Merging polymers of intrinsic microporosity and porous carbon-based zinc oxide composites in novel mixed matrix membranes for efficient gas separation

Mixed matrix membranes(MMMs)have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers.However,achieving a simultaneous enhancement of permeability and selectivity remains a formidable challenge,due to the difficulty of achieving an optimal match between polymers and fillers.In this study,we incorporate a porous carbon-based zinc oxide composite(C@ZnO)into high-permeability polymers of intrinsic microporosity(PIMs)to fabricate MMMs.The dipole–dipole interaction between C@ZnO and PIMs ensures their exceptional compatibility,mitigating the formation of non-selective voids in the resulting MMMs.Concurrently,C@ZnO with abundant interconnected pores can provide additional low-resistance pathways for gas transport in MMMs.As a result,the CO_(2) permeability of the optimized C@ZnO/PIM-1 MMMs is elevated to 13,215 barrer,while the CO_(2)/N_(2) and CO_(2)/CH_(4) selectivity reached 21.5 and 14.4,respectively,substantially surpassing the 2008 Robeson upper bound.Additionally,molecular simulation results further corroborate that the augmented membrane gas selectivity is attributed to the superior CO_(2) affinity of C@ZnO.In summary,we believe that this work not only expands the application of MMMs for gas separation but also heralds a paradigm shift in the application of porous carbon materials.

High-performance and robust high-temperature polymer electrolyte membranes with moderate microphase separation by implementation of terphenyl-based polymers

Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.

Preparation of a zeolite-palladium composite membrane for hydrogen separation:Influence of zeolite film on membrane stability

With the development of hydrogen energy,palladium-based membranes have been widely used in hydrogen separation and purification.However,the poor chemical stability of palladium composite membranes limits their commercial applications.In this study,a zeolite-palladium composite membrane with a sandwich-like structure was obtained by using a TS-1 zeolite film grown on the surface of palladium membrane.The membrane microstructure was characterized by SEM and EDX.The effects of the TS-1 film on the hydrogen permeability and stability of palladium composite membrane were investigated in details.Benefited from the protection of the TS-1 zeolite film,the stability of palladium composite membrane was enhanced.The results indicate that the TS-1-Pd composite membrane was stable after eight cycles of the temperature exchange cycles between 773 K and 623 K.Especially,the loss of hydrogen permeance for TS-1-Pd composite membrane was much smaller than that of the pure palladium membrane when the membrane was tested in the presence of C3H6atmosphere.It indicated that the TS-1-Pd composite membrane had better chemical stability in comparison with pure palladium membrane,owing to its sandwich-like structure.This work provides an efficient way for the deposition of zeolite film on palladium membrane to enhance the membrane stability.

The robust design of PMIA braided tube reinforced PFA hollow fiber membranes with graphene doping for water-in-oil separation

In order to solve the problem of oily wastewater,the poly(m-phenyleneisophthalamide)(PMIA)braided tube reinforced(PBR)poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether)(PFA)hollow fiber membrane with thermal and solvent resistant property was prepared via no-solvent green method.The membrane surface and pore structure was optimized by changing the sintering temperature and graphene(GE)content.The morphologies showed that the spherical surface with good lipophilicity was formed,and the excellent mechanical strength with a favorable interface bonding state could be obtained due to the PFA melts permeating into the supporting layer.The doping of GE produced synergistic effects with the sintering temperature owing to its good thermal conductivity and pore formation.The PBR-PFA/GE hollow fiber membrane exhibited good hydrophobicity and lipophilicity with more than 97%separation efficiency for different oil products at-0.02 MPa.With the addition of GE,the average pore size first increases and then decreases,and the porosity gradually decreases.In addition,the hollow fiber membrane showed high separation ability to the water-in-oil emulsion,and maintained a stable flux recovery rate after recycling,making it possible to apply in the field of oily wastewater treatment.

