Modification of PES/PU membrane by supercritical CO2 to enhance CO2/CH4 selectivity: Fabrication and correlation approach using RSM

Integrally skinned asymmetric gas separation membranes of polyethersulfone (PES)/polyurethane (PU) blend were prepared using supercritical CO₂ (SC-CO₂) as a nonsolvent for the polymer solution. The membrane consisted of a dense and a porous layer, which were conjoined to separate CO₂ from CH₄. The FTIR, DSC, tensile and SEM tests were performed to study and characterize the membranes. The results revealed that an increase in SC-CO₂ temperature causes an increment in permeance and a decrease in membrane selectivity. Furthermore, by raising the pressure, both permeance and selectivity increased. The modified membrane with SC-CO₂ had much higher selectivity, about 5.5 times superior to the non-modified membrane. This higher selectivity performance compared to previous works was obtained by taking the advantages of both using partial miscible blend polymer due to the strong polar–polar interaction between PU PES and SC-CO₂ to fabricate the membrane. The response surface methodology (RSM) was applied to find the relationships between several explanatory variables and CO₂ and CH₄ permeance and CO₂/CH₄ selectivity as responses. Finally, the results were validated with the experimental data, which the model results were in good agreement with the available experimental data.     

Fabrication and characterization of polyetherimide/polyvinyl acetate polymer blend membranes for CO2/CH4 separation

This article presents fabrication, characterization, and performance evaluation of polyetherimide (PEI)/polyvinyl acetate (PVAc) blend membranes. Polymer blend membranes with various blend ratios of PEI/PVAc were prepared by solution casting and evaporation technique. Morphology and miscibility of polymer blend membranes were characterized by field emission scanning electron microscope (FESEM) and differential scanning calorimetry (DSC), respectively. The interaction between blend polymers was analyzed by FTIR analysis. Gas separation performance was evaluated in terms of permeability and selectivity. FESEM results revealed that pure polymer and blend membranes were homogeneous and dense in structure. A single glass transition temperature of polymer blend membranes was found in DSC analysis which indicated the miscibility of PEI/PVAc blend. FTIR analysis confirmed the presence of molecular interaction between blend polymers. The permeation results showed that the presence of PVAc (3 wt%) in blend membranes has improved CO₂ permeability up to 95% compared to pure PEI membrane. In addition, CO₂/CH₄ selectivity was found to be 40% higher than pure PEI membrane. This study shows that blending a small fraction of PVAc can improve the gas separation performance of PEI/PVAc blend membranes. POLYM. ENG. SCI., 59:E293–E301, 2019. © 2018 Society of Plastics Engineers     

Polyurethane-SAPO-34 mixed matrix membrane for CO2/CH4 and CO2/N2 separation

SAPO-34 nanocrystals (inorganic filler) were incorporated in polyurethane membranes and the permeation properties of CO₂, CH_4, and N₂ gases were explored. In this regard, the synthesized PU-SAPO-34 mixed matrix membranes (MMMs) were characterized via SEM, AFM, TGA, XRD and FTIR analyses. Gas permeation properties of PU-SAPO-34 MMMs with SAPO-34 contents of 5 wt%, 10 wt% and 20 wt% were investigated. The permeation results revealed that the presence of 20 wt% SAPO-34 resulted in 4.45%, 18.24% and 40.2% reductions in permeability of CO_2, CH_4, and N₂, respectively, as compared to the permeability of neat polyurethane membrane. Also, the findings showed that at the pressure of 1.2 MPa, the incorporation of 20 wt% SAPO-34 into the polyurethane membranes enhanced the selectivity of CO₂/CH₄ and CO₂/N₂, 14.43 and 37.46%, respectively. In this research, PU containing 20 wt% SAPO-34 showed the best separation performance. For the first time, polynomial regression (PR) as a simple yet accurate tool yielded a mathematical equation for the prediction of permeabilities with high accuracy (R² > 99%).     

