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.

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.

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.

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.

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.

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.

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.

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.

Electrokinetic phenomena of poly(vinyl butyral) hollow fiber membranes in different electrolyte solutions

The streaming potential of poly（vinyl butyral） （PVB） hollow fiber membrane was studied in different electrolyte solutions （including NaCl, KCl, CaCl2 and MgCl2）, the effects of ionic strength, ion valence and pH value on the streaming potential （SP） of the membrane were investigated. The zeta potentials and surface charge densities of the membrane were estimated on the basis of Helmholtz-Smoluchowski equation and Gouy-Chapmann theory. The results show that the PVB membrane has a weak negative charge due to the specific adsorption of ions. Moreover, the streaming potential, the zeta potential and the surface charge density of the membrane depend strongly on the salt concentration and the type and valence of ions. The iso-electric point （IEP） of the PVB membrane is arotmd 3.0 in the monovalent media （NaC1 and KC1） and 3.5 in divalent electrolytes （CaCl2 and MgCl2）. A few retentions were obtained for PVB membrane in low concentration solutions. This result verifies that the negative charged membrane surface can reject inorganic solutes by means of electrostatic repulsion effect even though the size of membrane pores is much larger than the size of salts.

PREPARATION OF POLYVINYLIDENE FLUORIDE/POLYVINYL DIMETHYLSILOXANE COMPOSITE HOLLOW FIBER MEMBRANES AND THEIR SEPARATION PROPERTIES

Microporous polyvinylidene fluoride(PVDF)hollow fibre membranes were spun using the dry-wet phaseinversion method.By means of dip-coating technique,a uniform coating with thickness of around 5-12 μm of polyvinyldimethylsiloxane(PVDMS)was formed on the surface of porous PVDF hollow fibers.The structural parameters of PVDFsubstrate membrane were estimated by gas permeation test.Using N_2/O_2 as the medium,the separation properties ofPVDMS-PVDF composite hollow fiber membranes were also evaluated experimentally.The experimental data of bothpermeability and selectivity are in good agreement with the theoretical results predicted by the presented pore-distributionmodel.In order to obtain the compact composite membrane free of defects by the dip-coating technique,the thickness ofPVDMS skin must be higher than 5 μm.

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.

Preparation of Hydrophilic UHMWPE Hollow Fiber Membranes by Chemically Bounding Silica Nanoparticles

In this work, ultra-high molecular weight polyethylene (UHMWPE) microfiltration hollow fiber membranes prepared via the thermally induced phase separation (TIPS) method were modified by chemically bounding hydrophilic silica (SiO2) nanoparticles onto the surface to improve anti-fouling performance. A range of testing techniques including attenuated total reflection Flourier transformed infrared spectroscopy(ATR-FTIR), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), water contact angle, mechanical test,filtration and anti-fouling performance were carried out to discuss the influence of different modification conditions on the properties of the membranes. The prepared hollow fiber membranes display the significantly excellent performance when the vinyl trimethoxy silane (VTMS) concentration was 13%, the pH value of the hydrolyzate was 4 and the hydrolysis reaction time was 6 h. In particular, the hydrophilicity of modified membranes was improved effectively, resulting in the enhancement of membrane anti-fouling properties. The results of this work can be consulted for improving the anti-fouling performance of the UHMWPE microfiltration hollow fiber membrane applied in the field of water purification.

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.

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.

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.

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.