Preparation of CO_2 selective composite membranes using Pebax/CuBTC/PEG-ran-PPG ternary system

Three phase Pebax~? MH 1657/PEG-ran-PPG/CuBTC(polymer/liquid/solid) was successfully deposited as a selective layer on a porous Polysulfone(PSF) support. In fact, the beneficial properties of PEG(high selectivity) with those of PPG(high permeability, amorphous) have been combined with superior properties of mixed matrix membrane(MMMs). The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by CO_2 and CH_4adsorption test. Statistically based experimental design(central composite design, CCD) was applied to analyze and optimize the effect of PEG-ran-PPG(10–50 wt%) and CuBTC(0–20 wt%) mass contents on the CO_2 permeance and CO_2/CH_4 ideal selectivity. Based on the regression coefficients of the obtained models, the CO_2 permeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO_2/CH_4 ideal selectivity. Under the optimum conditions(PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%), nearly 620% increase in the CO_2 permeance and43% enhancement in the CO_2/CH_4 ideal selectivity was observed compared to the neat Pebax. The effect of pressure(3, 9 and 15 bar) on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of CO_2 in the membranes resulted in the enhancement of CO_2 permeability with increase in gas pressure.     

NaA分子筛膜催化剂上CO和C2H4混合气的选择性氧化反应

Defect-free zeolite NaA membranes were coated onto the surface of spherical Pt/Al2O3 particles using a two-step hydrothermal method. The structure and morphology of the synthesized composite catalysts were characterized using XRD and SEM techniques, respectively. The results indicated a layer of compact and uniform NaA molecular sieve membrane with a thickness of about 20 滋m was coated on the spherical Pt/Al2O3 particles after the two-step hydrothermal synthesis. The prepared NaA membrane coated catalysts were used in the oxidation of a mixture of CO and C2H4 to study the reactant selectivity over the coated zeolite NaA membranes. Under the optimized conditions, the oxidation selectivity for CO over C2H4 on the composite catalyst was as high as 96%. The feasible application of this composite membrane coated catalyst to the selective removal of CO in the presence of C2H4 was anticipated.     

Hydrophilic nanofiltration membranes with self-polymerized and strongly-adhered polydopamine as separating layer

Inspired by the self-polymerization and strong adhesion characteristics of dopamine in aqueous conditions,a novel hydrophilic nanofiltration（NF） membrane was fabricated by simply dipping polysulfone（PSf） ultrafiltration（UF） substrate in dopamine solution.The changes in surface chemical composition and morphology of membranes were determined by Fourier transform infrared spectroscopy（FTIR-ATR）,X-ray photoelectron spectroscopy（XPS）,scanning electron microscopy（SEM） and atomic force microscopy（AFM）.The experimental results indicated that the self-polymerized dopamine formed an ultrathin and defect-free barrier layer on the PSf UF membrane.The surface hydrophilicity of membranes was evaluated through water contact angle measurements.It was found that membrane hydrophilicity was significantly improved after coating a polydopamine（pDA） layer,especially after double coating.The dyes filtration experiments showed that the double-coated membranes were able to reject completely the dyes of brilliant blue,congo red and methyl orange with a pure water flux of 83.7 L/（m²·h） under 0.6 MPa.The zeta potential determination revealed the positively-charged characteristics of PSf/pDA composite membrane in NF process.The salt rejection of the membranes was characterized by 0.01 mmol/L of salts filtration experiment.It was demonstrated that the salts rejections followed the sequence:NaCl2SO₄422,and the rejection to CaCl₂ reached 68.7%.Moreover,the composite NF membranes showed a good stability in water-phase filtration process.     

A novel CHS/ALG bi-layer composite membrane with sustained antimicrobial efficacy used as wound dressing

<正>A membrane composed of an alginate(ALG) layer and a chitosan(CHS) layer with sustained antimicrobial efficacy was prepared.Ciprofloxacin HC1(CIP) was incorporated into the ALG layer.Morphological feature of the composite membrane was analyzed by scanning electron microscopy(SEM).Water uptake capacity,in vitro drug release,and in vitro antimicrobial activity were evaluated.The composite membrane exhibited perfect binding characteristic between the two layers.The water uptake capacity of all the membranes was above 800%.The CIP could release from the composite membranes for 48 h.The membrane could control the bacterial growth persistently.The results suggested that this CHS/ALG composite membrane incorporated with CIP had the potential for wound dressing application.     