Composite mixed matrix membranes incorporating microporous carbon molecular sieve as filler in polyethersulfone for CO2/CH4 separation

Membrane technology has been considered a key factor for sustainable growth in high-efficiency gas separation. Current mixed matrix membranes (MMMs) technology is rising, but these membranes in the dense structure are having difficulties in operating at high pressures and scale up for commercialization. The purpose of this research is to synthesize composite MMMs (CMMMs) consisting of polyethersulfone (PES), carbon molecular sieve (CMS 1–5 wt %), and Novatex 2471 nonwoven fabric (support layer). The membranes' physical, chemical, and thermal properties were evaluated by different analytical equipment. The morphology of both PES and PES-CMS composite membranes had a porous and asymmetric structure, in which CMS was uniformly distributed in the polymer matrix. The thermal properties showed that the membranes were stable up to 350 °C with a single glass transition temperature. The functional groups in the membrane were confirmed by spectral analysis. The gas performance results showed that carbon dioxide permeance increased with increased CMS concentration and methane permeance decreased due to the hindering effect of CMS under similar operating conditions. The highest selectivity achieved was 12.774 using CMMM of 5 wt % of CMS at 10 bar, which on average was 137.80%, improved selectivity compared to pure PES membrane. The support layer was able to withstand high operating pressures and showed the ability to scale up. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48476.     

Development of antifouling properties and performance of nanofiltration membranes modified by interfacial polymerisation

Two types of bisphenol monomers, Bisphenol A (BPA) and Tetramethyl Bisphenol A (TMBPA), with different concentrations of bisphenol aqueous solution (0.5% to 2.%w/v) and various interfacial polymerisation times (10 s, 30 s and 60 s) in the fixed 0.15%w/v organic solution of trimesoyl chloride (TMC)-hexane were studied. Irreversible fouling of both unmodified polyethersulfone NFPES10 and modified polyester thin-film composite polyethersulfone membranes were studied using humic acid model solutions at two different pH values, pH 7 and pH 3. It was observed that polyester thin-film composite membranes prepared by BPA exhibited fewer tendencies for irreversible fouling by humic acid molecules at neutral environment compared to unmodified NFPES10 and TMBPA-polyester series. This is most probably due to high electrostatic repulsion force between negatively charged of BPA-polyester layer and highly negative charged of humic acid at pH7. However, some modified membranes with rougher surfaces were severely fouled by humic acid molecules at acidic environment, pH 3. Under this acidic environment, carboxylic acid groups of humic acid lost their charge and the macromolecules of humic acid have smaller macromolecular configuration due to the increased hydrophobicity and reduced inter-chain electrostatic repulsion. Thus the molecules of humic acid may be preferentially accumulated at the valleys of the rougher membrane surface blocking them and resulting in a more severe fouling. In addition, the modification also affected membrane pore size and pore size distribution as shown by AFM images. It was also observed that the smaller pore size generated after modification does not have significant effect on humic acid removal due to the larger size of humic acid molecules. All the modified membranes posses smaller pore size than the unmodified NFPES10 (1.47 nm) in the range of 0.8–1.34 nm.     

离子液体支撑液膜的CO2/CH4分离性能

由于离子液体对CO₂具有较好的溶解选择性,离子液体支撑液膜分离CO₂越来越受到关注。比较了含3种不同阴离子的常规离子液体([bmim][BF₄]、[bmim][PF₆]、[bmim][Tf₂N])作为支撑液膜的液膜相分离CO₂/CH₄的性能,考察了咪唑环上烷基链长对离子液体支撑液膜性能的影响。考虑向离子液体中引入胺基和羧基等亲CO₂基团,制备了1-丁基-3-甲基咪唑丙氨酸离子液体([bmim][β-Ala]),考察了 [bmim][β-Ala]支撑液膜分离CO₂/CH₄的性能,并对在CO₂渗透测试前后的支撑液膜进行了FT-IR分析,发现氨基酸离子液体中的-NH₂和CO₂的较强作用以及该离子液体的高黏性影响了CO₂的透过性,使[Bmim][β-Ala]支撑液膜的CO₂透过率低。     

Preparation and characterization of symmetric and asymmetric pure polysulfone membranes for CO2 and CH4 separation

Preparation of pure polysulfone (PSf) membrane for CO₂/CH₄ separation was aimed in this study. Accordingly, the effects of different variables such as: type and concentration of alcohol as external nonsolvent in the coagulation bath, solvent type in the casting solution and also presence of butanol (BuOH) as internal nonsolvent in polymer solution were examined. CO₂ and CH₄ permeabilities of prepared membranes in different coagulation baths follow this order: ethanol‐50% (EtOH‐50%) > isopropyl alcohol‐50% (IPA‐50%) > ethanol‐100% (EtOH‐100%) > IPA‐100%. According to scanning electron microscopy photographs, membrane asymmetry decreased in higher concentration of alcohols and a high symmetric membrane was prepared using IPA‐100% as external nonsolvent. CO₂/CH₄ selectivity improved in the following order: IPA‐100% > EtOH‐100% > IPA‐50% > EtOH‐50%. Then, a high CO₂/CH₄ selectivity (36.40) was obtained employing pure IPA in coagulation bath. When a mixture of NMP/THF was used instead of NMP as solvent, CO₂/CH₄ selectivity increased from 7.10 to 18.50. Thickness of membranes decreased from 124.70 to 72.11 μm by addition of BuOH concentration from 0 to 10 wt% as internal nonsolvent. Consequently, an enhancement in gas permeability was observed in higher BuOH concentrations. POLYM. ENG. SCI., 54:1686–1694, 2014. © 2013 Society of Plastics Engineers     

