An atomistic simulation towards molecular design of silica polymorphs nanoparticles in polysulfone based mixed matrix membranes for CO2/CH4 gas separation

Incorporation of inorganic fillers into Polysulfone (PSF) to constitute mixed matrix membranes (MMMs) has become a viable solution to prevail over limitations of the pristine materials in natural gas sweetening process. Nevertheless, preparation of MMMs without defects and empirical investigation of membrane that exhibits characteristic of improved CO₂/CH₄ separation performance at experimental scale are difficult that require prior knowledge on compatibility between the filler and polymer. A computational framework has been conducted to construct validated PSF based MMMs using silica (SiO₂) as inorganic fillers. It is known that nanosized SiO₂ can coexist in varying polymorph configurations (ie, α-Quartz, α-Cristobalite, α-Tridymite) but molecular simulation study of SiO₂ polymorphs to form MMMs is limited. Therefore, this work is a pioneering study to elucidate feasibility in facile utilization of polymorphs to improve gas separation performance of MMMs. Physical properties and gas transport behavior of the simulated PSF based MMMs with different SiO₂ polymorphs and loadings have been elucidated. The optimal MMM has been found to be PSF/25 wt% α-Cristobalite at 55°C. The success in molecular simulation has shed light on how computational tools can provide understandings at molecular level to elucidate compatibility between varying pristine materials to MMMs for natural gas processing.     

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.     

Synthesis,characterization, and performance evaluation of PES/EDA‐functionalized TiO2 mixed matrix membranes for CO2/CH4 separation

Poor adhesion between hydrophobic polymers and hydrophilic inorganic fillers is a challenge that encumbers a high separation performance of mixed matrix membrane (MMM). In this study, Titanium(IV) oxide (TiO₂) nanoparticles were functionalized using ethylenediamine (EDA) before embedment in poly(ether sulfone) (PES) polymer matrix. MMMs were synthesized through dry phase inversion technique. Membranes morphology and nanoparticles dispersion was drastically enhanced posterior amine modification indicating an improved adhesion between the polymer and filler particles. Membranes thermal stability was likewise improved as higher degradation temperatures were perceived for PES/EDA–TiO₂ MMMs. Gas separation evaluation for pure carbon dioxide (CO₂) and methane (CH₄) gases revealed a remarkably enhanced separation performance upon amine‐grafting of TiO₂ as EDA‐TiO₂ MMMs exhibited a higher separation performance as compared to MMMs with pristine TiO₂. The highest ideal separation factor achieved was 41.52 with CO₂ permeability of 10.11 Barrer at an optimum loading of 5% wt of EDA‐TiO₂ which is threefold higher as compared to neat PES membrane and approximately twofold higher than MMMs with pristine TiO₂, respectively, at the same filler loading. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45346.     

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.     

Fabrication of mixed‐matrix membranes with MOF‐derived porous carbon for CO2 separation

Mixed‐matrix membranes (MMMs) have shown great advantages but still face some challenges, such as the trade‐off between permeability and selectivity, stability, and the lack of efficient ways to enhance them simultaneously. Here, the fabrication of MMMs with metal‐organic frameworks derived porous carbons (MOF‐PCs) as fillers which exhibit selective‐facilitating CO₂ transport passage originating from interactions between fillers and CO₂ is showed. With the aid of the developed multicalcination method, MOF‐PCs with variable N‐contents were prepared and incorporated into PPO‐PEG matrix for the first time to prepare MMMs, which show excellent separation performance for CO₂/CH₄ mixture with a tunable separation performance by combining different N‐contents and surface areas of MOF‐PCs. Moreover, the developed MMMs have hydrothermal and chemical stability. This work not only presents a series of MMMs with both good separation properties and stability, it also provides useful information for guiding the fabrication of high performance MMMs for practical application. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3400–3409, 2018     

Effect of the ZIF‐8 Distribution in Mixed‐Matrix Membranes Based on Matrimid® 5218‐PEG on CO2 Separation

