Preparation and characterization of CO2-selective Pebax/NaY mixed matrix membranes

CO₂-selective Pebax/NaY mixed matrix membranes (MMMs) were prepared by incorporating NaY zeolite into Pebax matrix. The morphology, chemical groups, thermal stability, and microstructure of the MMMs were investigated by scanning electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction, respectively. The effects of zeolite loading amount, permeation temperature and pressure on the CO₂/N₂ separation performance of the resultant membranes were studied. The as-prepared MMMs are much superior to the pristine Pebax membranes in terms of permeability and selectivity. The CO₂ permeability and CO₂/N₂ selectivity can respectively reach to 131.8 Barrer and 130.8 for MMMs made by the starting materials containing 40 wt % NaY. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48398.     

Enhanced CO2 selectivity of polyimide membranes through dispersion of polyethyleneimine decorated UiO-66 particles

Branched polyethyleneimine (PEI) functionalized UiO-66 were synthesized and used as fillers to fabricated mixed-matrix membranes (MMMs) for CO₂/CH₄ separation. The purpose of introducing amino-functional groups in the filler is to improve the interfacial compatibility of the filler with the polymer through the formation of hydrogen bonds with the carbonyl group of 6FDA-ODA. Additionally, the amino group can facilitate CO₂ transport through a reversible reaction, enhancing the CO₂/CH₄ separation properties of MMM. The chemical structure and morphology of fillers and membranes were characterized by employing X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), thermogravimetric (TGA), Derivative thermogravimetry (DTG) and scanning electron microscope (SEM). Furthermore, the effects of filler loading and feed pressure on CO₂ permeability and CO₂/CH₄ selectivity have been investigated. MMMs present higher gas separation performance than pure 6FDA-ODA due to the presence of amino groups and the improvement of interface morphology. In particular, the MMM with 15 wt% loading of UiO-66-PEI shows optimum CO₂ permeability of 28.23 Barrer and CO₂/CH₄ selectivity of 56.49. Therefore, post-synthetic modification of UiO-66 particle with PEI is a promising alternative to improved membrane performance.     

Fabrication of Pebax/SAPO mixed matrix membranes for CO2/N2 separation

Mixed matrix membranes (MMMs) were prepared by solvent evaporation method using Pebax-1074 polymer as matrix and inorganic zeolite SAPO-23 as dopant. The morphology, surface functional groups, microstructure, thermal stability, and separation performance of MMMs were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and gas permeation, respectively. The effects of dopant loading amount, permeation temperature, and permeation pressure on the structure and properties of MMMs were investigated. The results showed that the introduction of SAPO zeolite reduced the crystallinity of the MMMs and improved the CO₂/N₂ selectivity. Under the conditions of 30°C and 0.15 MPa, the MMMs prepared by incorporating with 5% SAPO zeolite in content exhibited the highest CO₂/N₂ selectivity of 72.0 together with the CO₂ permeability of 98.2 Barrer.     

Fabrication and testing of mixed matrix membranes of UiO-66-NH2 in cellulose acetate for CO2 separation from model biogas

Mixed Matrix Membranes (MMMs) of UiO-66-NH₂ nanoparticles dispersed in Cellulose Acetate (CA) were prepared with filler loading of 2–20 wt%. MMMs were tested for the upgradation of model biogas (60%–40%) mixture of CH₄/CO₂ at a feed pressure of 2 bar and 1.5 bar. Detailed characterization of MMMs was performed with Fourier transform infrared spectroscopy (FTIR), Thermo-gravimetric analysis (TGA), Differential scanning calorimetry (DSC), and Field emission scanning electron microscopy (FESEM) to investigate the physical and thermal properties. MMMs formed are defects-free, voids-free, and without polymer rigidification, indicating a better filler polymer interface. MMMs showed improved CO₂ permeability while retaining the CO₂/CH₄ selectivity. The 10 wt.% UiO-66-NH₂/CA MMM showed optimum gas separation performance with CO₂ permeability of 11 Barrer and CO₂/CH₄ selectivity of 10. The UiO-66-NH₂/CA MMMs performed better when compared to the pure CA membrane. The experimental permeability and selectivity data were compared with the predicted data using Maxwell, Lewis–Nielsen, Higuchi, and Bruggeman's model.     

