are extraordinarily worth developing and studying.

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.

MORPHOLOGIES AND GAS SEPARATION PROPERTIES OF MELT-SPUN ASYMMETRIC POLY(4-METHYL-1-PENTENE)HOLLOW FIBER MEMBRANES

Poly(4-methyl-1-pentene) (PMP) hollow fiber membranes were prepared by the melt-spun and cold-stretch(MSCS) method. Scanning electronic microscopy (SEM) was used to characterize the section and surface structures of themembranes with special asymmetric structure. The preliminary results of gas permeation measurements indicated that the resultant hollow fiber membranes have the potential ability for oxygen/nitrogen separation.

Polydimethylsiloxane (PDMS) Composite Membrane Fabricated on the Inner Surface of a Ceramic Hollow Fiber: From Single-Channel to Multi-Channel

The fabrication of a separation layer on the inner surface of a hollow fiber (HF) substrate to form an HF composite membrane offers exciting opportunities for industrial applications, although challenges remain. This work reports on the fabrication of a polydimethylsiloxane (PDMS) composite membrane on the inner surface of a single-channel or multi-channel ceramic HF via a proposed coating/crossflow approach. The nanostructures and transport properties of the PDMS HF composite membranes were optimized by controlling the polymer concentration and coating time. The morphology, surface chemistry, interfacial adhesion, and separation performance of the membranes were characterized by fieldemission scanning electron microscope (FE-SEM), attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy, the nano-indentation/scratch technique, and pervaporation (PV) recovery of bio-butanol, respectively. The formation mechanism for the deposition of the PDMS layer onto the inner surface of the ceramic HF was studied in detail. The optimized inner surface of the PDMS/ceramic HF composite membranes with a thin and defect-free separation layer exhibited a high flux of ~1800 gm-2h-1 and an excellent separation factor of 35–38 for 1 wt% n-butanol/water mixtures at 60
C. The facile coating/cross-flow methodology proposed here shows great potential for fabricating inner-surface polymer-coated HFs that have broad applications including membranes, adsorbents, composite materials, and more.

Enhanced gas separation performance of mixed matrix hollow fiber membranes containing post-functionalized S-MIL-53

Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and membrane plasticization.Herein,lab-synthesized MIL-53 was post-functionalized by aminosilane grafting and subsequently incorporated into Ultem-1000 polymer matrix to fabricate high performance MMHFMs.SEM,DLS,XRD and TGA were performed to characterize silane-modified MIL-53（S-MIL-53）and prepared MMHFMs.Moreover,the effect of MOFs loading was systematically investigated first;then gas separation performance of MMHFMs for pure and mixed gas was evaluated under different pressures.MMHFMs containing post-functionalized S-MIL-53 achieved remarkable gas permeation properties which was better than model predictions.Compared to pure HFMs,CO2permeance of MMHFM loaded with 15%S-MIL-53 increased by 157%accompanying with 40%increase for CO2/N2selectivity,which outperformed the MMHFM filled with naked MIL-53.The pure and mixed gas permeation measurements with elevated feed pressure indicated that incorporation of S-MIL-53 also increased the resistance against CO2plasticization.This work reveals that post-modified MOFs embedded in MMHFMs facilitate the improvement of gas separation performance and suppression of membrane plasticization.

Enhancement of the flux for polypropylene hollow fiber membrane in a submerged membrane-bioreactor by surface modification