In theory, the combination of inorganic materials and polymers may provide a synergistic performance for mixed‐matrix membranes (MMMs); however, the filler dispersion into the MMMs is a crucial technical parameter for obtaining compelling MMMs. The effect of the filler distribution on the gas separation performance of the MMMs based on Matrimid®‐PEG 200 and ZIF‐8 nanoparticles is demonstrated. The MMMs were prepared by two different membrane preparation procedures, namely, the traditional method and non‐dried metal‐organic framework (MOF) method. In CO₂/CH₄ binary mixtures, the MMMs were tested under fixed conditions and characterized by various methods. Finally, regardless of the MMM preparation procedure, the incorporation of 30 wt % ZIF‐8 nanoparticles allowed to increase the CO₂ permeability in MMMs. The ZIF‐8 dispersion influenced significantly the separation factor.     

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.     

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.     

Pebax–polydopamine microsphere mixed‐matrix membranes for efficient CO2 separation

Novel facilitated‐transport mixed‐matrix membrane (MMM) were prepared through the incorporation of polydopamine (PDA) microspheres into a poly(amide‐b‐ethylene oxide) (Pebax MH 1657) matrix to separate CO₂–CH₄ gas mixtures. The Pebax–PDA microsphere MMMs were characterized by Fourier transform infrared spectroscopy, scanning electron microcopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The PDA microspheres acted as an adhesive filler and generated strong interfacial interactions with the polymer matrix; this generated a polymer chain rigidification region near the polymer–filler interface. Polymer chain rigidification usually results in a larger resistance to the transport of gas with a larger molecular diameter and a higher CO₂–CH₄ selectivity. In addition, the surface of PDA microspheres contained larger numbers of amine, imine, and catechol groups; these were beneficial to the improvement of the CO₂ separation performance. Compared with the pristine Pebax membrane, the MMM with a 5 wt % PDA microsphere loading displayed a higher gas permeability and selectivity; their CO₂ permeability and CO₂–CH₄ selectivity were increased by 61 and 60%, respectively, and surpassed the 2008 Robeson upper bound line. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44564.     

Effect of different organic amino cations on SAPO‐34 for PES/SAPO‐34 mixed matrix membranes toward CO2/CH4 separation

Mixed matrix membranes (MMMs) embedded with functionalized SAPO‐34 were successfully synthesized and characterized. Two different types of organic amino cation, namely ethylenediamine (EDA) and hexylamine (HA), were used to functionalize SAPO‐34 particles prior to MMM synthesis. In this work, the effects of different functionalizing agents on the membrane morphology, pore size, and CO₂/CH₄ gas separation properties were investigated. Surface modification of SAPO‐34 was confirmed via X‐ray photoemission spectroscopy (XPS) where the presence of nitrogen atom was observed for the samples functionalized with amino cations. The dispersion of EDA‐functionalized SAPO‐34 particles was found to have better polymer/filler interface morphology as shown by field emission scanning electron microscopy (FESEM) analysis. The gas separation performance revealed that PES containing EDA‐functionalized SAPO‐34 exhibited better CO₂/CH₄ separation performance as compared to the MMMs containing HA‐functionalized SAPO‐34. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43387.     

Study of morphology and gas separation properties of polysulfone/titanium dioxide mixed matrix membranes

Polysulfone (PSf)‐based mixed matrix membranes (MMMs) with the incorporation of titanium dioxide (TiO₂) nanoparticles were prepared. Distribution and agglomeration of TiO₂ in polymer matrix and also surface of membranes were observed by scanning electron microscopy, transmission electron microscopy, and energy dispersive X‐ray. Variation in surface roughness of MMMs with different TiO₂ loadings was analyzed by atomic force microscopy. Physical properties of membranes before and after cross‐linking were identified through thermal gravimetric analysis. At low TiO₂ loadings (≤3 wt%), both CO₂ and CH₄ permeabilities decreased and consequently gas selectivity improved and reached to 36.5 at 3 bar pressure. Interestingly, PSf/TiO₂ 3 wt% membrane did not allow to CH₄ molecules to pass through the membrane and this sample just had CO₂ permeability at 1 bar pressure. Gas permeability increased considerably at high filler contents (≥5 wt%) and CO₂ permeance reached to 37.7 GPU for PSf/TiO₂ 7 wt% at 7 bar pressure. It was detected that, critical nanoparticle aggregation has occurred at higher filler loadings (≥5 wt%), which contributed to formation of macrovoids and defects in MMMs. Accordingly, MMMs with higher gas permeance and lower gas selectivity were prepared in higher TiO₂ contents (≥5 wt%). POLYM. ENG. SCI., 55:367–374, 2015. © 2014 Society of Plastics Engineers     