Accelerating CO2 capture of highly permeable polymer through incorporating highly selective hollow zeolite imidazolate framework

The implementation of high-performance membranes in large-scale CO₂ capture has the potential to significantly decrease the capture cost and reduce the environmental footprints. However, highly permeable polymers rarely have sufficient selectivity for energy-efficient carbon capture. In this study, zeolite imidazolate framework hollow nanoparticles (ZIF-HNPs) were synthesized and embedded into highly permeable polymers as versatile fillers to prepare mixed matrix membranes (MMMs). The interior hollow architecture minimizes transport resistance of gas diffusion through the fillers while its molecular-sieving shell provides high selectivity. With 28 vol% loading of ZIF-HNPs, the membrane exhibits CO₂ permeability of 7,128 Barrer and CO₂/CH₄ selectivity of 16.4 (57.7% and 31.4% higher than these of pristine membrane), which surpass the upper bound of the state-of-the-art reported polymeric membranes. Meanwhile, we proposed a modified Maxwell model based on the hierarchical structure of the MMM to analyze the effects of cavity size and loading on gas transport behaviors within membranes.     

Methoxy poly (ethylene glycol) methacrylate-TiO2/poly (methyl methacrylate) nanocomposite: an efficient membrane for gas separation

Polymer/nanoparticle mixed matrix membranes (MMMs) is one of the most important topics in gas separation field. In this study, to improve gas separation efficiency, methoxy poly(ethylene glycol) methacrylate (MPEG) was grafted on TiO₂ surface and was used for synthesis of poly (methyl methacrylate) (PMMA) MMMs. Gas permeation and separation properties of PMMA/PMPEG-TiO₂ MMMs were studied for CO₂, CH₄, O₂, and N₂ gases. The results showed that the MMM filled with 5 wt% PMPEG-TiO₂ nanoparticle exhibited optimal separation performance with CO₂ permeability of 32.48 Barrer and CO₂/N₂ selectivity of 56.98, which are higher than pure polymer (2.75 Barrer and 36.71).     

Efficient CO2 Separation Using a PIM-PI-Functionalized UiO-66 MOF Incorporated Mixed Matrix Membrane in a PIM-PI-1 Polymer

Metal–organic framework (MOF) incorporated mixed–matrix membranes (MMMs) attract great interest for gas separation applications because they overcome limitations faced by typical polymer membranes, including permeability–selectivity trade-off, aging effect, and plasticization phenomenon. However, optimal MOF–polymer interface compatibility is the key challenge in fabricating defect-free high-performance gas-separation MMMs. Here, a surface modification strategy of the UiO-66-NH₂ MOF using a covalently bound PIM-PI-oligomer is developed to engineer interface compatibility with the polymer that has an identical chemical structure (PIM-PI-1) in the MMMs. A series of MMMs are prepared with different loadings of homogeneously distributed PIM-PI-functionalized MOFs (PPM). Significant improvements in CO₂/N₂ and CO₂/CH₄ selectivity and permeability are achieved with these MMMs, ranging from 5 to 10 wt% of the PPM loadings. The MMM with 10 wt% loading (PPM-10@MMM) shows a CO₂ permeability of 3827.3 Barrer and a CO₂/N₂ and CO₂/CH₄ selectivity of 24 and 13.4, respectively. This surpasses the 2008 Robeson upper bound for CO₂/N₂ and is very close to the 2008 upper bound for CO₂/CH₄. The experimental results are further compared using Maxwell's equation for MMMs. The resulting MMMs show a plasticization resistance against CO₂ up to 25 atm pressure and anti-aging performance for 180 h.     

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.     

High speed spin coating in fabrication of Pebax 1657 based mixed matrix membrane filled with ultra-porous ZIF-8 particles for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation

Modified ultra-porous ZIF-8 particles were used to prepare novel ZIF-8/Pebax 1657 mixed matrix membranes (MMMs) on PES support for separation of CO₂ from CH₄ using spin coating method. TEM and SEM were used to characterize modified ZIF-8 particles. SEM was also used to investigate the morphology of synthesized MMMs. The MMMs with thinner selective layer showed higher CO₂ permeability and lower CO₂/CH₄ selectivity in permeation tests compared to MMMs with thicker selective layer. The plasticization was recognized as the main reason for rise in CO₂ permeability and drop in CO₂/CH₄ selectivity of thinner MMMs. The gas sorption results showed that the high permeability of CO₂ in MMMs is mainly due to the high solubility of this gas in MMMs, leading to high CO₂/CH₄ solubility selectivity for MMMs. The fractional free volume and void volume fraction of MMMs increased as the thickness of membrane decreased. Applying higher mixed feed pressures and permeation tests temperatures resulted in increase in CO₂ permeability and decrease in CO₂/CH₄ selectivity. At highest testing temperature (60 °C), the CO₂ permeability of synthesized MMMs with thinner selective layer remarkably increased.     