Enhancement of current density using effective membranes electrode assemblies for water electrolyser system

The goal of this study was to develop and design a composite proton exchange membrane(PEM) and membrane electrode assembly(MEA) that are suitable for the PEM based water electrolysis system. In particular,it focuses on the development of sulphonated polyether ether ketone(SPEEK) based membranes and caesium salt of silico-tungstic acid(Cs Si WA) matrix compared with one of the transition metal oxides such as titanium dioxide(TiO_2), silicon dioxide(SiO_2) and zirconium dioxide(ZrO_2). The resultant membranes have been characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, ion exchange capacity(IEC), water uptake and atomic force microscopy. Comparative studies on the performance of MEAs were also conducted utilizing impregnation-reduction and conventional brush coating methods. The PEM electrolysis performance of SPEEK-Cs Si WA-ZrO_2 composite membrane was more superior than that of other membranes involved in this study. Electrochemical characterization shows that a maximum current density of 1.4 A/cm~2 was achieved at 60 °C, explained by an increased concentration of protonic sites available at the interface.     

Synthesis of ethylidene diacetate from dimethyl ether,CO and H_2

Ethylidene diacetate was prepared by reacting dimethyl ether,acetic acid and syngas in the presence of a catalytic system comprising RhI3,PPh3 and CH3I.The effects of reaction temperature,pressure,time and the CO/H2 molar ratio on the conversion of dimethyl ether and the product selectivity were investigated under the same catalyst formulation.Results showed that a maximum conversion of dimethyl ether was obtained when a mixture consisting of 0.3 mol dimethyl ether and 120 ml acetic acid was reacted at 180 ℃ and 3.0 MPa for 10 h at a stirring speed of 600 rpm under a syngas flow with a CO/H2 molar ratio of 2.5,which was catalyzed by a catalyst mixture comprising 0.3 g RhI3,6 g PPh3 and 1.3 g CH3I.The selectivity of ethylidene diacetate increased with temperature,decreased with the CO/H2 molar ratio and exhibited a maximum with pressure.     

Simulation and model design of pipe-shell reactor for the direct synthesis of dimethyl ether from syngas

The simulation was made based on the model of pipe-shell reactor that was established by the model of global kinetics of synthesis of dimethyl ether from syngas over a bifunctional catalyst. The results of simulation showed that the selectivity for dimethyl ether （DME） and the conversion of CO were higher but the hot spot was kept below the temperature limit of the pipe-shell reactor. The suitable diameter of the pipe was φ38×2 mm, and the length of the pipe was 5.8 m. The optimal process conditions of the reactor were that the pressure was 5 MPa, the temperature of the cooling water was 240 ℃, and the temperature of the raw gas at inlet of the reactor was 220 ℃. The production of this reactor was 102800 t/y （ton per year） under these conditions.     

Poly(amide-6-b-ethylene oxide)/SAPO-34 mixed ma-trix membrane for CO2separation

In this paper, poly（amide-6-b-ethylene oxide） （Pebax1657）/SAPO-34 mixed matrix membranes （MMMs） were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax ma- trix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was en- hanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs （50 wt% SAPO-34） increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.     

Preparation and Properties of Poly（ether ether ketone）/Carbon Nanotube Modified Polypropylene Janus Composite Separator北大核心CSCD