Preparation and characterization of hyperthin-skinned and high performances asymmetric polyethersulfone membrane for gas separation

Defect-free high performance membranes for O₂/N₂ separation were prepared by coating the porous polyethersulphone (PES) membrane of hyperthin-skin layer with silicone rubber. The combined effects of fabrication parameters in dry/wet phase inversion process and of the casting dope rheology enabled improved of membrane performance in O₂ and N₂ separation, i.e. the optimum range was found to be from 149 to 447 s^{− 1} and 10 to 14 s, respectively, for the shear rate and the evaporation time to prepare the hyperthin-skinned asymmetric polyethersulfone membranes. The optimum polymer concentration was 32 wt.% , 61 wt.% and 7 wt.% for PES, 1-methyl-2-pyrrolidone and water respectively. The thinnest skin layer thickness was 538 ± 95.6 Å. Evaporation time and casting shear have been identified as the dominant fabrication parameters in controlling skin layer thickness and skin integrity.     

Polysulfone/zinc oxide nanoparticle mixed matrix membranes for CO2/CH4 separation

Preparation and characterization of novel polysulfone/zinc oxide (PSf/ZnO) mixed matrix membranes (MMMs) with different ZnO loadings for high selective CO₂/CH₄ separation were aimed in this study. Scanning electron microscopy photographs demonstrated that spongy and small tear like pores in plain PSf membrane (0 wt % of ZnO) replaced with large tear like pores close to surface layer by increasing ZnO content up to 0.1 and 1 wt %. In contrast, a dense and less free volume structure was obtained in membranes having 3 and 5 wt % of ZnO. Membrane porosity increased from 28.68 to 50.51% with increasing ZnO content from 0 to 1 wt %. Then, a reduction in porosity was observed for membranes containing 3 and 5 wt % of ZnO. Atomic force microscopy images presented variation in membrane surface roughness. Surface roughness decreased from 67.64 nm for plain PSf to 47.86 nm for membrane containing 1 wt % of ZnO. While, surface roughness increased and reached to 115.5 and 122.4 nm for MMMs having 3 and 5 wt % of ZnO. Gas separation properties of PSf/ZnO MMMs were examined and CO₂/CH₄ selectivity of MMMs containing 3 and 5 wt % of ZnO were 22.29 and 54.29, respectively, in 1 bar feed pressure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39745.     

The preparation of SPEEK/phosphate salts membranes and application for CO2/CH4 separation

SPEEK/phosphate salts membranes were prepared and utilized for CO₂/CH₄ separation. SPEEK with abundant –SO₃H groups and EO groups on polymer chains would be beneficial for CO₂ transport. The doped phosphate salts (NaH₂PO₄, Na₂HPO₄ and Na₃PO₄) with different acid‐base properties increased the water content in the membrane, and water was expected to increase both the solubility and diffusivity of CO₂ in the membrane. All membranes were characterized by FTIR, TGA, and XRD. The CO₂ permeability and CO₂/CH₄ selectivity of SPEEK/Na₃PO₄ membranes were higher than that of SPEEK/NaH₂PO₄ and SPEEK/Na₂HPO₄ membranes. Compared to the pure SPEEK membrane, the CO₂ permeability and CO₂/CH₄ selectivity of SPEEK/Na₃PO₄?10 membrane were increased by 144% and 65%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43399.     

Synthesis and characterization of diethanolamine-impregnated cross-linked polyvinylalcohol/glutaraldehyde membranes for CO2/CH4 separation

In this research, the cross-linking of diethanolamine (DEA) impregnated poly(vinyl alcohol) (PVA) on polytetrafluoroethylene (PTFE) by glutaraldehyde (GA) with different blend compositions (GA/PVA: 0.5, 1, 3, 5, 7 ratio%) was performed in the absence of an acid catalyst and organic solvents in order to avoid any interference in CO₂ facilitation reaction with DEA. The fabricated membranes were characterized by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). Furthermore, the effects of cross-linking agent content, feed pressure and composition as well as stability on CO₂/CH₄ transport properties were investigated in both pure and mixed gas experiments. The cross-linked membranes showed reasonable CO₂/CH₄ permselectivities in comparison with uncross-linked membranes. The best-yield CO₂-selective membranes (DEA-PVA/GA(1 wt%)/PTFE) represented the best CO₂/CH₄ selectivity of 91.13 and 665 for pure and mixed gas experiments, respectively.     