Tuning the gas separation performance of fluorinated and sulfonated PEEK membranes by incorporation of zeolite 4A

Mixed matrix membranes (MMMs) containing fluorinated‐sulfonated poly(ether ether ketone) (F‐SPEEK) and zeolite 4A filler, were prepared by solution casting. F‐SPEEK with a fixed degree of sulfonation (40%) was used for membrane synthesis. The SEM pictures showed good interfacial adhesion between filler particles and polymer, which was also confirmed by the increase in glass transition temperature of MMMs with increase in filler particles. Pure and mixed gas permeation experiments were carried out to investigate the potential of this membrane material. The results revealed that addition of zeolite 4A fillers enhanced both permeability and selectivity owing to the intrinsic nature of polymer and modified membrane morphology due to filler. The highest permeability obtained for CO₂ at 30% filler loading was 49.2 Barrer, while highest selectivities obtained for CO₂/CH₄ and CO₂/N₂ were 55 and 58 compared to 47 and 51 for the unfilled polymer, respectively. Intrinsic CO₂ solubility of F‐SPEEK was observed to be decreased from 10.7 to 1.9 (10^?2) cm³ (STP)/cm³ cmHg with the addition of Zeolite 4A. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45952.     

Effect of gas permeation temperature and annealing procedure on the performance of binary and ternary mixed matrix membranes of polyethersulfone,SAPO‐34, and 2‐hydroxy 5‐methyl aniline

This study investigated the effect of annealing time and temperature on gas separation performance of mixed matrix membranes (MMMs) prepared from polyethersulfone (PES), SAPO‐34, and 2‐hydroxy 5‐methyl aniline (HMA). A postannealing period at 120°C for a week extensively increased the reproducibility and stability of MMMs, but for pure PES membranes no post‐annealing was necessary for stable and reproducible performance. The effect of operation temperature was also investigated. The permeabilities of H₂, CO₂, and CH₄ increased with increasing permeation temperature from 35°C to 120°C, yet CO₂/CH₄ and H₂/CH₄ selectivities decreased. PES/SAPO‐34/HMA ternary and PES/SAPO‐34 binary MMMs exhibited the highest ideal selectivity and permeability values at all temperatures, respectively. For H₂/CO₂ pair, when temperature increased from 35°C to 120°C, selectivity increased from 3.2 to 4.6 and H₂ permeability increased from 8 to 26.5 Barrer for ternary MMM, demonstrating the advantage of using this membrane at high temperatures. The activation energies were in the order of CH₄ > H₂ > CO₂ for all membranes. PES/SAPO‐34/HMA membrane had activation energies higher than that of PES/SAPO‐34 membrane, suggesting that HMA acts as a compatibilizer between the two phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40679.     

Fabrication of Homogenous Polymer‐Zeolite Nanocomposites as Mixed‐Matrix Membranes for Gas Separation

Interfacial void‐free mixed‐matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano‐zeolites and tested for gas separation purposes. Fabrication of a void‐free polymer‐zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO₂/N₂ and CO₂/CH₄ selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO₂/CH₄ and CO₂/N₂ at the three examined feed pressures of 4, 8 and 12 atm.     

Mixed matrix membranes based on 6FDA polyimide with silica and zeolite microsphere dispersed phases

Mixed matrix membranes (MMMs) prepared with 6FDA‐DAM polymer using ordered mesoporous silica MCM‐41 spheres (MSSs), Grignard surface functionalized MSSs (Mg‐MSSs) and hollow zeolite spheres are studied to evaluate the effects of surface modification on performance. Performance near or above the so‐called permeability‐selectivity trade‐off curve was achieved for the H₂/CH₄, CO₂/N₂, CO₂/CH_4, and O₂/N₂ systems. Two loadings (8 wt % and 16 wt %) of MSSs were tested using both constant volume and Wicke–Kallenbach sweep gas permeation systems. Besides single gas H₂, CO₂, O₂, N₂, and CH₄ tests, mixed gas (50/50 vol %) selectivities were obtained for H₂/CH₄, CO₂/N₂, CO₂/CH₄, and O₂/N₂ and found to show enhancements vs. single gases for CO₂ including cases. Mg‐MSS/6FDA‐DAM was the best performing MMM with H₂/CH₄, CO₂/N₂, CO₂/CH₄, and O₂/N₂ separation selectivities of 21.8 (794 Barrer of H₂), 24.4 (1214 Barrer of CO₂), 31.5 (1245 Barrer of CO₂), and 4.3 (178 Barrer of O₂), respectively. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4481–4490, 2015     