Lithium-ion batteries （LIBs）have attracted wide attention because of their broad prospects in electric vehicles. However,the safety problems and low multiplier performance of the commercial polyolefin separator limit their further development,due to the poor dimensional thermal stability and low electrolyte absorption rate. Poly（ether ether ketone）（PEEK）and carbon nanotube（CNT）are compounded to coat on polypropylene （PP） to prepare Janus composite separator （PP@C） through the phase inversion method. PP@C composite separator does not deform at 180 ℃ for 0. 5 h（only slight deformation）,illustrating excellent thermal stability. The electrolyte absorption rate of PP@C2 is 193. 8%. The electrolyte uptake rate of the PP@C2 composite membrane was 193. 8%,which was 64. 5% higher than the PP membrane,showing a superduper electrolyte permeability. As a result,the specific discharge capacity of LIBs assembled with PP@C2 composite separator is 157. 6 mA·h/g at 0. 2 C and 129. 8 mA·h/g at 2 C,showing good rate performance with the capacity recovery rate of more than 99%. This might be attributed to the ultra-high thermal stability of PEEK,the good affinity of the electrolyte,the high conductivity of CNT,as well as the uniform dispersion of Li+ ,so that the separator can have excellent electrochemical performance while improving safety. © 2022, Science Press (China). All rights reserved.     

用水热法在氧化铝陶瓷膜管上原位合成丝光沸石膜

The mordenite membrane was prepared on a α-Al 2O 3 tube by in situ hydrothermal synthesis. The crystallization was carried out at 443 K for 2～4 days. Silica sol and sodium aluminate were used as the sources of silica and alumina, respectively, and tetraethylammonium bromide (TEABr) as the template. The molar composition of the parent solution was 11 4Na 2O∶1 0Al 2O 3∶40SiO 2∶2500H 2O∶1 5TEABr. SEM and XRD were used to characterize the powder product and the composite membrane. The synthesized mordenite membrane proved to be in a full coverage and an excellent intergrowth. The mordenite crystals were about 20～30 μm and the thickness of the mordenite membrane was 30～40 μm. Based on the SEM pictures of the membrane in the early stage of hydrothermal synthesis, a growth model for the mordenite membrane was assumed. At first a gel layer was formed on the surface of the alumina tube. Nucleation took place in the gel layer but not at the interface of the gel layer and bulk solution. The gel layer provided the nutrients for the growth of zeolite crystals. After the gel layer was consumed completely, the zeolite crystals or membrane were exposed to the bulk solution. The membrane separation test on the mordenite membrane showed that the permeances of pure H 2 and N 2 at 298 K were 6 92×10 -7 and 1 81×10 -7 mol/(m 2·s·Pa), respectively. The ideal selectivity of H 2/N 2 was 3 82, which is higher than that of Knudsen mechanism. It suggested that the mordenite membrane had the ability of molecular sieving.     

Preparation of composite poly(ether block amide)membrane for CO_2 capture

In this study, a poly(ether block amide)(Pebax 1657) composite membrane applied for CO2 capture was prepared by coating Pebax 1657 solution on polyacrylonitrile(PAN) ultrafiltration membrane. Ethanol/water mixture was used as the solvent of Pebax and the effects of ethanol/water mass ratios and Pebax concentration on the permeation properties of composite membrane were studied. To enhance the composite membrane permeance, the gutter layer, made from reactive amino silicone crosslinking with polydimethylsiloxane(PDMS), was designed. The influence of crosslinking degree of the gutter layer on membrane performance was investigated. As a result, a Pebax/aminoPDMS/PAN multilayer membrane with hexane resistance was developed, showing CO2 permeance of 350 GPU and CO2/N2 selectivity over50. The blend of polyethylene glycol dimethyl ether(PEG-DME) with Pebax as coating material was studied to further improve the membrane performance. After being combined with PEG-DME additive, CO2 permeance of the final Pebax-PEG-DME/amino-PDMS/PAN composite membrane reached 400 GPU above with CO2/N2 selectivity over 65.     

