A polyvinyl alcohol-based mixed matrix membrane with uniformly distributed Schiff base network-1 for ethanol dehydration

In this study, Schiff base network (SNW)-1 nanoparticles with high hydrophilicity and large specific surface area were used to prepare polyvinyl alcohol (PVA)-based mixed matrix membranes (MMMs), which were evaluated for ethanol dehydration. Because of the low difference of density between SNW-1 and PVA, the as-prepared nanoparticles can be uniformly distributed into the PVA active layer. The effects of SNW-1 loading, feed temperature, and water concentration on pervaporation (PV) performance were further studied. The results showed the MMM with 10 wt% of SNW-1 loading exhibited a separation factor of 1,501 and a permeation flux of 187 g m⁻² h⁻¹ for feeding 95 wt% ethanol/water binary solution at 75°C. Overall, the SNW-1/PVA MMMs showed great prospect in ethanol dehydration via PV.     

Modified ZSM‐5/polydimethylsiloxane mixed matrix membranes for ethanol/water separation via pervaporation

In this article, chlorosilane‐modified ZSM‐5 particles were incorporated into polydimethylsiloxane (PDMS) to form mixed matrix membranes (MMMs) for ethanol/water mixture separation via pervaporation (PV). The membranes were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and mechanical performance testing. The maximum loading and dispersion of ZSM‐5 into PDMS were improved by chlorosilane modification. To evaluate the PV performance, the MMMs were used to separate an aqueous ethanol solution. The effect of zeolite loading and operational conditions on PV performance was investigated in detail. The separation factor of the composite membranes filled with modified ZSM‐5 increased considerably versus unmodified membrane, while the total flux decreased to some degree. Of all the chlorosilane‐modified membranes, dodecyltrichlorosilane modified ZSM‐5 filled PDMS showed the best separation factor of 15.8 for ethanol. POLYM. COMPOS., 37:1282–1291, 2016. © 2014 Society of Plastics Engineers     

Liquid–liquid interface induced PDMS-PTFE composite membrane for ethanol perm-selective pervaporation

Pervaporation has great potential in the separation of many significant mixtures. However, excessive penetration of separation layer into the substrate pores enhances the transport resistance of solvent molecules, which impedes the development of pervaporation membrane. In this study, a facile floating-on-water (FOW) method was used to prepare poly(dimethylsiloxane) (PDMS)/polytetrafluoroethylene (PTFE) composite membranes. The formation of separation layer and preparation of composite membrane were step-by-step completed through this liquid–liquid interface induced method. The PDMS layer thickness could be precisely regulated from 0.5 to 8 μm. Moreover, the pore penetration could be controlled by optimizing pre-crosslinking density, crosslinking time on water and polymer solution volume. The obtained PDMS/PTFE composite membrane exhibited a high flux of 2016 g·m⁻²·h⁻¹ with the separation factor of 12 when separating ethanol from a 5 wt% ethanol/water mixture. The performance of the membrane could be stable for over 200 h, exhibiting great potential in ethanol perm-selective pervaporation.     

Preparation and characterization of Silicalite‐1/PDMS surface sieving pervaporation membrane for separation of ethanol/water mixture

To improve the pervaporation performance of Silicalite‐1/PDMS composite membrane by adding a small amount of Silicalite‐1 zeolite, novel Silicalite‐1/PDMS surface sieving membranes (SSMs) were prepared by attaching Silicalite‐1 particles on the PDMS membrane surface. The obtained membranes and traditional mixed‐matrix membranes (MMMs) were characterized by SEM, XRD, TGA, FT‐IR, and pervaporation separation of ethanol–water mixture. Effects of Silicalite‐1 particles content, feed temperatures, and feed compositions on the separation performance were discussed. From the cross‐section view SEM images of SSMs, a two‐layer structure was observed. The thickness of the Silicalite‐1 layer was about 300 nm to 2 μm. The TGA analysis indicates that the zeolite concentration in 3 wt % SSM is lower than 10 wt % MMMs. In the ethanol/water pervaporation experiment, the separation factor of Silicalite‐1/PDMS SSMs increased considerably compared with pure PDMS membrane. When the suspensions concentrations of Silicalite‐1 particles reached 3 wt %, the separation factor was about 217% increase over pure PDMS membrane and 52.9% increase over 10 wt % Silicalite‐1/PDMS MMMs. As the ethanol concentration in the feed increases, the separation factor of SSMs increases, whereas permeation flux decreases. At the same time, with increasing operating temperature, the permeation flux of SSMs increased. The stability of SSMs at high temperature is better than the traditional MMMs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42460.     