Mixed matrix membranes containing polymer-embedded metal-organic framework microspheres

The controlling filler aggregation and strengthening interfacial interaction are of great scientific significance for mixed matrix membranes (MMMs). In this study, the polymer-embedded metal-organic framework (pMOF) microspheres (MSs) are designed by one-pot synthesis and employed as microfillers for improving separation performance of MMMs. Through adding polymer during solvothermal crystallization, the polymer chains are embedded into the MOF materials, and the morphologies of the MOFs are transformed from nanopaticles to polycrystalline MSs. Since the embedding of the identical polymer promotes the compatibility of polymeric matrixes and fillers, as well as the micrometer-sized porous MSs offer additionally superior and permanent transport pathways, the resulted MMMs display simultaneously enhanced selectivity and permeability for carbon capture. The CO₂/CH₄ selectivity and CO₂ permeability of the pMOF MMMs are achieved at 1.3 and 2.2 times as those of the pure polymeric membranes, and 1.5 and 1.2 times as those of the MOF MMMs, respectively.     

Fabrication and characterization of silica modified polyimide–zeolite mixed matrix membranes for gas separation properties

In this study, new monomers having silica groups were synthesized as an intermediate for the preparation of poly(imide siloxane)-zeolite 4A and 13X mixed matrix membranes (MMMs). The effects of membrane preparation steps, zeolite loading, precursor’s composition, and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. The new diamine monomer was prepared from 3,5-diaminobenzoic acid (3,5-DABA), 3-aminopropyltrimethoxysilane (3-APTMS), and zeolite 4A and zeolite 13X in N-methyl-2-pyrollidone (NMP) at 180 °C. Poly(imide siloxane)-zeolite 4A and 13X MMMs were synthesized from pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) in NMP using a two-step thermal imidization. SEM images of the MMMs show the interface between polymer and zeolite phases getting closer when surface modified zeolite is used. The increase in glass transition temperature (T _g) confirms the polymer chain becoming more rigid induced by the presence of zeolite. The experimental results indicated that a higher zeolite loading resulted in a decrease in gas permeability and an increase in gas pair selectivity. In terms of O₂ and N₂ permeance and ideal selectivity, the separation performances of poly(imide siloxane)-zeolite MMMs were related to the zeolite type and zeolite pore dimension.     

A novel ternary mixed-matrix membrane comprising Pebax-1657, [HMIM][NTf2] IL,and Al2O3 nanoparticles for efficient CO2 separation

An innovative technique to efficiently remove CO₂ involves introducing a third component with a positive affinity with CO₂ into a binary mixed-matrix membrane (MMM) and eliminating interfacial defects in its structure. In this research, novel ternary MMMs (TMMMs) were synthesized by embedding 1–Hexyl–3–methylimidazolium bis(trifluoromethylsulfonyl)imide ([HMIM][NTf₂]) ionic liquid (IL) and aluminum oxide (γ–Al₂O₃) nanoparticles into poly (ether-block-amide) (Pebax-1657) matrix for enhancing CO₂ removal from light gases. FESEM, DSC, ATR-FTIR, and XRD analyses were used to evaluate the fabricated MMMs structurally. The permeation tests of gases (CH₄, N₂, and CO₂) through prepared membranes were conducted at 25°C and 4, 6, 8, and 10 bar pressures. In accordance with the permeation outcomes, the ternary MMMs exhibited enhanced CO₂ separation performances compared to the unloaded polymeric membrane. Also, the optimized MMM comprising 10 wt.% of the IL and 6 wt.% of the nanoparticles obtained a CO₂ permeability of 173.90 Barrer, as well as CO₂/N₂ and CO₂/CH₄ selectivities of 77.98 and 24.29 at 10 bar and 25°C, which are higher by about 51%, 23%, and 22%, respectively than those of the pristine polymeric membrane. Based on these results, the prepared membrane appears to be a promising choice for separating CO₂ from light gases.     