Preparation of a self-supported zeolite glass composite membrane for CO_(2)/CH_(4)separation

The low porosity of metal-organic framework glass makes it difficult to prepare membranes with high permeability.To solve this problem,we fabricated a series of self-supported zeolite glass composite membranes with different 4A zeolite loadings using the abundant pore structure of the zeolite.The 4A zeolite embedded in the zeolite glass composite membrane preserved the ligand bonds and chemical structure.The self-supported zeolite glass composite membranes exhibited good interfacial compatibility.More importantly,the incorporation of the 4A zeolite significantly improved the CO_(2)adsorption capacity of the pure a_(g)ZIF-62 membranes.In addition,gas separation performance measurements showed that the(a_(g)ZIF-62)_(0.7)(4A)_(0.3)membrane had a permeability of 13,329 Barrer for pure CO_(2)and an ideal selectivity of 31.7 for CO_(2)/CH_(4),which exceeded Robeson's upper bound.The(a_(g)ZIF-62)_(0.7)(4A)_(0.3)membrane exhibited good operational stability in the variable pressure test and 48 h long-term continuous test.This study provides a method for preparing zeolite glass composite membranes.

Membrane Separation Technology on Pharmaceutical Wastewater by Using MBR (Membrane Bioreactor)

This study demonstrated the feasibility of implementing of MBR in pharmaceutical wastewater independently, and concluded different applications of MBR in industries. Membrane bioreactor (MBR) technology was a new wastewater treatment technology with a combination of membrane separation technology and biological treatment technology, which had unique advantages on pharmaceutical wastewater treatment. The modified membrane rector design provided a significantly lower concentration of NH3-N, Phosphorous, Total Nitrogen and COD around the membranes, and subsequently a more sustainable membrane performance due to much lower overall fouling rates. In this paper, the classification and structure of biological waste water treatment by using MBR technology were summed up along with some examples of MBR in industrial wastewater treatment, which was emphatically analyzed and discussed. Finally, the prospect of MBR in industrial wastewater treatment was described. The industrial wastewater was a high-strength wastewater which had characteristics of complicated constituents, high organics concentration, highly toxic.

TREATMENT OF INDUSTRIAL WASTEWATER FROM AN ALUMINA PLANT BY MEMBRANE TECHNOLOGY(Ⅱ) ——Study on Technological Process

The experimental results of producing deionized water for the themoelectric factory from two types of the industrial wastewater of an alumina plant by using membrane technology are reported in this paper. For the treatment of the industrial wastewater with high salinity and pH value, the combination of electrodialysis (ED) and reverse osmosis (RO) is utilized, while for the treatment of the low salinity wastewater with low pH value, RO is directly used. The research results show that the above mentioned methods are effective. The technological process of the wastewater treatment with the capacity of 120 tons is designed on the basis of the experimental results.

Separation of Samarium(Ⅲ)and Gadolinium(Ⅲ)by A Push-pull Liquid Membrane System

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Controlling pore structures of Pd-doped organosilica membranes by calcination atmosphere for gas separation

Pd-doped organosilica membranes were prepared by controlling calcination atmospheres(i.e.POS-Air,POS-N2,POS-H2,POS-H2/N2)to tailor their networks for improving their gas separation performance.This study shows that Pd(Ⅱ)could be only maintained under non-reductive calcination atmosphere,while inert and reducing calcination atmosphere is more beneficial to maintain organosilica moieties in POS networks.POS-H2/N2 membrane showed the optimal H2 separation performance that its permselectivities for H2/CO2,H2/N2,H2/CH4 and H2/SF6 are 15.0,96.7,173.0 and 3400.0,re spectively.Moreover,it is found that H2 molecules pass through the four membranes based on activated diffusion,while CO2 molecules permeation through POS-N2 and POS-Air membrane is dominated by surface diffusion.This work may provide insight into the understanding of the calcination atmosphere effect on gas separation performance of metal-doped organosilica membranes.

Fabrication of Pd-Nb bimetallic doped organosilica membranes by different metal doping routes for H_(2)/CO_(2) separation

Monometallic doping has proved its superiority in improving either permselectivity or H_(2) permeability of organosilica membranes for H_(2)/CO_(2) separation,but it is still challenging to break the trade-off effect.Herein,we report a series of Pd-Nb bimetallic doped 1,2-bis(triethoxysilyl)ethane(Pd-Nb-BTESE,PNB)membranes with different metal doping routes for simultaneously improving H_(2) permeance and H_(2)/CO_(2) permselectivity by the synergetic effects of Pd and Nb.The doped Pd can exist in the BTESE network as nanoparticles while the doped Nb is incorporated into BTESE network forming Nb-O-Si covalent bonds.The metal doping routes significantly influence the microstructure of PNB networks and gas separation performance of the PNB membranes.We found that the PNB membrane with Pd doping priority(PNB-Pd)exhibited the highest surface area and pore volume,comparing with Nb doping priority(PNB-Nb)or Pd-Nb simultaneous doping(PNB-PdNb).The PNB-Pd membrane could not only exhibit an excellent H_(2) permeance of~10^(−6) mol·m^(−2)·s^(−1)·Pa^(−1) but also a high H_(2)/CO_(2) permselectivity of 17.2.Our findings may provide novel insights into preparation of bimetallic doped organosilica membranes with excellent H_(2)/CO_(2) separation performance.

