Size effects of graphene oxide on mixed matrix membranes for CO2 separation

Graphene oxide (GO)‐polyether block amide (PEBA) mixed matrix membranes were fabricated and the effects of GO lateral size on membranes morphologies, microstructures, physicochemical properties, and gas separation performances were systematically investigated. By varying the GO lateral sizes (100–200 nm, 1–2 μm, and 5–10 μm), the polymer chains mobility, as well as the length of the gas channels could be effectively manipulated. Among the as‐prepared membranes, a GO‐PEBA mixed matrix membrane (GO‐M‐PEBA) containing 0.1 wt % medium‐lateral sized (1–2 μm) GO sheets showed the highest CO₂ permeation performance (CO₂ permeability of 110 Barrer and CO₂/N₂ mixed gas selectivity of 80), which transcends the Robeson upper bound. Also, this GO‐PEBA mixed matrix membrane exhibited high stability during long‐term operation testing. Optimized by GO lateral size, the developed GO‐PEBA mixed matrix membrane shows promising potential for industrial implementation of efficient CO₂ capture. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2843–2852, 2016     

Fast-current-driven synthesis of ultrathin ZIF-8 membrane on ceramic tube for propene/propane separation

MOF membranes are very promising in molecular separation, but it is still a challenge for industrial applications due to the complex and time-consuming synthesis. We use the fast current-driven synthesis (FCDS) method to achieve controlled growth of ZIF-8 membranes on porous graphite-coated ceramic tubes by controlling the growth time and current density. Grown for 30 min at a current density of 0.74 mA/cm², the ZIF-8 membrane exhibits selectivity for C₃H₆/C₃H₈ up to 63 with C₃H₆ permeance of 6 × 10⁻⁹ mol/(m² s Pa). Furthermore, the ZIF-8 membrane exhibits a pressure resistance of up to 3 bar and good stability of ~96 h. This work realizes the breakthrough of the MOF membrane synthesis via FCDS method from the frequently-used expensive and fragile anodic aluminum oxide (AAO) disc substrate to the tough ceramic tubular substrate, which broadens the road for the industrialization of MOF membranes in gas separation fields.     

Recent Advances in Poly (Amide-B-Ethylene) Based Membranes for Carbon Dioxide (CO2) Capture: A Review

Polyamide-b-ethylene (Pebax) is a promising material for membrane-based gas separation application with excellent CO₂ capturing potential. Pebax is a rubbery elastomer which offers good mechanical support with its hard crystalline phase and excellent gas transport through its amorphous polyether phase. This review article includes recent advances in Pebax based membrane synthesis, solvent selection for membrane synthesis, compatible fillers with Pebax matrix and the improved gas separation performance of the prepared membranes. The literature review shows that Pebax based membranes are a good candidate for separation of CO₂ from flue gases and can be used for commercial applications.     

Preparation of graphene oxide/polyamide composite nanofiltration membranes for enhancing stability and separation efficiency

Polyamide (PA) NF membranes are synthesized on a hollow fiber support by the interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC). Then, GO is coated on the PA layer to decorate the NF membrane surface (denoted GO/PA-NF). This strategy aims to improve the hydrophilicity, chlorine resistance and separation stability of the membrane. The optimization, chemical composition, morphology, and hydrophilicity of the synthesized GO/PA-NF membrane are characterized. Results indicate that the optimized GO/PA-NF in terms of rejection rate and flux are with 0.05 wt% GO. The rejection of GO/PA-NF for Na2SO₄ and MgSO₄ is 99.4% and 96.9%, respectively. Even if the GO/PA-NF is immersed in 1000 ppm NaClO solution for 48 h, the NF membrane still maintains stable salt rejection. The developed NF membranes exhibit excellent treatment performance on dying wastewater. The permeate flux and rejection of GO/PA-NF toward Congo red solution are determined to be 44.2 L/m²h and 100%, respectively. Compared with the PA membrane, GO/PA-NF presents a higher rejection for Na₂SO₄ (99.4%) and a lower rejection for NaCl (less than 20%), which shows that the NF membranes have a better divalent/monovalent salt separation performance. This study highlights the superior performance of GO/PA-NF and shows its high potential for application in wastewater treatment.     

