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.

Atomic layer deposition of Al_2O_3 on porous polypropylene hollow fibers for enhanced membrane performances

Porous polypropylene hollow fiber(PPHF) membranes are widely used in liquid purification. However, the hydrophobicity of polypropylene(PP) has limited its applications in water treatment. Herein, we demonstrate that, for the first time, atomic layer deposition(ALD) is an effective strategy to conveniently upgrade the filtration performances of PPHF membranes. The chemical and morphological changes of the deposited PPHF membranes are characterized by spectral, compositional, microscopic characterizations and protein adsorption measurements. Al_2O_3 is distributed along the cross section of the PP hollow fibers, with decreasing concentration from the outer surface to the inner surface. The pore size of the outer surface can be easily turned by altering the ALD cycles. Interestingly, the hollow fibers become much more ductile after deposition as their elongation at break is increased more than six times after deposition with 100 cycles. The deposited membranes show simultaneously enhanced water permeance and retention after deposition with moderate ALD cycle numbers.For instance, after 50 ALD cycles a 17% increase in water permeance and one-fold increase in BSA rejection are observed. Moreover, the PP membranes exhibit improved fouling-resistance after ALD deposition.

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.

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.

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.

Effects of Additives and Coagulant Temperature on Fabrication of High Performance PVDF/Pluronic F127 Blend Hollow Fiber Membranes via Nonsolvent Induced Phase Separation

Poly（vinylidene fluoride） （PVDF） has become one of the most popular materials for membrane preparation via nonsolvent induced phase separation （NIPS） process. In this study, an amphiphilic block copolymer, Pluronic F127, has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fibermembranes to enhance the membrane permeability and hydrophilicity. The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F 127 membranes have also been investigated. The as-spun hollow fibers were characterized in terms of cross-sectional morphology, pure water permeation （PWP）, relative molecular mass cut-off （MWCO）, membrane chemistry, and hydrolphilicity. It was obsered that the addition of Pluronic F 127 significantly increased the PWP of as-spun fibers, while the membrane contact angle was reduced. However, the size of macrovoids in the membranes was undesirably large. The addition of a 2nd additive, including lithium chloride （LiC1） and water, or an increase in coagulant temperature was found to effectively suppress the macrovoid for- mation in the Pluronic-containing membranes. In addition, the use of LiC1 as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes, while the surface pore size became smaller. PVDF hollow fiber with a PWP as high as 2330 L·m-2·h-1·MPa-1, a MWCO of 53000 and＇a contact angle of 71 o was successfully fabricated with 3% （by mass） of Pluronic F127 and 3% （by mass） of LiC1 at a coagulant temperature of 25 ℃, which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.

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.

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.

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.

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.

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）.

Mathematic Model of Unsteady Penetration Mass Transfer in Randomly Packed Hollow Fiber Membrane Module

Based on the membrane-based absorption experiment of CO2 into water, shell-side flow distribution and mass transfer in a randomly packed hollow fiber module have been analyzed using subchannel model and unsteady penetration mass transfer theory. The cross section of module is subdivided into many small cells which contains only one hollow-fiber. The cross sectional area distribution of these cells is presented by the normal probability density distribution function. It has been obtained that there was a most serious non-ideal flow in shell side at moderate mean packing density, and the large amount of fluid flowed and transferred mass through a small number of large voids. Thus mass transfer process is dominated by the fluid through the larger void area. The mass transfer process in each cell is described by the unsteady penetration theory. The overall mass transfer coefficient equals to the probability addition of the mean mass transfer coefficient in each cell. The comparisons of the values calculated by the model established with the empirical correlations and the experimental data of this work have been done.The predicted overall mass transfer coefficients are in good agreement with experimental data.

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.

Effects of coagulation bath temperature on structure and performance of poly(vinyl butyral) hollow fiber membranes via thermally induced phase separation

Poly （vinyl butyral） （PVB） hollow fiber membranes were fabricated via thermally induced phase separation （TIPS）. The effects of coagulation bath temperature （CBT） on the structure and performance of membranes were investigated in detail. The morphologies of the membranes were studied by scanning electron microscopy （SEM）, the performances of water permeability, rejection, breaking strength and elongation were measured, respectively. The results indicate that all the membranes have the asymmetric morphology and the thickness of the skin layer decreases and the pore size of the outer layer increases with the increase of CBT. The permeability of membranes prepared at air gap 1.0 cm and take-up speed 0.253 m/s increases from 1.047×10-7 to 5.909×10-7 m3/（m2·s-kPa） with the CBT increasing from 20 ℃ to 40℃, and sharply increases to 35.226×10 7 m3/（m2.s.kPa）once the CBT arrives at 50 ℃. While the carbonic ink rejections have no significant decrease, totally exceed 98%, but that of acid-maleic acid copolymer greatly decreases with the increase of CBT. Both the breaking strength and elongation decrease with the increase of CBT.

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.

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.

Characterization of polysulfone hollow-fiber ultrafiltration membrane and its cleaning efficiency by streaming potential and flux method

Polysulfone(PS)hollow-fiber ultrafiltration membrane was characterized combined with flux and streaming potential in single electrolyte solutions.The effects of trans-membrane pressure,electrolyte concentration,ion valence and pH value of electrolyte solution on the streaming potential(SP)of the membrane were investigated.The zeta potential and surface charge density of the membrane were calculated on the basis of Helmholtz-Smoluchowski equation and Gouy-Chapmann theory.The results indicate that the valence and concentration of cation have a greater influence on the SP and surface charge density of PS membrane than those of anion,and the pH value of electrolyte solution has great effects on the SP and zeta potential of the membrane surface. Both the absolute value of the streaming potential and water flux of the adsorbed membrane decrease,compared with those of the clean membrane.The streaming potential and flux of the cleaned membrane can be completely recovered by cleaning with the mass fraction of 0.8%EDTA at pH=10.

Evaluation of hollow fiber T-type zeolite membrane modules for ethanol dehydration

This work presents the design of hollow fiber T-type zeolite membrane modules with different geometric configurations. The module performances were evaluated by pervaporation dehydration of ethanol/water mixtures. Strong concentration polarization was found for the modules with big membrane bundles. The concentration polarization was enhanced at high temperature due to the higher water permeation flux. The increase of feed flow could improve water permeation flux for the membrane modules with small membrane bundle.Computational fluid dynamics was used to visualize the flow field distribution inside of the modules with different configurations. The membrane module with seven bundles exhibited highest separation efficiency due to the uniform distribution of flow rate. The packing density could be 10 times higher than that of the tubular membrane module. The hollow fiber membrane module exhibited good stability for ethanol dehydration.