Hyperbranched polymer hollow-fiber-composite membranes for pervaporation separation of aromatic/aliphatic hydrocarbon mixtures

The separation of aromatic/aliphatic hydrocarbon mixtures is crucial in the petrochemical industry.Pervaporation is regarded as a promising approach for the separation of aromatic compounds from alkanes. Developing membrane materials with efficient separation performance is still the main task since the membrane should provide chemical stability, high permeation flux, and selectivity. In this study, the hyperbranched polymer(HBP) was deposited on the outer surface of a polyvinylidene fluoride(PVDF)hollow-fiber ultrafiltration membrane by a facile dip-coating method. The dip-coating rate, HBP concentration, and thermal cross-linking temperature were regulated to optimize the membrane structure.The obtained HBP/PVDF hollow-fiber-composite membrane had a good separation performance for aromatic/aliphatic hydrocarbon mixtures. For the 50%/50%(mass) toluene/n-heptane mixture, the permeation flux of optimized composite membranes could reach 1766 g·m^(-2)·h^(-1), with a separation factor of 4.1 at 60℃. Therefore, the HBP/PVDF hollow-fiber-composite membrane has great application prospects in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures.

Four-channel catalytic micro-reactor based on alumina hollow fiber membrane for efficient catalytic oxidation of CO

The traditional automotive catalytic converter using commercial ceramic honeycomb carriers has many problems such as high back pressure,low engine efficiency,and high usage of precious metals.This study proposes a four-channel catalytic micro-reactor based on alumina hollow fiber membrane,which uses phase inversion method for structural molding and regulation.Due to the advantages of its carrier,it can achieve lower ignition temperature under low noble metal loading.With Pd/CeO_(2) at a loading rate of 2.3%(mass),the result showed that the reaction ignition temperature is even less than 160℃,which is more than 90℃ lower than the data of commercial ceramic substrates under similar catalyst loading and airspeed conditions.The technology in turn significantly reduces the energy consumption of the reaction.And stability tests were conducted under constant conditions for 1000 h,which proved that this catalytic converter has high catalytic efficiency and stability,providing prospects for the design of innovative catalytic converters in the future.

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.

Highly Conductive Proton Selectivity Membrane Enabled by Hollow Carbon Sieving Nanospheres for Energy Storage Devices

Ion conductive membranes(ICMs)with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices.However,it is extremely challenging to construct fast proton-selective transport channels in ICMs.Herein,a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure(HCSNs)in a polymer matrix.Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities,this advanced membrane presented a proton conductivity(0.084 S·cm^(-1))superior to those of a commercial Nation 212(N212)membrane(0.033S·cm^(-1))and a pure polymer membrane(0.049 S·cm^(-1)).The corresponding proton selectivity of the membrane(6.68×10^(5) S·min·cm^(-3))was found to be enhanced by about 5.9-fold and 4.3-fold,respectively,compared with those of the N212 membrane(1.13×10^(5) S·min·cm^(-3))and the pure membrane(1.56×10^(5) S·min·cm^(-3)).Low-field nuclear magnetic resonance(LF-NMR)clearly revealed the fast protonselective transport channels enabled by the HCSNs in the polymeric membrane.The proposed membrane exhibited an outstanding energy efficiency(EE)of 84%and long-term stability over 1400 cycles with a0.065%capacity decay per cycle at 120 mA·cm^(-2) in a typical vanadium flow battery(VFB)system.

Research of Oxidation Resistance of PVDF Hollow Fiber Membrane Used in Water Treatment

[Objective] The aim was to research the influences of different formulations on oxidation resistance of PVDF hollow fiber membrane.[Method]The immersion precipitation phase inversion method was employed to make casting solution with different formulations into hollow fiber membrane.The membrane was immersed in 1% NaClO solution for testing its performance changes.[Result]The membrane made by materials with bigger molecular weight had better oxidation resistance performance;the surfactant tween-80 could increase water flux,but lead to lower rupture intension;Pore-forming agent PEG400 do better than PVP in the oxidation resistance of membrane.[Conclusion]This study will provide a good idea for the development of the PVDF membrane with high oxidation resistance.