Enhanced antipressure ability through graphene oxide membrane by intercalating g-C3N4 nanosheets for water purification

Graphene oxide (GO) membranes have shown great potential for water purification, but their permeability and antipressure ability are poor, which limits their practical applications. In this study, two-dimensional graphitic carbon nitride (g-C₃N₄) nanosheet-intercalated GO (GOCN) membranes were developed to improve the separation performance of GO membranes, especially under high operating pressure. After incorporation of the g-C₃N₄ nanosheets, the amount of permeable nanochannels (wrinkles or corrugation) in the membrane increased; hence, the water permeance was effectively improved (twice as high as that of GO membranes). Moreover, the antipressure performance of the GOCN membranes was significantly enhanced (even below 0.5 MPa pressure) as the nanochannels in the composite membranes become stable and rigid due to the support of the pressure-resistant g-C₃N₄ nanosheets. The good separation performance demonstrates that the intercalation of g-C₃N₄ is an effective strategy to improve the GO-based membrane properties, which can promote their application in water purification.     

Effect of graphene oxide on the behavior of poly(amide‐6‐b‐ethylene oxide)/graphene oxide mixed‐matrix membranes in the permeation process

Polyether‐block‐amide (Pebax)/graphene oxide (GO) mixed‐matrix membranes (MMMs) were prepared with a solution casting method, and their gas‐separation performance and mechanical properties were investigated. Compared with the pristine Pebax membrane, the crystallinity of the Pebax/GO MMMs showed a little increase. The incorporation of GO induced an increase in the elastic modulus, whereas the strain at break and tensile strength decreased. The apparent activation energies (E_p) of CO₂, N₂, H₂, and CH₄ permeation through the Pebax/GO MMMs increased because of the greater difficulty of polymer chain rotation. The E_p value of CO₂ changed from 16.5 kJ/mol of the pristine Pebax to 23.7 kJ/mol of the Pebax/GO MMMs with 3.85 vol % GO. Because of the impermeable nature of GO, the gas permeabilities of the Pebax/GO MMMs decreased remarkably with increasing GO content, in particular for the larger gases. The CO₂ permeability of the Pebax/GO MMMs with 3.85 vol % GO decreased by about 70% of that of the pristine Pebax membrane. Rather than the Maxwell model, the permeation properties of the Pebax/GO MMMs could be described successfully with the Lape model, which considered the influence of the geometrical shape and arrangement pattern of GO on the gas transport. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42624.     

Etching and acidifying graphene oxide membranes to increase gas permeance while retaining molecular sieving ability

Graphene oxide (GO) nanosheets stacked in parallel with subnanometer channels can exhibit an excellent size-sieving ability for membrane-based gas separation. However, gas molecules have to diffuse through the tortuous nanochannels, leading to low permeability. Herein we demonstrate two versatile approaches to modify the GO (before membrane fabrication by vacuum-filtration) to collectively increase gas permeability, etching using hydrogen peroxide to generate in-plane nanopores and acidifying using hydrochloric acid. For example, a membrane prepared at a pH of 5.0 using the 4-h-etched GO (HGO-4h) shows He permeability of 5.3 Barrer and He/CH₄ selectivity of 800, which are 5 times and 1.5 times those of the GO membranes, respectively. Decreasing the pH from 5.0 to 2.0 for HGO-4h enhances He permeability to 57 Barrer and He/CH₄ selectivity to 1,800. The HGO-4h prepared at the pH of 2.0 exhibits separation properties of H₂/CO₂, H₂/N₂, He/N₂, and He/CH₄ surpassing their corresponding upper bounds.     

Preparation and characterization of dimethyldichlorosilane modified SiO2/PSf nanocomposite membrane

Investigations on nanocomposite membranes imply that these hybrid materials recommend promising newgeneration membranes for gas separation in future. In this study, to investigate the effects of preparation parameters on the morphology and gas transport, various parameters including nanofiller content, surface modification and polymer concentration were considered. Two types of fumed silica nanoparticles (nonmodified and modified) were used to study the surface modification effect on agglomeration, void formation and gas separation properties of prepared membranes. Prepared nanocomposite membranes were characterized by scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and tensile strength techniques. The gas permeabilities of hydrogen, methane, and carbon dioxide through pure PSf and nanocomposites were measured as a function of silica volume fraction, and permeability coefficients were determined using a variable pressure/constant volume experimental setup. Results showed that gas permeabilities increase with silica content, and proper H₂/CH₄ and H₂/CO₂ selectivities can be achieved with modified type of silica nanoparticles due to inhibition of particle agglomeration and bonding with polymer network. Hydrogen selectivity was improved by using 15 wt% polymer content instead of 9 wt% in preparation of nanocomposite membrane with same silica content. Gas permeation results indicated that increasing of feed pressure from 3 bar to 6 bar has a positive effect on selectivity of H₂/CH₄ but negligible effect on that of H₂/CO₂ for modified silica/PSf membrane.     