Preparation and Characterization of Polycarbonate-Blend-Raw/Functionalized Multi-Walled Carbon Nano Tubes Mixed Matrix Membrane for CO2 Separation

Membrane composed of PC as base of polymer matrix with different ratio of multiwall carbon nano tubes (MWCNTs) as nanofillers and poly ethylene glycol (PEG) as second polymer was prepared by solution casting method. Both raw-MWCNTs (R-MWCNTs) and functionalized carboxyle-MWCNTs (C-MWCNTs) were used in membrane preparation. The MWCNTs loading ratio and pressure effects on the gas transport properties of membranes were examined in relation to pure He, N₂, CH₄, and CO₂ gases. Results showed that the use of C-MWCNT instead of R-MWCNTs in mixed matrix membranes (MMMs) fabrication with base of PC provides better performance and also it increases (CO₂/CH₄) and (CO₂/N₂) selectivities to 27.38 and 25.42 from 25.45 and 19.24, respectively (at 5 wt% of MWCNTs). PEG as the second rubbery polymer was utilized to improve the separation performance and mechanical properties. In blend MMMs, highest (CO₂/CH₄) selectivity at 2 bar pressure increased to 35.64 for PC/PEG/C-MWCNT blend MMMs which was 27.28 for PC/MWCNTs MMMs at 10 wt%. Increase of feed pressure led to gas permeability and gas pair selectivity improvement in approximately all of membranes. Analysis of mechanical properties showed improvement in tensile modules with the increase of MWCNTs loading ratio and use of PEG in prepared MMMs.     

Preparation and characterization of mixed matrix membranes based on poly(vinylidene fluoride) and zeolite 4A for gas separation

Zeolite 4A was incorporated into poly(vinylidene fluoride) (PVDF) matrix to prepare mixed matrix membranes (MMMs). The objective of this study was to investigate the effects of the inorganic filler on the structural properties of the MMMs. The resulting membranes were characterized using thermogravimetric analysis, differential scanning calorimetry, X‐ray diffraction, contact angle tests, and scanning electron microscopy (SEM). The mechanical properties of the membranes were determined using a tensile stress–strain machine. To fully study the interface properties between the inorganic fillers and polymer chains, the densities of the membranes were experimentally determined and compared with the theoretical values. The experimental densities of the composite membranes were lower than those of the theoretical values. The void volume fractions were calculated accordingly. The single gas (He, CO₂, O₂, and N₂) permeabilities of the resulting membranes were carried out. The highest permeabilities of 14.65, 6.62, 1.01, and 0.3 Barrer for He, CO₂, O₂, and N₂, respectively, were obtained by PVDF/4A 32% composite membrane; whereas the highest selectivities of 105.5, 31.5, and 3.3 for He/N₂, CO₂/N₂, and O₂/N₂, respectively, were obtained using PVDF/4A 16% composite membrane. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Flow behaviour and microstructure evolution in novel SiO2/PP/LCP ternary composites: effects of filler properties and mixing sequence

When silica (SiO₂) fillers were introduced into the polypropylene (PP) and liquid‐crystalline polymer (LCP) blend, it was found that the mixing sequence, the filler size, and the filler surface nature affected the rheology of the composites and the morphology of the LCP phase in the ternary composite. In particular, the compatibility between the filler and the PP matrix was found to exert a strong influence on the droplet‐fibril transition. The incorporation of the hydrophobic silica to the LCP/PP blend facilitated the fibrillation of LCP because the hydrophobic filler demonstrated affinity towards the hydrophobic PP matrix. The preferential residence of the hydrophobic silica in the PP phase would minimise the LCP domain disruption leading to the formation of LCP fibrils with high aspect ratios. The use of fine filler and in situ blending, which promoted the filler–LCP interaction, could prevent coalescence, inhibit deformation and hinder fibril development as well. © 2003 Society of Chemical Industry     