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.

Removal of Aniline from Wastewater Using Hollow Fiber Renewal Liquid Membrane

Hollow fiber renewal liquid membrane(HFRLM) method was proposed based on the surface renewal theory for removal of aniline from waste water. The system of aniline + D2 EHPA in kerosene + HCl was used. Aqueous layer diffusion in the feed phase is the rate-control step, and the influence of lumen side flow rate on the mass transfer is more significant than that on the shell side. The resistance of overall mass transfer is greatly reduced because of the mass transfer intensification in the renewal of liquid membrane on the lumen side. The driving force of mass transfer can be considered as a function of distribution equilibrium, and the overall mass transfer coefficient increases with the increase of p H in the feed solution, HCl concentration and D2 EHPA concentration, and decreases with the increase of initial aniline concentration. A mass transfer model is developed for HFRLM based on the surface renewal theory. The calculated results agree well with experimental results. The HFRLM process is a promising method for aniline wastewater treatment.

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.

Effect of Diluent on the Morphology and Performance of IPP Hollow Fiber Microporous Membrane via Thermally Induced Phase Separation

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.

Effects of F127 on Properties of PVB/F127 Blend Hollow Fiber Membrane via Thermally Induced Phase Separation

Hydrophilic poly(vinyl butyral)(PVB) /Pluronic F127(F127) blend hollow fiber membranes were prepared via thermally induced phase separation(TIPS) ,and the effects of blend composition on the performance of hydrophilic PVB/F127 blend hollow fiber membrane were investigated.The addition of F127 to PVB/polyethylene glycol(PEG) system decreases the cloud point temperature,while the cloud point temperature increases slightly with the addition of F127 to 20%(by mass) PVB/F127/PEG200 system when the concentration of F127 is not higher than 5%(by mass) .Light scattering results show that the initial inter-phase periodic distance formed from the phase separation of 20%(by mass) PVB/F127/PEG200 system decreases with the addition of F127,so does the growth rate during cooling process.The blend hollow fiber membrane prepared at air-gap 5mm,of which the water permeability increases and the rejection changes little with the increase of F127 concentration.For the membrane prepared at zero air-gap,both water permeability and rejection of the PVB/F127 blend membrane are greater than those of PVB membrane,while the tensile strength changes little.Elementary analysis shows that most F127 in the polymer solution can firmly exist in the polymer matrix,increasing the hydrophilicity of the blend membrane prepared at air-gap of 5mm.

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.

Removal of 2,4-dichlorophenol from wasterwater by vacuum membrane distillation using hydrophobic PPESK hollow hiber membrane

2,4-Dichlorophenol was removed from wasterwater using a new hydrophobic poly（phthalazinone ether sulfone ketone） （PPESK） hollow fiber membrane by vacuum membrane distillation （VMD）.

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.

Extraction and Separation of Thorium and Ytterbium with Bis(2,4,4-Trimethylpentyl) Phosphinic Acid Using a Hollow Fiber Membrane Extractor

The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The separation operation of Th 4+ and Yb 3+ mixture was carried out by two successive extraction and stripping simultaneously. The concentration ratio of Th 4+ to Yb 3+ is 16 74 in the stripping solution. The recovery and purity of Th 4+ are 71 6% and 95 74% respectively.

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.

Transport Study of Cu （Ⅱ） Through Hollow Fiber Supported Liquid Membrane

The transport of Cu(II)from aqueous solutions containing buffer media through hollow fiber supported liquid membrane(HFSLM)using di(2-ethylhexyl)phosphoric acid(D2EHPA)dissolved in kerosene as membrane phase and hydrochloric acid as striping phase was investigated.A set of factors were studied,including tube side velocity,shell side velocity,pH of the feed phase,Cu(II)concentration in the feed phase,buffer media concentration and D2EHPA concentration in the membrane phase.Experimental results indicate that the mass transfer coefficient increases with increasing both carrier concentration in the organic phase and flow rates on the tube side and shell side,and decreases with increasing initial Cu(II)concentration in the feed phase.With increasing pH value and acetate concentration in the feed phase,the mass transfer coefficient reaches a maximum value then decreases.The optimal operating conditions are obtained at pH value of 4.44 and 0.1 mol·L -1 acetic ion concentration in feed phase,and carrier volume fraction of around 10%in kerosene as organic phase.A mathematical model of the transport mechanism through HFSLM is developed.The modeled results agree well with the experimental ones.