Pebax/TSIL blend thin film composite membranes for CO_2 separation

In this study a thin film composite (TFC) membrane with a Pebax/Task-specific ionic liquid (TSIL) blend selective layer was prepared. Defect-free Pebax/TSIL layers were coated successfully on a polysulfone ultrafiltration porous support with a polydimethylsiloxane (PDMS) gutter layer. Different parameters in the membrane preparation (e.g. concentration, coating time) were investigated and optimized. The morphology of the membranes was studied by scanning electron microscopy (SEM), while the thermal properties and chemical structures of the membrane materials were investigated by thermo-gravimetric analyzer (TGA), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The CO₂ separation performance of the membrane was evaluated using a mixed gas permeation test. Experimental results show that the incorporation of TSIL into the Pebax matrix can significantly increase both CO₂ permeance and CO₂/N₂ selectivity. With the presence of water vapor, the membrane exhibits the best CO₂/N₂ selectivity at a relative humidity of around 75%, where a CO₂ permeance of around 500 GPU and a CO₂/N₂ selectivity of 46 were documented. A further increase in the relative humidity resulted in higher CO₂ permeance but decreased CO₂/N₂ selectivity. Experiments also show that CO₂ permeance decreases with a CO₂ partial pressure increase, which is considered a characteristic in facilitated transport membranes.     

Fabrication of polymer/fluoride-containing salts blend composite membranes for CO_2 separation

Poly (N,N-dimethylaminoethyl methacrylate)-poly (ethylene glycol methyl ether methacrylate) (PDMAEMA-PEGMEMA) and cesium fluoride (CsF) were blended and used as the separation material of composite membranes.Hollow fiber composite membranes were fabricated by coating the blend on polysulfone (PSf) hollow fiber substrate.Introduction of fluorine ion improved the separation performance of the membrane.The concentration of coating solution was adjusted to obtain a membrane with high permeance.The composite membrane showed good performance with the CO2 permeance of 30.4 GPU (1 GPU=10-6 cm3 (STP)/(cm 2 s cmHg)),and selectivities to CO2/N2,CO2/CH4,CO2/H2 and O2/N2 of 47.2,37.6,1.75 and 4.70,respectively.Potassium fluoride (KF),due to its low cost,was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF.The effect of operating temperature on the permeation properties of the composite membrane was also investigated.     

Fabrication of polymer/fluoride-containing salts blend composite membranes for CO2 separation

Poly (N, N-dimethylaminoethyl methacrylate)-poly (ethylene glycol methyl ether methacrylate) (PDMAEMA-PEGMEMA) and cesium fluoride (CsF) were blended and used as the separation material of composite membranes. Hollow fiber composite membranes were fabricated by coating the blend on polysulfone (PSf) hollow fiber substrate. Introduction of fluorine ion improved the separation performance of the membrane. The concentration of coating solution was adjusted to obtain a membrane with high permeance. The composite membrane showed good performance with the CO2 permeance of 30.4 GPU (1 GPU = 10^-6 cm³(STP)/(cm²·s·cmHg)), and selectivities to CO2/N2, CO2/CH4, CO2/H2 and O2/N2 of 47.2, 37.6, 1.75 and 4.70, respectively. Potassium fluoride (KF), due to its low cost, was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF. The effect of operating temperature on the permeation properties of the composite membrane was also investigated.     

PEBAX®2533/PSf中空纤维复合膜制备及阻力性能

采用浸渍涂层法制备了聚醚共聚酰胺(PEBAX®2533)/聚砜(PSf)中空纤维复合膜. 考察了涂层液浓度、 温度和基膜预处理对复合膜结构、 阻力及渗透性能的影响, 并考察了操作压力对膜渗透性能的影响. 实验结果表明, 随着涂层液浓度的增加, 复合膜致密层厚度及阻力增大, 复合膜总阻力及支撑层阻力先增大后减小, CO2渗透速率先减小后增大, 分离系数增大. 随着涂层温度升高, 复合膜致密层厚度及阻力减小, 支撑层阻力增大, 复合膜总阻力先减小后增大, 分离系数和渗透速率先增大后减小. 经过预处理, 复合膜致密层厚度减小、 阻力大幅度减小, CO2渗透速率增大58%, 分离系数略有下降. 复合膜支撑层阻力过大, 尤其是支撑层的致密结构影响复合膜的塑化行为.     

