• Membrane and Water Treatment
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• v.14 no.4
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• pp.175-180
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• 2023

Mixed matrix membranes (MMMs) can be a promising alternative for the solution of dye removal from coloured effluents. Polymeric membranes are widely used due to their good film-forming ability, flexibility, separation properties, and cost. However, they have low mechanical, chemical, and thermal resistances. Moreover, the fouling of polymeric membranes is high because of their hydrophobic nature. Hence, there is an increasing interest in organic-inorganic hybrid membranes as a new-generation membrane material. It has been shown that carbon nanotubes have the potential to increase the material properties of polymers with their low density, high strength, hardness, and exceptional aspect ratio. In this work, carbon nanotubes blended MMMs were prepared and methyl orange removal efficiency of them was investigated. Compared to the bare membranes, MMMs showed not only increased hydrophilicity, water content, and pure water flux but also increased methyl orange rejection and flux recovery

• Membrane Journal
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• v.23 no.6
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• pp.432-438
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• 2013

Mixed-matrix membranes (MMMs) containing MIL-100(Fe), a MOF type, were fabricated in this study. MMMs up to 30 wt% MOF loading were prepared, and their gas permeabilities were tested. $H_2$, $CO_2$, $O_2$, $N_2$, and $CH_4$ gas permeabilities increased with the MOF loading, while $SF_6$, the largest kinetic diameter in this study, exhibited reduction of gas permeability with the loading. Ideal gas selectivity of $N_2/SF_6$ improved by 40% as compared with pure polyimide membrane, suggesting the proposed MMMs were suitable for $N_2/SF_6$ separation.

• Applied Chemistry for Engineering
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• v.34 no.3
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• pp.213-220
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• 2023

Mixed-matrix membranes (MMMs), which are composed of a polymer matrix filled with high-performance fillers as a dispersed phase, have been intensively studied for gas separations for the past 30 years. It has been demonstrated that MMMs exhibit superior gas separation performance compared to polymer membranes and are more scalable than polycrystalline membranes. Despite their potential, the commercialization of MMMs has yet to be reported due to several challenging issues. One of the major challenges of MMMs is the non-ideal interface between the continuous polymer phase and dispersed phase, which can result in defect formation (i.e., interfacial voids, etc.). With respect, many MMM studies have focused on addressing the issues through scientific approaches. The engineering approaches for facile and effective large-scale fabrication of MMMs, however, have been relatively underestimated. In this review paper, a novel strategy for fabricating MMMs in a facile and scalable manner using in situ metal-organic framework (MOF) formation is introduced. This new MMM fabrication methodology can effectively address the issues facing current MMMs, likely facilitating the commercialization of MMMs.

• Membrane Journal
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• v.25 no.5
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• pp.373-384
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• 2015

In the past few decades, polymeric membrane has played an important role in gas separation applications. For the separation of $CO_2$, one of greenhouse gases, high permselectivity, long-term stability and scale-up are needed. However, conventional polymeric membranes have shown a trade-off relation between permeability and selectivity while inorganic materials are highly permeable but expensive. Mixed matrix membranes (MMMs) combining the advantages of both polymeric and inorganic materials have become a possible breakthrough for the next-generation gas separation membranes. The MMMs could be either symmetric or asymmetric but the latter is more preferred to improve the permeance. Important factors influencing the MMM fabrication include homogeneous distribution of inorganic particles and good interfacial contact between inorganic filler and organic matrix. Recently, metal organic frameworks (MOFs) have received much attention as a new class of porous crystalline materials and a potential candidate for $CO_2$ separation. Zeolitic imidazolate frameworks (ZIFs), a sub-branch of MOFs, are the most widely used in MMMs due to small particle size and appropriate pore size for $CO_2$ separation. One of the major issues associated with the incorporation of porous particles in a polymeric membrane is to control the microstructure of the porous particle materials such as particle size, orientation, and boundary conditions etc. In this review, major challenges surrounding MMMs and the strategies to tackle these challenges are given in detail.

• Membrane and Water Treatment
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• v.10 no.2
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• pp.165-178
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• 2019

Mixed matrix membranes (MMMs) of poly (vinyl alcohol) (PVA) containing certain amounts of H-${\beta}$ zeolite for pervaporation were manufactured by using a solution casting protocol. These zeolite-embedded membranes were then characterized with scanning electron microscope (SEM), X-ray diffraction (XRD) and swelling tests. The membrane separation performance has been examined by means of isopropanol (IPA) dewatering from its highly concentrated aqueous solutions via response surface methodology (RSM). The results have demonstrated that the influences of feed IPA composition (85-95 wt.%), feed temperature ($50-70^{\circ}C$), zeolite loading (15-25 wt.%) and their interactive influences are all statistically significant on both pervaporation flux ($398-1228g/m^2{\cdot}h$) and water/isopropanol separation factor (617-2001). The quadratic models based on the RSM analysis have performed excellently to correlate experimental data with very high determination coefficients and very low relative standard deviations. The optimal pervaporation predictions given by using the RSM models demonstrate a total flux of $953g/m^2{\cdot}h$ and separation factor of 1458, and are excellently verified by experimental results. As reflected by these results, PVA MMMs embedded with hydrophilic $H-{\beta}$ zeolite entities have performed considerably better than its pure counterpart and indicated great potential for isopropanol dehydration applications.