Preparation and Characterization of the Modified Polyvinylidene Fluoride (PVDF) Hollow Fibre Microfiltration Membrane

A novel thermally induced graft polymerization technique was used to modify a polyvinylidene fluoride （PVDF） hollow fibre microfiltration membrane. An artificial neural network （ANN） was applied to optimize the prepared condition of the membrane. The optimized dosing of acrylic acid （AA）, acrylamide （AM）, N, N＇- methylenebisacrylamide （NMBA） and potassium persulphate （KSP） designed by ANN was that AA was 40.63 ml/L; AM acted as 6.25 g/L; NMBA was 1.72 g/L and KSP was 1.5 g/L, respectively. The thermal stability of the PVDF modified hollow fibre membrane （PVDF-PAA） was investigated by thermogravimetric （TG） and differential scanning calorimetry （DSC） analysis. The polycrystallinity of the PVDF-PAA membrane was evaluated by X-ray diffraction （XRD） analysis. The complex formation of the modified membrane was ascertained by Fourier transform infrared spectroscopy （FTIR）. The morphology of the PVDF-PAA membrane was studied by environmental scanning electron microscopy （ESEM）. The surface compositions of the membrane were analyzed by X-ray photoelectron spectroscopy （XPS）. The adsorption capacity of Cu^2＋ ion on the PVDF-PAA hollow fibre membrane was also investigated.

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 side was developed to describe pervaporation dehydration through scaled-up hollow fiber supported NaA zeolite membrane. It was 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 he neglected. The effect of geometric size on pervaporation dehydration could be more significant under higher vacuum pressure in the permeate side. The transfer resistance in the lumen increases with the hollow fiber length but decreases with lumen diameter. The geometric structure could be optimized in terms of the ratio of lumen diameter to membrane length. A critical value of d1/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.

Synergistic action of non-solvent induced phase separation in preparation of poly(vinyl butyral) hollow fiber membrane via thermally induced phase separation

A systematic study of air gap distance effects on the structure and properties of poly(vinyl butyral)hollow fiber membrane via thermally induced phase separation(TIPS)has been carried out.The results show that the hollow fiber membrane prepared at air gap zero has no skin layer; the pore size near the outer surface is larger than that near the inner surface; and the special pore channel-like structure near the outer surface is formed,which is quite different with the typical sponge-like structure caused by TIPS and the finger-like structure caused by non-solvent induced phase separation(NIPS),because of the synergistic action of non-solvent induced phase separation at air gap zero.The pore size gradually decreases from outer surface layer to the intermediate layer,but increases gradually from intermediate layer to the inner surface layer.With the increase of air gap distance,the pore size near the outer surface gets smaller and a dense skin layer is formed,and the pore size gradually increases from the outer surface layer to the inner surface layer.Water permeability of the hollow fiber membrane decreases with air gap distance,the water permeability decreases sharply from 45.50×10-7 to 4.52×10-7 m3/(m2·s·kPa)as air gap increases from 0 to 10 mm at take-up speed of 0.236 m/s,further decreases from 4.52×10-7 to 1.00×10-8 m3/(m2·s·kPa)as the air gap increases from 10 to 40 mm.Both the breaking strength and the elongation increase with the increase of air gap distance.The breaking strength increases from 2.25 MPa to 4.19 MPa and the elongation increases from 33.9% to 132.6% as air gap increases from 0 mm to 40 mm at take-up speed 0.236 m/s.