Synthesis and Characterization of Ceramic Membranes (W‐Type Zeolite Membranes)

In this article, effects of synthesis parameters (synthesis temperature, synthesis time, and number of layers) on W‐type zeolite membranes synthesized over flat SUS supports for O₂/SF₆ gas separation were experimentally investigated. Experiments were carried out at these levels of synthesis temperature: 165°C, 185°C, and 200°C; synthesis time: 6, 12, and 18 h and number of layers: 1 and 2. Permeation measurements, XRD and SEM analysis were used for characterization of the synthesized membranes. The results showed that increasing synthesis temperature from 165°C up to 185°C increases separation factor of O₂/SF₆, however, further increasing decreases the separation performance. The same trend was observed for synthesis time for the single layer synthesized zeolite W membrane, although for the double layer synthesized zeolite W membrane, separation factor increased with increasing synthesis time. Repetition of layering has a net positive effect on separation factor of O₂/SF₆, and negative effect on permeation flux through the membranes. This behavior was attributed to the dual effect of synthesis temperature and synthesis time on selectivity. More zeolite crystals are deposited and larger crystals are formed at higher synthesis temperatures and longer synthesis times. Well W‐type zeolite membrane was synthesized at 185°C for 18 h with two repeating layers with a high separation factor of 20.1.     

Fabrication of graphene oxide composite membranes and their application for pervaporation dehydration of butanol

As a new kind of 2D nanomaterials, graphene oxide (GO) with 2–4 layers was fabricated via a modified Hummers method and used for the preparation of pervaporation (PV) membranes. Such GO membranes were prepared via a facile vacuum-assisted method on anodic aluminium oxide disks and applied for the dehydration of butanol. To obtain GO membranes with high performance, effects of pre-treatments, including high-speed centrifugal treat-ment of GO dispersion and thermal treatment of GO membranes, were investigated. In addition, effects of oper-ation conditions on the performance of GO membranes in the PV process and the stability of GO membranes were also studied. It is of benefit to improve the selectivity of GO membrane by pre-treatment that centrifuges the GO dispersion with 10000 r·min?1 for 40 min, which could purify the GO dispersion by removing the large size GO sheets. As prepared GO membrane showed high separation performance for the butanol/water system. The separation factor was 230, and the permeability was as high as 3.1 kg·m?2·h?1 when the PV temperature was 50 °C and the water content in feed was 10%(by mass). Meanwhile, the membrane still showed good stabil-ity for the dehydration of butanol after running for 1800 min in the PV process. GO membranes are suitable candidates for butanol dehydration via PV process.     

Modification of poly(vinylidene fluoride) membranes with aluminum oxide nanowires and graphene oxide nanosheets for oil–water separation

To improve the hydrophilic and oleophobic properties of membrane, we adopted aluminum oxide (Al₂O₃) nanowires and graphene oxide (GO) nanosheets to modify poly(vinylidene fluoride) (PVDF) membranes. The experimental results show that the intercalation of Al₂O₃ nanowires between GO nanosheets effectively improved the roughness of the GO–Al₂O₃–PVDF membrane, and the permeability of the membrane with an optimal mass ratio of Al₂O₃ to GO of 7.5 was 31 times that of the GO–PVDF membrane. Furthermore, the addition of Al₂O₃ nanowires significantly enhanced both the hydrophilic and oleophobic properties of the GO–Al₂O₃–PVDF membrane. On the basis of the extended Derjaguin–Landau–Verwey–Overbeek theory, the energy barriers between the oil droplets and GO–PVDF and GO–Al₂O₃–PVDF membranes were 0.63 and 0.9 KT, respectively; this indicated improvements in the anti-oil-fouling ability of the GO–Al₂O₃–PVDF membranes. We also found that both the GO–PVDF and GO–Al₂O₃–PVDF membranes had great oil–water separation rates (97.9 and 99.4%, respectively) with an initial oil concentration of 200 mg/L. The findings of this study show that the GO–Al₂O₃–PVDF membrane is a promising oil–water separation membrane, and further investigation of the cleaning procedure is needed to promote its practical application in oil–water separation. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47493.     