SEPARATION OF THORIUM FROM YTTERBIUM WITH CYANEX272 BY USING A HOLLOW FIBER MEMBRANE EXTRACTOR

The based membrane extraction of Th(IV) and Yb(III) was studied with HBTMPP in heptane. The separation process of Th(IV) and Yb(III) was considered to be a kinetics competition one. The separation for the mixture of Th(IV) and Yb(III) was carried out by successive membrane extraction and stripping simultaneously. The concentration ratio of Th(IV) and Yb(III) is 16.74 in the stripping solution. The recovery of Th(IV) is 71.6%. The purity of Th(IV) is 95.74%. The separation factor of Th(IV) and Yb(III) is 2.52×106, which was obtained by interfacial kinetics.

SEPARATION OF PROPANE FROM PROPANE/NITROGEN MIXTURES USING PDMS COMPOSITE MEMBRANES BY VAPOR PERMEATION

This study deals with polydimethylsiloxane(PDMS)/polyvinylidene fluoride(PVDF) composite membranes for propane separation from propane/nitrogen mixtures,which is relevant to the recovery of propane in petroleum and chemical industry.The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope(SEM).The surface morphology of PDMS/PVDF composite membranes is very dense.There are three layers,the thin dense top layer,finger-like porous middle layer and s...

STUDIES ON REVERSE OSMOSIS SEPARATION OF AQUEOUS ORGANIC SOLUTIONS BY PAA/PSF COMPOSITE MEMBRANE

The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids, ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. It was found that the separation results for aliphatic alcohols, amines and aldehydes are satisfactory, the solute rejection (R-a) and the volume fluxes of solutions (J(V)) for 1000 ppm ethanol, ethylamine and ethyl aldehyde are 66.2%, 61.0%, 84.0% and 0.90 x 10(-6), 0.35 x 10(-6), 0.40 X 10(-6) m(3)/m(2) . s, respectively, at 5.0 MPa and 30 degrees C. R-a increased with increasing molecular weights of alcohols, amines and aldehydes, and the R-a for n-amyl alcohol, n-butylamine and n-butyl aldehyde reached 94.3%, 88.6% and 96.0%, respectively. Satisfactory separation results (R-a > 70%) for ketones, esters, phenols and polyols have been obtained with the PAA/PSF composite membrane. The effect of operating pressure on the properties of reverse osmosis has also been investigated. Analysis of experimental data with Spiegler-Kedem's transport model has been carried out and the membrane constants such as reflection coefficient sigma, solute and hydraulic permeabilities omega and L-p for several organic solutes have been obtained.

Numerical Study of Oil/Water Separation by Ceramic Membranes in the Presence of Turbulent Flow

Disposal of produced water during petroleum extraction causes serious environmental damage, hence the need to complete the water treatment before being disposed to environment within the criteria set established by environmental agencies in the countries. Ceramics membranes have been highlighted as a good device for separating oil/water. These act as a barrier to oil in the aqueous stream, because their essential properties for filtration, such as chemical inertness, biological stability and resistance to high temperatures. The limitation of the separation process is the decay of permeate flux during operation, due to concentration polarization and fouling. In this sense, this paper aims to evaluate numerically the feasibility of the process of separating oil/water by means of ceramic membranes in the presence of a turbulent flow induced by a tangential inlet. The results of the velocity, pressure and volumetric fraction distributions for the simulations different by varying the mass flow rate inlet and different geometric characteristics of the membrane are presented and analyzed.

SEPARATION OF FORMIC ACID-WATER AZEOTROPIC MIXTURES BY MEMBRANE DISTILLATION

The azeotrope disappeared when the formic acid-water mixtures were treated by membrane distillation. Membrane distillation were used for separation of formic acid-water azeotropic mixtures for the first time.