To improve its limiting flux and antifouling characteristics in a submerged membrane-bioreactor （SMBR） for wastewater treatment, polypropylene hollow fiber microporous membrane （PPHFMM） was surface-modified by the plasma-induced immobilization of poly （N-vinyl-2-pyrrolidone） （PVP） and the plasma treatment with different gases respectively. Attenuated total reflection-Fourier transform infrared spectroscopy （FT-IR/ATR）, X-ray photoelectron spectroscopy （XPS） and field emission scanning electron microscope （FE-SEM） were used to characterize the structural and morphological changes on the membrane surface. Water contact angle was measured by the sessile drop method. It was found that the water contact angle was 128.8, 72.3, 62.7, 74.4, 79.1, 86.3, and 71.3° for the nascent, PVP-immobilized, air, 02, Ar, CO2 and H2O plasma treated PPHFMM, respectively. The SMBR was operated at fixed transmembrane pressure to determine the limiting flux for the PPHFMM before and after surface modification. Results showed that the limiting flux appeared to be 103, 159, 117, 133, 136, 121 and 152 L/（m^2· h） for the nascent, PVP-immobilized, air, O2, At, CO2 and H2O plasma treated PPHFMM, respectively. After continuous operation for about 50 h in the SMBR, the antifouling characteristics were improved to some extent.

Numerical Simulation of a Mathematical Model for Dry/Wet-Spun Nascent Hollow Fiber Membrane

In an effort to find the effect of mass transfer, surface tension and drag forces on the velocity distribution, the mathematical model of the velocity profile of a nascent hollow fiber during membrane formation in the air gap region was numerically simulated by using the Runge-Kutta method (fourth-order method). The effect of mass transfer on velocity distribution based on the complicated function (G(Cs h)) was presented and the effects of a complicated function were studied in two cases: in the first case, G(Cs h) was constant; in the second, G(Cs h) was variable. The latter was done by varying with the concentration of solvent in a nascent hollow fiber through the air-gap region. One empirical equation was used to describe this change and the predicted values had a better agreement with the experimental values. To verify the model hypotheses, hollow fiber membranes were spun from 20∶80 polybenzimidazole/polyetherimide dopes with 25.6 wt% solid in N, N-dimethylacetamide (DMAc) using water as the external and internal coagulants. Based on the experimental results of dry-jet wet-spinning process for the fabrication of hollow fiber membranes, it is found that the model calculated values were in a good agreement with the experimental values.

Preparation and Surface Modification of High-Density Chitosan/Functionalized Multi-walled Carbon Nanotubes Hollow Fibers

Functionalized multi-walled carbon nanotubes( fMWNTs) were prepared with chitosan via controlled surface deposition and crosslinking process and scanning electron microscopy( SEM),Fourier translation infrared spectroscopy( FT-IR) and Xray diffraction( XRD) are used to character properties. A novel high-density chitosan( HCS) was dissolved in f-MWNTs dispersed dilute acetic acid with a maximal concentration of 5. 8%. The hollow fibers can be made by extruding the solution into a dilute alkali solution through a wet-spinning process and the tensile properties of the materials were evaluated by universal tester. The surface property of fibers,pretreated by Helium( He) and the following grafted with gelatin was evaluated with X-ray photoelectron spectroscopy( XPS).As the hollow fibers were intended for neural tissue engineering,its suitability was evaluated in vitro using rat Schwann cells( RSC96) as model cells. The cells attachment,proliferation and morphology,were studied by various microscopic techniques. Based on the results,the gelatin grafted HCS / f-MWNTs hollow fibers could be used as a potential cell carrier in neural tissue engineering.

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(CEPw),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.CEPw 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 SGMDtest,the developed membrane represented a maximumpermeate 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-termSGMD 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.

A CONDENSED REVIEW ON THE FABRICATION OF HOLLOW FIBER MEMBRANES FOR GAS SEPARATION:HISTORICAL DEVELOPMENT AND TECHNOLOGY CHALLENGES AHEAD

A review on the polymeric hollow fibers membranes for gas separation has been conducted. In order to deyelop high performance membranes for gas separation, there are a few technology challenges awaiting the chemical engineers to overcome. There are four major challenges, namely: 1) material selection and synthesis; 2) fabrication of hollow fiber membranes with an ultra- thin dense selective layer; 3) materials against plasticization; and 4) aging. In each area, we summarize the scientific accomplishments and technical difficulties.