Investigation of the effect of functionalized carbon nanotube and graphene oxide in guar gum-based mixed matrix membrane for gas separation application

The present study deals with preparing mixed matrix membranes (MMMs), a new polysaccharide-based natural polymer used as a matrix with functionalized carbon nanotubes (FCNTs) and graphene oxide (GO) used as an inorganic filler. This work identified the effect of the inorganic fillers (FCNTs or GO) with naturally occurring polymer for gas separation. The incorporation of fillers improves the gas separation performance of MMMs. In GG/FCNTs MMMs, the selectivities of CO₂/N₂ and CO₂/H₂ were enhanced by 55.24% and 57.89%, respectively. Moreover, in GG/GO MMMs, the selectivities of CO₂/N₂ and CO₂/H₂ were improved by 99.50% and 50%, respectively. The membrane was characterized by scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR). The SEM analysis of GG/GO MMMs reveals layered structure, and GG/FCNTs MMMs create passages to transport gases. The Universal testing machine (UTM) is used to analyze the mechanical properties of pristine and modified membranes.     

Carbon molecular sieve membranes derived from trimethylsilyl substituted poly(phenylene oxide) for gas separation

Carbon molecular sieve membranes for gas separation prepared using poly(phenylene oxide) (PPO) as precursor have been examined. The PPO precursor was modified by introducing a trimethylsilyl (TMS) substituent and its effect on the gas transport property of the resulting carbon membrane was examined. TMS-substituted PPO (TMSPPO) was prepared in a high yield by a simple one-step reaction, and its carbon membrane was successfully fabricated. The modification improved the gas permeability of the resulting membrane which also exhibited excellent O₂/N₂ and CO₂/CH₄ separation performance comparable to those of polyimide-derived carbon membranes. From the analysis of the microstructure of the TMSPPO carbon membranes, it is believed that the TMS groups improve gas diffusivity by increasing the micropore volume.     

一步法制备含氨基化合物的非对称CO2分离膜

采用一步相分离法,制备以聚醚砜（PES）为主体材料,二乙醇胺（DEA）为添加剂和氨基载体的膜,用于CO₂分离。考察了PES浓度、DEA浓度、膜厚度对CO₂/N₂分离性能的影响,同时考察了膜性能的长时间稳定性。当涂膜液中DEA/PES的质量比为12/26、刮刀与无纺布的距离为300 μm、进料气压力为0.11 MPa（表压）时,膜的CO₂渗透速率可达274 GPU,CO₂/N₂分离因子可达50。测试温度低于40℃时,DEA/PES膜的CO₂渗透速率和CO₂/N₂分离因子保持稳定。另外,对CO₂/N₂分离性能较好的DEA/PES膜（质量比为12/27）进行CO₂/CH₄分离性能测试,在1 MPa（表压）下性能优于商品膜。上述结果表明,本文研制的DEA/PES膜制备步骤简单,易于规模化制备,性能较优,在CO₂分离领域具有良好的应用前景。     

Recent developments on catalytic membrane for gas cleaning

Catalytic membrane, a novel membrane separation technology that combines catalysis and separation, exhibits significant potential in gas purification such as formaldehyde, toluene and nitrogen oxides(NO_x). The catalytic membrane can remove solid particles through membrane separation and degrade gaseous pollutants to clean gas via a catalytic reaction to achieve green emissions. In this review, we discussed the recent developments of catalytic membranes from two aspects: preparation of catalytic membrane and its application in gas cleaning.Catalytic membranes are divided into organic catalytic membranes and inorganic catalytic membranes depending on the substrate materials. The organic catalytic membranes which are used for low temperature operation(less than 300 °C) are prepared by modifying the polymers or doping catalytic components into the polymers through coating, grafting, or in situ growth of catalysts on polymeric membrane. Inorganic catalytic membranes are used at higher temperature(higher than 500 °C). The catalyst and inorganic membrane can be integrated through conventional deposition methods, such as chemical(physical) vapor deposition and wet chemical deposition. The application progress of catalytic membrane is focused on purifying indoor air and industrial exhaust to remove formaldehyde, toluene, NO_x and PM2.5, which are also summarized. Perspectives on the future developments of the catalytic membranes are provided in terms of material manufacturing and process optimization.     