Effective gas separation through graphene oxide containing mixed matrix membranes

In the present study, graphene oxide (GO) was incorporated into poly(vinylidene fluoride) (PVDF) and chemically modified PVDF (M‐PVDF) to prepare mixed matrix membranes (MMMs) for gas separation application. Performed analyses proved appropriate dispersion of exfoliated GO sheets in polymer matrices and sufficient compatibility at the interfacial phases. M‐PVDF based MMMs were thermally and mechanically more stable relative to the PVDF‐based MMMs. The oxygen containing functional groups in M‐PVDF was probably the main reason for this more stability. PVDF/GO MMMs rendered low gas permeability and high selectivity. Both impermeable GO sheets and crystalline phases of PVDF were responsible for such behavior. On the other hand, interestingly gas permeability of M‐PVDF/GO MMMs was enhanced while no substantial decline was recorded in gas selectivity. For instance, He and CO₂ permeability was increased 12.46% and 25.89%, respectively, compared to the pure PVDF membrane. This behavior originated from functional groups of M‐PVDF and the interaction of these groups with GO sheets. Since GO often amplified gas barrier properties of polymers, such increscent would be appreciable. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46271.     

Poly(vinyl alcohol)/ZIF‐8‐NH2 mixed matrix membranes for ethanol dehydration via pervaporation

Ethanediamine‐modified zeolitic imidazolate framework (ZIF)‐8 particles (ZIF‐8‐NH₂) is synthesized and incorporated in the poly(vinyl alcohol) (PVA) matrix to fabricate novel PVA/ZIF‐8‐NH₂ mixed matrix membranes (MMMs) for pervaporation dehydration of ethanol. The PVA/ZIF‐8‐NH₂ MMMs exhibit enhanced membrane homogeneity and separation performance because of the higher hydrophilicity and restricted agglomeration of the particles, as compared to corresponding MMMs loaded with unmodified particles. The effect of ZIF‐8‐NH₂ loading in the MMMs is studied and the MMM with a 7.5 wt % ZIF‐8‐NH₂ loading shows the best pervaporation performance for ethanol dehydration at 40°C. Various characterization techniques (Fourier transform infrared, scanning electron microscope, contact angle, sorption test, etc.) are used to investigate the MMMs loaded with ZIF‐8 and ZIF‐8‐NH₂ particles. The impact of operation conditions on pervaporation performance is also performed. The performance benchmarking shows that the MMMs have superior separation factors and comparable flux to most other PVA hybrid membranes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1728–1739, 2016     

混合基质膜在碳捕集领域的研究进展

膜分离技术因其低成本、低能耗及高效率的优势被认为是最具有前景的碳捕集技术之一。混合基质膜结合了有机材料与无机材料两方面的优势，是同时提升渗透性和选择性的有效手段。本文从气体在混合基质膜中的传递机制出发，以常见的无孔型与多孔型无机填料为基础，总结了近年来混合基质膜在二氧化碳捕集领域的研究进展，介绍了不同类型的填料在高分子基质中所起到的微结构调节作用，并着重阐述了在混合基质膜制备过程中无机填料与高分子基质之间所存在的相容性问题及其解决方法。最后，提出混合基质膜应在继续致力于填料结构设计、填料分散、构效关系等方面的同时，加强二维填料、微囊填料和促进传递机制等方面的研究。     

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.     

Enhanced compatibility and selectivity in mixed matrix membranes for propylene/propane separation

Mixed matrix membranes (MMMs) based on metal–organic framework (MOF) have great promising application in separation of gas mixtures. However, achieving a good interfacial compatibility between polymer and MOF is not straightforward. In this work, focusing on one of the most challenging olefin/paraffin separations: propylene/propane (C₃H₆/C₃H₈), we demonstrate that modification of the MOF filler via dopamine polymerization using a double solvent approach strongly improves interfacial compatibility. The resulting membranes show an outstanding separation performance and long-term stability with propylene permeability nearly 90 Barrer and propylene/propane selectivity close to 75. We anticipate that similar MOF modification strategies may help solve the problem of interface defects in the manufacture of MMMs and be extended to other porous fillers.     

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.