Effect of Polyvinylidene Fluoride Hollow Fiber Membranes on Mass Transfer of Samarium

The influence of swelling and stripping acidity on the mass transfer coefficient based on water phase and the inner diameters of membranes were studied with P507-HCl-Sm as working system in the two different kinds of hollow fiber membranes. Effects of extractant concentration, H+ concentration in aqueous phase and Sm3+ concentration on extraction rate were discussed and the corresponding reaction series were obtained. According to the investigations on the interfacial kinetics, the reaction kinetics equation and reaction rate constant were obtained.

Electrolyte transfer separation of hollow fiber composite nanofiltration membrane

Using Donnan Steric Partitioning Model(DSPM),the data for the rejection of four salts having common co-ion(LiCl, NaCl,KCl,Na2SO4)were obtained and they show the characters of the polyethersulfone(PES)nanofiltration(NF)membrane in terms of three parameters:an effective pore radius(rp),the ratio of effective thickness over porosity(λ/Ak)and an effective charge density(X).Good agreement between experimental data and prediction data using the three parameters mentioned above was obtained.A theoretical model was developed to predict the transport performance of electrolyte through the hollow fiber composite NF membrane.The model prediction is in good agreement with experimental results based on the method by modern numerical solution.

Covalent Immobilization of Lipase on Poly(acrylonitrile-co-maleic acid) Ultrafiltration Hollow Fiber Membrane

Lipase from Candida rugosa was covalently immobilized on the surface of an uhrafihration hollow fiber membrane fabricated from poly （ acrylonitrile-co-maleic acid） （ PANCMA ） in which the carboxyl groups were activated with 1-ethyl-3-（ dimethylaminopropyl ） carbodiimide hydrochloride （ EDC ） and dicyclohexyl carbodiimide （ DCC ）/ N-hydroxyl succinimide（NHS）, respectively. The properties of the immobilized lipase were assayed and compared with those of the free enzyme. The maximum activities were observed in a relatively broader pH value range at high temperatures for the immobilized lipase compared to the free one. It was also found that the thermal and pH stabilities of lipase were improved upon immobilization and at 50 ℃ the thermal inactivation rate constant values are 2. 1 × 10^ -2 for the free lipase, 3.2 × 10^-3 for the immobilized lipase on the EDC-activated PANCMA membrane and 3.5 × 10^-3 for the immobilized lipase on the DCC/NHS-activated PANCMA membrane, respectively.

THE MASS TRANSFER BEHAVIORS OF FE(Ⅲ), CO(Ⅱ) AND NI(Ⅱ) IN SULFURIC ACID WITH CYANEX302 BY USINGMICROPOROUS HOLLOW FIBER

In this paper the mass transfer behaviors of Fe(Ⅲ), Co(Ⅱ) and Ni(Ⅱ) with Cyanex302(bis(2,4,4- trimethylpentyl)monothiophosphinic acid) from sulfate medium by using hollow fiber membrane in counter-currently circulating operation were studied. The effect of acidity in aqueous solution and the extractant concentration on the mass transfer coefficient (Kw) was discussed. The reaction mechanism of membrane extraction was considered as a false one series reaCtion and the rate controlling step was membrane resistance. When the value of Kw arrived at 1.0 × 10-6 m/s, △pH:CoFe equaled tO 6.225, and △pH:NiFe was bigger than △p HCoFe.

CHARACTERIZATION OF MIXED GAS PERMEATION THROUGH HOLLOW FIBERS

We have studied the mixed gas permeation in hollow fiber membrane modules using two approaches: namely, the co- current plug flow model and the complete mixing model with the combination of experimental data. Elucidation was made to determine the permeance of CO2 and CH4 and the selectivity of CO2/CH4 in a polyimide hollow fiber membrane permeator It is found that the intrinsic gas separation properties of hollow fibers for mixed gases can be accurately determined based on (1) the cocurrent plug now model, and (2) the complete mixing model with the assumption of averaged retentate concentration of the feed and the retentate outlet.