• Membrane Journal
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• v.28 no.1
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• pp.55-61
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• 2018

With vigorous development of petroleum and chemical industry, emission of carbon dioxide has attracted tremendous attention globally due to global warming problem and abnormal climate change. To address these problems, in this study, a PEGBEM-g-POEM graft copolymer with high $CO_2$ affinity was synthesized and $CaCO_3$ was incorporated to form mixed matrix membranes (MMMs) for enhancement of $CO_2$ permeance. By varying the addition weight of $CaCO_3$ in MMMs, high separation performance of $CO_2$ over $N_2$ was obtained. At 50 wt% loading of $CaCO_3$, the greatest separation performance was obtained with an enhanced $CO_2$ permeance from 22.5 to 28.16 GPU and slightly increased $CO_2/N_2$ selectivity from 44.7 to 45.42. It resulted from the increased $CO_2$ solubility of MMMs due to specific interaction between $CaCO_3$ and $CO_2$ molecules. Upon excess loading of $CaCO_3$, MMMs exhibited loss of $CO_2$ separation performance due to the formation of interfacial defects. Based on this result, it is considered that the proper addition of $CaCO_3$ is crucial for improvement of $CO_2$ separation performance.

• Membrane Journal
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• v.30 no.5
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• pp.319-325
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• 2020

In this study, we developed mixed matrix membranes by blending thermoplastic elastomer, i.e. polystyreneblock-polybutadiene-block-polystyrene (SBS) block copolymer with the synthesized UiO-66 particles for CO₂/N₂ gas separation. To investigate the effect of UiO-66 particles in the SBS matrix, we prepared different mixed matrix membranes (MMMs) by varying the mass ratio of SBS and UiO-66 in the blend. To fabricate well-dispersed UiO-66, the SBS/UiO-66 mixture was sonicated and stirred thoroughly. The physico-chemical properties of prepared membranes were characterized by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM). The gas separation performance was measured by time-lag method. The permeability of the MMMs increased significantly as the content of UiO-66 increased, but the CO₂/N₂ selectivity did not decrease significantly. The membranes containing 20% of UiO-66 particles showed the best performance with the CO₂ permeability and CO₂/N₂ selectivity of 663.8 barrer and 13.3, respectively. This result showed performance closer to upper bound than pure SBS membrane in the Robeson plot, as the added UiO-66 particles did not significantly sacrifice selectivity and more than doubled gas permeability.

• Membrane Journal
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• v.29 no.1
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• pp.44-50
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• 2019

In this paper, we developed mixed matrix membranes (MMMs) consisting of SBS-g-POEM block-graft copolymer, ionic liquid (EMIMTFSI) and ZIF-8 nanoparticles to separate a $CO_2/N_2$ gas pair. The SBS-g-POEM is a rubbery block-graft copolymer synthesized through low-cost free-radical polymerization. The EMIMTFSI was dissolved into the SBS-g-POEM matrix and solution synthesized ZIF-8 nanoparticles were also dispersed into the copolymer matrix. The physico-chemical properties of manufactured membranes were characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X-ray diffraction (XRD), which showed that the components were compatible with each other. The gas separation performance was confirmed by time-lag measurements showing $CO_2$ permeability of 537.0 barrer and $CO_2/N_2$ selectivity of 15.2. The result represents the EMIMTFSI and ZIF-8 nanoparticles improves the gas permeability more than two-times, without significantly sacrificing the $CO_2/N_2$ selectivity.

• Membrane Journal
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• v.32 no.4
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• pp.218-226
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• 2022

Hydrogen, a carrier of large-capacity chemical and clean energy, is an important industrial gas widely used in the petrochemical industry and fuel cells. In particular, hydrogen is mainly produced from fossil fuels through steam reforming and gasification, and carbon dioxide is generated as a by-product. Therefore, in order to obtain high-purity hydrogen, carbon dioxide should be removed. This review focused on free-standing polymeric membranes and mixed-matrix membranes (MMMs) that separate hydrogen from carbon dioxide reported in units of Barrer [1 Barrer = 10^-10 cm³ (STP) × cm / (cm² × s × cmHg)]. By analyzing various recently reported papers, the structure, morphology, interaction, and preparation method of the membranes are discussed, and the structure-property relationship is understood to help find better membrane materials in the future. Robeson's upper bound limits for hydrogen/carbon dioxide separation were presented through reviewing the performance and characteristics of various separation membranes, and various MMMs that improve separation properties using technologies such as crosslinking, blending and heat treatment were discussed.

• Membrane Journal
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• v.28 no.6
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• pp.379-387
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• 2018

This study was conducted to improve the membrane characteristics and performance by increasing hydrophilicity by adding additives to the ultrafiltration polysulfone (PSf) hollow fiber membrane. The mixed matrix membranes (MMMs) were prepared by dispersing 15 nm of fumed silica (FS) in the spinning solution at 0.1, 0.3 and 0.5 wt%. SEM analysis was carried out to confirm the cross-section and surface condition. It was confirmed that mean pore radius of the hollow fiber increased by 4 nm as FS was added. In addition, contact angle measurement was carried out for the hydrophilicity analysis of hollow fiber membranes, and it was confirmed that the hydrophilicity of MMMs were increased by adding of FS. In the case of water permeability, the membrane including FS showed 91~96 LMH and showed 5~11% more increase than PSf membrane. In the antifouling performance test, relative flux reduction ratios of FS mixed hollow fiber membranes were lower than that of PSf membranes, and it was confirmed that increase of hydrophilicity hinders adsorption of hydrophobic BSA on the membrane surface.