一维直孔道MOFs对CH4/N2和CO2/CH4的分离

非常规天然气未来可以作为常规天然气的有效补充,其中低浓度煤层气和生物质燃气分别需要脱除大量的N₂ 和CO₂以达到富集和纯化CH₄的目的。本研究针对CH₄/N₂这一对较难分离的气体组合,选取了具有一维菱形孔道的MOFs材料Cu(INA)₂作为吸附剂,将合成的样品做了XRD和TG表征,测试了纯气体CO₂、CH₄和N₂的吸附曲线,利用巨正则系综蒙特卡罗(GCMC)分子模拟和理想吸附溶液理论(IAST)计算了气体的吸附热和该材料对于CH₄/N₂和CO₂/CH₄的吸附选择性系数;3 MPa压力下制备的颗粒样品填装吸附分离装置,进行了混合气体CH₄/N₂ (50%/50%)和CO₂/CH₄ (50%/50%)的穿透试验,分离的结果显示,Cu(INA)₂不仅高选择性地吸附CH₄/N₂混合物中的CH₄(S_CH4/N2=10),而且对CH₄/N₂的分离效果优于CO₂/CH₄。     

PBI/Clinoptilolite mixed-matrix membranes for binary (N2/CH4) and ternary (CO2/N2/CH4) mixed gas separation

In this work, polybenzimidazole (PBI)-based mixed matrix membranes (MMMs) with natural zeolite were prepared and their transport properties for binary (N₂/CH₄) and ternary (CO₂/N₂/CH₄) mixed-gas separation were studied. The MMMs, were prepared with PBI as polymeric matrix and Mexican natural zeolite clinoptilolite enriched with cations of Ca²⁺ as filler. The thermal properties analysis of the PBI and MMMs studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) indicates that the MMMs membranes have Tg higher than 350°C and decomposition temperatures above 600°C compared with the pristine membranes. PBI membrane and MMMs were analyzed by X-Ray Diffraction (XRD) and the diffraction patterns showed the zeolite signals combine with the amorphous dome from the polymeric matrix. In addition, the perm-selectivity properties of the polymeric membranes and MMMs were tested with binary (N₂/CH₄; 10/90 mol%) and ternary (CO₂/N₂/CH₄; 5/10/85 mol%) gas mixtures at different pressure rates (50, 150 and 300 psi). The perm-selectivity properties of the MMMs membranes show an improvement in their values about 30% higher compared to the PBI polymeric membranes, favoring the permeation of CO₂ and N₂.     

Membranes for CO2 /CH4 and CO2/N2 Gas Separation

Membrane technology has emerged as a leading tool worldwide for effective CO₂ separation because of its well-known advantages, including high surface area, compact design, ease of maintenance, environmentally friendly nature, and cost-effectiveness. Polymeric and inorganic membranes are generally utilized for the separation of gas mixtures. The mixed-matrix membrane (MMM) utilizes the advantages of both polymeric and inorganic membranes to surpass the trade-off limits. The high permeability and selectivity of MMMs by incorporating different types of fillers exhibit the best performance for CO₂ separation from natural gas and other flue gases. The recent progress made in the field of MMMs having different types of fillers is emphasized. Specifically, CO₂/CH₄ and CO₂/N₂ separation from various types of MMMs are comprehensively reviewed that are closely relevant to natural gas purification and compositional flue gas treatment     

Adsorption of CO2, CH4, CO2/N2 and CO2/CH4 in novel activated carbon beads: Preparation,measurements and simulation