Synthesis and Separation Performance of Y-type Zeolite Membranes by Pre-Seeding Using Electrophoresis Deposition Method

Y-type zeolite membranes were synthesized by a two-step approach in which a particle seed layer was prepared by electrophoresis deposition(EPD) at first, followed by densification through secondary growth. The pre-seeding adopted the directing agent for Y-type zeolite synthesis serving as seeds. The effects of aging time of the directing agent, electrophoresis voltage and electrophoresis deposition time on seed layers quality as well as the quality of zeolite membranes were investigated. The results indicated that the zeolite seeds derived from the directing agent could be evenly deposited on substrate under certain EPD conditions. The XRD patterns of the seeded substrates after the secondary growth showed that the pure as-synthesized Y-type zeolite membranes had successfully grown on the substrates. The SEM images indicated that the substrate was covered by the highly intergrown zeolite crystals when the seeding solution employed the directing agent with an aging time of 2 days. The separation performance of zeolite membrane was evaluated using a CO_2/N2 mixture(with a mole ratio of 1:1) at different temperatures. Furthermore, the pervaporation measurements were carried out for the dehydration of isopropanol aqueous solutions with different mass fractions. The as-synthesized Y-type zeolite membranes exhibited a relatively high selectivity of water from isopropanol and sustainable permeation flux.

Extraction and Separation of Oxysophocarpine from Sophora alopecuroides by Reverse Three-phase Membrane Cycle Method

[Objectives] To establish the high performance liquid chromatography( HPLC) determination method for oxysophocarpine and optimize the extraction and purification technology of oxysophocarpine from Sophora alopecuroides by inverse three-phase membrane cycle.[Methods]Based on the single-factor experiment,the effects of aqueous phase and organic phase volume ratio,the concentration of sodium hydroxide,concentration of hydrochloric acid and extraction cycle time on extraction process of oxysophocarpine were investigated using orthogonal design method,to determine the optimal extraction process. [Results]The oxysophocarpine was determined by Shim-pack VP-ODS chromatographic column( 4. 6 mm × 250 mm,5 μm),mobile phase was methanol-0. 2% phosphoric acid aqueous solution( 7∶ 93),gradient elution,flow rate was 1 m L/min,the sample size was 5 μm,column temperature was 30℃,detection wavelength was 221 nm. Aqueous phase and organic phase volume ratio was 1∶ 1,hydrochloric acid concentration was 0. 3 mol/L,sodium hydroxide concentration was 0. 75 mol/L,water pump flow rate was 6 m L/min,60 min cycle time. The extraction rate of oxysophocarpine 98. 21 % within 60 min under the best experimental conditions. Oxysophocarpine has good linearity relationship within the range of 0. 01-0. 7 mg/m L( r^2= 0. 9978,n = 6),the respective average recovery rate was 97. 47%( RSD = 1. 95%). [Conclusions] This extraction process is simple in operation,the organic solvent has low consumption,and can be used for extraction of alkaloid.

MATHEMATICAL AND EXPERIMENTAL ANALYSIS OF AIR SEPARATION BY HOLLOW FIBER MEMBRANES

Approximate solutions for gas separation by hollow fiber membranes have been developedby several investigators.However,there are few reports of experimental verification of the models forhigh stage cut separations.In this work,an approximate mathematical model was developed and wasexperimentally verified for high stage cut air separation.Both countercurrent and cocurrent now pat-terns were used.In addition,the applicability of feed-inside mode for low stage cut air separation byhollow fiber membrane was examined.It was found that feed-inside mods was more advantageousthan feed-outside mode when used for the generation of oxygen-enriched air.

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.

Facile fabrication of durable superhydrophobic fabrics by silicon polyurethane membrane for oil/water separation

Nowadays, oil contamination has become a major reason for water pollution, and presents a global environmental challenge. Although many efforts have been devoted to the fabrication of oil/water separation materials, their practical applications are still hindered by their weak durability, poor chemical tolerance,environmental resistance, and potential negative impact on health and the environment. To overcome these drawbacks, this work offers a facile method to fabricate the eco-friendly and durable oil/water separation membrane fabrics by alkaline hydrolysis and silicon polyurethane coating. The X-ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy results demonstrate that silicon polyurethane membrane could be coated onto the surface of hydrolyzed polyester fabric and form a micro-/nano-scaled hierarchical structure. Based on this, the modified fabric could have a stable superhydrophobic property with a water contact angle higher than 150°, even after repeated washing and mechanical abrasion 800 times, as well as chemical corrosion. Moreover, the modified fabrics show excellent oil/water separation efficiency of up to 99% for various types of oil–water mixture. Therefore, this durable, eco-friendly and cost-efficient superhydrophobic fabric has great potential in large-scale oil/water separation.