Preparation and characterization of SAPO-34 – Matrimid 5218 mixed matrix membranes for CO2/CH4 separation

Different SAPO-34 zeolite loaded Matrimid^® 5218 mixed matrix membranes (MMMs) were prepared by solution casting method and characterized using XRD and SEM analysis. Findings showed that semi crystalline neat polymer becomes more crystalline after thermal treatment at higher temperatures close to Matrimid^® 5218 glass transition temperature. Furthermore, incorporation of crystalline filler particles of SAPO-34 zeolite resulted in more and more crystallinity of the MMMs. SEM images also exhibited acceptable contacts between the filler particles and the polymer chains. Permeation measurement showed that CO₂ permeabilities and CO₂/CH₄ selectivities of the MMM with 20 wt% loading of SAPO-34 zeolite particles up to 6.9 (Barrer) and 67, respectively. This can be attributed to size discrimination of SAPO-34 pores that falls between CO₂ and CH₄ kinetic diameters.     

Effect of fractional free volume and Tg on gas separation through membranes made with different glassy polymers

The aim of this work is to study how the characteristics of the polymer used to manufacture gas separation membranes influence its permeability and selectivity. It has been shown that the gas diffusivity decreases with the kinetic diameter of the gas except for CO₂, probably due to its high condensability. While solubility increases with the gas condensation temperature and clearly with the glass transition temperature of the polymer for each gas. The permeabilities of CO₂, CH₄, O₂, N₂ increase for increasing glass transition temperatures. Nevertheless only the selectivity of CO₂ versus the other gases increases significantly when polymers with high glass transition are used. The Robeson limit in a selectivity‐versus‐permeability plot is approached for CO₂/CH₄ when T_g increases. This distance to the Robeson limit, for this pair of gases, results to decrease for increasing T_g. For the case of the O₂/N₂ selectivity remains approximately constant with an appreciable increase in permeability for polymers with increasing T_g. Permeability increases due to the corresponding increase in fractional free volume, FFV, that appears for increasing glass transition temperatures, T_g. This correlation of FFV with T_g has been confirmed by obtaining FFV by different methods. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Carbon molecular sieve gas separation membranes based on an intrinsically microporous polyimide precursor

We report the physical characteristics and gas transport properties for a series of pyrolyzed membranes derived from an intrinsically microporous polyimide containing spiro-centers (PIM-6FDA-OH) by step-wise heat treatment to 440, 530, 600, 630 and 800 °C, respectively. At 440 °C, the PIM-6FDA-OH was converted to a polybenzoxazole and exhibited a 3-fold increase in CO₂ permeability (from 251 to 683 Barrer) with a 50% reduction in selectivity over CH₄ (from 28 to 14). At 530 °C, a distinct intermediate amorphous carbon structure with superior gas separation properties was formed. A 56% increase in CO₂-probed surface area accompanied a 16-fold increase in CO₂ permeability (4110 Barrer) over the pristine polymer. The graphitic carbon membrane, obtained by heat treatment at 600 °C, exhibited excellent gas separation properties, including a remarkable CO₂ permeability of 5040 Barrer with a high selectivity over CH₄ of 38. Above 600 °C, the strong emergence of ultramicroporosity (<7 Å) as evidenced by WAXD and CO₂ adsorption studies elicits a prominent molecular sieving effect, yielding gas separation performance well above the permeability-selectivity trade-off curves of polymeric membranes.     

Highly permselective MIL‐68(Al)/matrimid mixed matrix membranes for CO2/CH4 separation

With global appeal to green and efficient utilization of energies, metal‐organic frameworks based mixed matrix membranes are standing out in applications such as gas and liquid separation because of the integration of size/shape selectivity of MOFs with processability and mechanical stability of polymers. In the present work, a novel MIL‐68(Al) (MIL = Material of Institute Lavoisier) based mixed matrix membrane (MMM) was developed by adding porous MIL‐68(Al) into Matrimid for the separation of CO₂/CH₄ mixture. The MIL‐68(Al)/Matrimid MMM displays a high CO₂ permselectivity. For the separation of an equimolar CO₂/CH₄ mixture at 373 K and 1 bar, the CO₂ permeability and the CO₂/CH₄ selectivity are 284.3 Barrer and 79.0, respectively, which far exceed the Robeson upper bound limit and those of the previously reported MMMs. Both the operation pressure and temperature have great influence to the separation performance of the MIL‐68(Al)/Matrimid MMM. Further, the MIL‐68(Al)/Matrimid MMM shows a high stability in the long‐term separation of CO₂/CH₄. These properties recommend the MIL‐68(Al)/Matrimid MMM as a promising candidate for the purification of natural gases. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43485.