Inkjet Printing of Microporous Silica Gas Separation Membranes

Inkjet printing was applied to manufacture silica‐based gas separation membranes, which were coated on a pore‐graduated alumina substrate with a mesoporous γ‐alumina interlayer. A silica sol diluted by 1‐propanol was used to print the membrane layer followed by thermal treatment in a rapid thermal processing furnace. The membrane thickness was varied between 30 and 110 nm by conducting one, two, and three coating steps. In the latter case, H₂ permeance in the range of 2.0 × 10^?8–3.3 × 10^?8 mol/s·m²·Pa combined with H₂/CO₂ selectivities in the range of 15–25 were achieved, proving the concept that inorganic gas separation membranes can be successfully processed by inkjet printing.     

Effect of Water Content of Synthetic Hydrogel on Dehydration Performance of Nanoporous LTA Zeolite Membranes

Nanoporous LTA‐type zeolite membranes were synthesized on α‐Al₂O₃ disk as substrate using secondary growth method. A gel formula of 1 Al₂O₃: 2 SiO₂: 3.4 Na₂O: W H₂O in molar basis was chosen while its water content (W) was varied. Four levels of water contents of 140, 155, 175, and 200 were selected for membrane synthesis. The results showed that the best membrane was synthesized with water content of 155. The most efficient zeolite membrane showed a permeation flux of 0.5 kg/m²/h and a separation factor of 3800 in dehydration of a 5/95 (wt%) water/isopropanol mixture at 298 K.     

Role of critical concentration of PEI in NMP solutions on gas permeation characteristics of PEI gas separation membranes

In preparation of polymeric gas separation membranes by phase inversion method, polymer concentration is one of the most important variables which can change membrane morphology and behavior. In this research, critical concentration of the polyetherimide (PEI) solutions in N-methyl-2-pyrrolidone (NMP) as a solvent was determined by viscometric method. The influence of temperature on critical concentration was studied. Three asymmetric PDMS/PEI membranes with different concentrations of PEI were prepared and characterized for H₂/CH₄ separation. The results showed that the membranes with higher concentrations than critical concentration were more suitable for gas separation. In addition, the viscosity data were fitted by appropriate equations and the densities were satisfactorily correlated by a simple first-order polynomial with respect to temperature and the PEI mass fraction. The prepared membrane showed the selectivity of 26 for H₂/CH₄ separation at 1 bar and 25 °C for pure gas and 24.8 for mixed gas. The influence of the pressure on the H₂ and CH₄ permeance and the selectivity for a mixed binary gas showed that the permeance of both gases declined by pressure enhancement and the selectivity increased.     

Effects of pressure and temperature on fixed-site carrier membrane for CO2 separation from natural gas

In this paper, the effect of testing temperature on the performance of fixed carrier membrane for CO₂ separation were studied. The blend composite membranes were developed respectively with a blend of PEI-PVA (polyetheleneimine-polyvinyl alcohol) as separation layer and PS (polysulfone) ultrafiltration membranes as the substrates. The permselectivity of the membranes was measured with CO₂/CH₄ mixed gas. The effect of testing temperature on membrane separation performance was investigated. The results showed that both the permeances of CO₂ and CH₄ decreased with the increase of temperature, and the permeances decreased more quickly under low pressure than those under high pressure. At the feed pressure of 0.11 MPa, the CO₂/ CH₄ selectivity of PEI-PVA/PS blend composite membrane reduced along with temperature increment. Under the feed pressure of 0.21 MPa, as well as 1.11 MPa, the selectivity decreased with the increase of temperature.     

Interfacial polymerization of facilitated transport polyamide membrane prepared from PIP and IPC for gas separation applications

A facilitated transport polyamide (PA) membrane was developed for gas separation by interfacial polymerization reaction of piperazine (PIP) and isophthaloyl chloride (IPC) supported on polysulfone (PSF) membrane previously prepared by dry/wet phase inversion method. The properties of the prepared membranes were characterized by SEM, FT-IR, TGA, and XRD. SEM images showed that a defect-free PSF, and rough PA membranes were fabricated, while the FT-IR spectra confirmed the formation of PA layer on top of the PSF support. The separation performance of the thin film PA and PSF membranes was evaluated using four gasses (CO₂, CH₄, N₂, and O₂). Compared to the PSF membrane, the PA membrane demonstrated an increased selectivity of CO₂/CH₄ and CO₂/N₂ by 178%, 169%, respectively. This improvement was attributed to the presence of amine functional groups, which acted as a fixed carrier to facilitate the transport of CO₂ gas across the membrane. However, building the PA layer on top of PSF support reduced the membrane permeance of CO₂ from 2.41 to 2.12 GPU as a result of the increased mass transfer resistance. Furthermore, the effect of operating temperature and pressure on the separation performance of the membranes was investigated.