A series of high performance carbonaceous mesoporous materials: activated carbon beads (ACBs), have been prepared in this work. Among the samples, ACB‐5 possesses the BET specific surface area of 3537 m² g^?1 and ACB‐2 has the pore volume of 3.18 cm³ g^?1. Experimental measurements were carried out on the intelligent gravimetric analyzer (IGA‐003, Hiden). Carbon dioxide adsorption capacity of 909 mg g^?1 has been achieved in ACB‐5 at 298 K and 18 bar, which is superior to the existing carbonaceous porous materials and comparable to metal‐organic framework (MOF)‐177 (1232 mg g^?1, at 298 K and 20 bar) and covalent‐organic framework (COF)‐102 (1050 mg g^?1 at 298 K and 20 bar) reported in the literature. Moreover, methane uptake reaches 15.23 wt % in ACB‐5 at 298 K and 18 bar, which is better than MOF‐5. To predict the performances of the samples ACB‐2 and ACB‐5 at high pressures, modeling of the samples and grand canonical Monte Carlo simulation have been conducted, as is presented in our previous work. The adsorption isotherms of CO₂/N₂ and CO₂/CH₄ in our samples ACB‐2 and 5 have been measured at 298 and 348 K and different compositions, corresponding to the pre‐ and postcombustion conditions for CO₂ capture. The Dual‐Site Langmuir‐Freundlich (DSLF) model‐based ideal‐adsorbed solution theory (IAST) was also used to solve the selectivity of CO₂ over N₂ and CH₄. The selectivities of ACBs for CO₂/CH₄ are in the range of 2–2.5, while they remain in the range of 6.0–8.0 for CO₂/N₂ at T = 298 K. In summary, this work presents a new type of adsorbent‐ACBs, which are not only good candidates for CO₂ and CH₄ storage but also for the capture of carbon dioxide in pre‐ and postcombustion processes. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Amine-impregnated natural zeolite as filler in mixed matrix membranes for CO2/CH4 separation

Flat mixed matrix membranes (MMMs) comprising polysulfone and clinoptilolite-type natural zeolite were prepared by casting. Zeolite was modified with three alkylamines: ethanolamine (EA), bis(2-hydroxypropyl)amine (BHPA), and polyethylenimine (PEI) by the impregnation method. Impregnated zeolite samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and N₂ adsorption–desorption. The alkylamine loading extent determined by thermogravimetric analysis was 5.2, 4.8, and 8.5% for EA, BHPA, and PEI, respectively. Analyses of MMMs showed that the incorporation of impregnated zeolite affected the glass-transition temperature (T_g) and mixed-gas transport properties. In this regard, a decreasing trend of the T_g values from 185.5 °C for the polymeric membrane up to 176.6 °C for Clino-EA-based MMM was recorded. In addition, the gas separation performance was evaluated at two different feed pressures. At 50 psi, MMMs showed an enhancement up to 30% on the CO₂ permeability (22.79 Barrer) and 55% on the CO₂/CH₄ selectivity (45.78) in comparison with the polymeric membrane (CO₂ permeability 17.34 Barrer; CO₂/CH₄ selectivity 29.38). These values varied depending on the alkylamine, BHPA being the most selective. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48286.     

Study of CO2 and CH4 Permeation Properties through Prepared and Characterized Blended Pebax-2533/PEG-200 Membranes

This study demonstrates how incorporation of polyethylene glycol (PEG-200) into poly (ether-block-amide) (Pebax-2533) can improve the prepared membrane performance in separating CO₂from CH₄. Additionally, the effect of various PEG-200 loadings on CH₄and CO₂permeability and CO₂/CH₄selectivity values was investigated. The prepared membranes were examined using Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. Permeation experiments of the gasses through the neat Pebax and the blended (Pebax-2533/PEG-200) membranes were carried out at a temperature of 25 ^∘C and pressure range of 2 to 10 bar. The gas permeation experiments indicated that the performance of blended membranes is better than that of the neat membrane. As an example, CO₂permeability and ideal CO₂/CH₄selectivity values for the blended membrane with 40 wt.% of PEG-200 loading are 351.65 and 9.17 Barrer, while those values for the neat membrane are 187.54 and 7.28 Barrer, respectively.

     

The effect of ZIF-90 particle in Pebax/Psf composite membrane on the transport properties of CO2, CH4 and N2 gases by Molecular Dynamics Simulation method

Nowadays, mixed matrix membranes (MMMs) have considered by many researchers to overcome the problems of polymeric membranes. In addition, molecular dynamics (MD) and Monte Carlo (MC) simulation Methods are suitable tools for studying transport properties and morphology in MMMs. For this purpose, in this study using material studio 2017 (MS) software, the transport properties of CO₂, CH₄ and N₂ in Pebax, Psf neat Pebax/Psf composite and Pebax/Psf composite filled with ZIF-90 particles have been investigated. By adding Psf to Pebax matrix, the selectivity of CO₂/CH₄ and CO₂/N₂ gases has significantly increased. In addition, adding ZIF-90 particles to the Pebax/Psf composite increased the permeability of CO₂, CH₄ and N₂ compared to neat and composite membranes. The morphological properties of the membranes, such as the fractional free volume (FFV), radial distribution function (RDF), glass transition temperature (T_G), X-ray diffraction (XRD) and equilibrium density have calculated and acceptable results have obtained.