Interfacially formed poly(N,N-dimethylaminoethyl methacrylate)/polysulfone composite membranes for CO2/N2 separation

Interfacially formed poly(N,N-dimethylaminoethyl methacrylate)/polysulfone (PDMAEMA/PSF) composite membranes were developed for CO₂/N₂ separation. A layer of PDMAEMA was deposited on a microporous PSF substrate by the solution coating technique, followed by crosslinking with p-xylylene dichloride (XDC) at the interface between the PDMAEMA solid layer and the crosslinking solution. The hydrophilicity and surface free energy of the membranes were analyzed by contact angle measurements with different probe liquids. The permselectivity of the membrane was shown to be affected by the PDMAEMA deposition time, interfacial crosslinking reaction time, and the PDMAEMA and XDC concentrations in the polymer coating solution and the crosslinking solution, respectively. The composite membrane showed a CO₂ permeance of 85 GPU and a CO₂/N₂ ideal separation factor of 50 at 23 °C and 0.41 MPa of CO₂ feed pressure.     

具有界面交联结构藻酸钠复合膜的制备与性能

报道了一种具有界面交联结构的新型藻酸钠复合膜及其对醇水和其它有机物水体系的渗透汽化分离性能.该膜的活性层为藻酸钠,支撑层为氨化聚丙烯腈(PAN)多孔膜,在这两层之间存在着界面交联结构.研究了PAN多孔膜的水解时间、进行氨基化的二元胺种类及浓度对复合膜分离性能的影响,用己二胺进行氨基化所得到的复合膜的分离性能明显优于用乙二胺的结果.扫描电镜照片显示水解及氨基化改变了PAN超滤膜的孔结构,这也是影响新型复合膜性能的一个重要原因.     

Preparation and characterization of (Pebax 1657 + silica nanoparticle)/PVC mixed matrix composite membrane for CO<Subscript>2</Subscript>/N<Subscript>2</Subscript> separation

In this work, the films of poly(ether-block-amide) (Pebax 1657) and hydrophilic/hydrophobic silica nanoparticles (0–10 wt%) were coated on a poly(vinyl chloride) (PVC) ultrafiltration membrane to form new mixed matrix composite membranes (MMCMs) for CO₂/N₂ separation. The membranes were characterized by SEM, FTIR, DSC and XRD. Successful formation of a non-porous defect-free dense top layer with ~4 μm of thickness and also uniform dispersion of silica nanoparticles up to 8 wt% loading in Pebax matrix were confirmed by SEM images. The gas permeation results showed an increase in the permeance of all gases and an increase in ideal CO₂/N₂ selectivity with the increase in silica nanoparticle contents. Comparison between the incorporation of hydrophilic and hydrophobic silica nanoparticle into Pebax matrix revealed that the great enhancement of CO₂ solubility is the key factor for the performance improvement of Pebax + silica nanoparticle membranes. The best separation performance of the hydrophilic silica nanoparticle-incorporated Pebax/PVC membrane for pure gases (at 1 bar and 25 °C) was obtained with a CO₂ permeability of 124 barrer and an ideal CO₂/N₂ selectivity of 76, i.e., 63 and 35% higher than those of neat Pebax membrane, respectively. The corresponding values for hydrophobic silica nanoparticle-incorporated Pebax/PVC membrane were 107 barrer for CO₂ permeability and 61 for ideal CO₂/N₂ selectivity. Also the performances of MMCMs improved upon pressure increase (1–10 bar) owing to the shift in plasticizing effect of CO₂ towards the higher pressures. In addition, an increase in permeabilities with a decrease in ideal selectivity was observed upon temperature increase (25–50 °C) due to the intensification of chain mobility.     

Matrimid®5218/PSf双层非对称中空纤维膜的制备及其气体分离性能研究

以商业化聚酰亚胺Matrimid®5218作为功能层材料, 聚砜作为支撑层材料, 采用共挤出法制备双层非对称中空纤维气体分离膜. 所制备的双层非对称中空纤维膜具有致密无缺陷的超薄皮层, 致密皮层厚度约为0.21 μm. 在25 ℃, 0.5 MPa下, CO2/CH4的选择性系数达51.39, CO2的渗透系数为46.29 GPU, O2/N2的选择性系数达到7.13, O2的渗透速率为6.38 GPU. 考察了温度和压力对膜的渗透系数和选择性系数的影响, 并考察了物理老化对膜性能的影响.