Binary metal oxides incorporated polyethersulfone ultrafiltration mixed matrix membranes for the pretreatment of seawater desalination

In this study, an attempt was made to pretreat seawater using polyethersulfone (PES) mixed matrix membranes (MMMs) incorporated with titania-based binary metal oxides. Two different titania-based binary metal oxides were prepared, namely titania-zirconia (TiZr) and titania-zinc oxide (TiZn). The influence of hydrophilic and negatively charged sulfonated poly(ether ether ketone) (SPEEK) polymer as additive of PES MMMs was also studied. Morphological and elemental analysis revealed that both ZrO₂ and ZnO were well dispersed in the as-prepared binary metal oxide TiZr and TiZn, respectively._. Thermogravimetry analysis indicated the good compatibility of TiZr and TiZn with the SPEEK/PES polymer. The binary metal oxide incorporated SPEEK/PES MMMs exhibited improved hydrophilic properties with a low water contact angle of 57° ± (0.6). SPEEK/PES MMMs incorporated with 0.5 wt% TiZr exhibited the highest permeability of 3.11 × 10⁻⁷ ± (0.2) m/s·kPa. Seawater pretreatment performance of membranes evaluated using natural organic matters containing high salinity feed water. TiZr and TiZn incorporated SPEEK/PES MMMs exhibited 95% rejection for humic acid. SPEEK/PES MMMs loaded with 0.5 wt% TiZr also showed the highest water flux and 87% water recovery within 90 min of seawater filtration. Both PES/SPEEK/TiZr and PES/SPEEK/TiZn MMMs exhibited superior antibacterial activity.     

Mixed Matrix Silicone and Fluorosilicone/Zeolite 4A Membranes for Ethanol Dehydration by Pervaporation

The ability of homogeneous and mixed matrix membranes prepared using standard silicone rubber, poly(dimethylsiloxane) (PDMS), and fluorosilicone rubber, poly(trifluoropropylmethylsiloxane) (PTFPMS), to dehydrate ethanol by pervaporation was evaluated. Although PDMS is generally considered to be the benchmark hydrophobic membrane material in pervaporation, water/ethanol molar permselectivity of a pure PDMS membrane was found to be 0.89 for a feed containing 80/20 w/w ethanol/water at 50°C, indicating a slight selectivity for water. Fluorinated groups in PTFPMS improved the water-ethanol permselectivity to 1.85, but decreased the water permeability from 9.7 × 10^?12 kmol · m/m² · s · kPa in PDMS to 5.1 × 10^?12 kmol · m/m² · s · kPa (29,000 and 15,200 Barrer, respectively). These water permeabilities are attractive, particularly since the rubbery materials should not experience the steep declines in water permeability observed with most standard dehydration membranes as water concentration in the feed decreases. However, the water selectivity is lower than desired for most applications. Particles of hydrophilic zeolite 4A were loaded into both PDMS and PTFPMS matrices in an effort to boost water selectivity and further improve water permeability. Water-ethanol permselectivities as high as 11.5 and water permeabilities as high as 23.2 × 10^?12 kmol · m/m² · s · kPa were observed for the PTFPMS/zeolite 4A mixed matrix membranes?6 times higher than for the unfilled PTFPMS membrane.     

Three‐component mixed matrix organic/inorganic hybrid membranes for pervaporation separation of ethanol–water mixture

Mixed matrix membranes (MMMs) were made by incorporating vinyltrimethoxysilane (VTMS)‐modified Silicalite‐1 zeolite nanoparticles (V‐Silicalite‐1 NPs) into fluorinated polybenzoxazine (F‐PBZ) modified polydimethylsiloxane (PDMS) polymer through in situ polymerization method. The membrane morphology, surface wettability, and pervaporation performance were systematically investigated. The addition of F‐PBZ into PDMS membranes resulted in substantially improved flux and marginal increase of separation factor, which is the result of higher free volume and higher hydrophobicity caused by the addition of F‐PBZ. The modification of Silicalite‐1 NPs improved the interfacial contact between zeolite crystals and polymer phase. The incorporation of hydrophobic V‐Silicalite‐1 zeolite NPs into the PDMS membranes led to much higher separation factor but reduced flux, which is the result of increased hydrophobicity and reduced free volume. The three‐component MMMs with V‐Silicalite‐1 zeolite NPs in the F‐PBZ fluorinated PDMS exhibited separation factor of 28.7 and flux of 0.207 kg m^?2 h^?1 for 5 wt % ethanol aqueous solution at 50 °C, while the pure PDMS membranes only had separation factor of 4.8 and flux of 0.088 kg m^?2 h^?1. The substantial increase of both flux and separation factor were attributed to the higher hydrophobicity and free volume caused by the incorporation of both hydrophobic zeolite crystals and F‐PBZ polymer into the PDMS membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44753.     

Preparation and characterization of nanoparticle-filled,mixed-matrix membranes for the pervaporation dehydration of isopropyl alcohol

Novel polymeric mixed-matrix membranes (MMMs) were prepared by the incorporation of different amounts of 13X zeolite into a sodium carboxymethylcellulose (NaCMC)/poly(vinyl alcohol) (PVA) blend matrix. The resulting MMMs were characterized by attenuated total reflectance–Fourier transform infrared spectroscopy to analyze the possible chemical reactions between NaCMC, PVA, zeolites, and glutaraldehyde. Scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction were used to analyze the surface morphology, thermal stability, and crystallinity, respectively, of the membranes. Swellings studies were performed at 35°C, and we found that membranes containing 20 wt % zeolite showed higher values (960 kg m⁻² h⁻¹) at 17.5 wt % water in an isopropyl alcohol (IPA)/water mixture. Pervaporation (PV) experiments were also performed to evaluate the membrane performance in different compositions of the IPA/water mixture at 35°C. The mechanical properties were also tested, and we found that the optimum mechanical strength and percentage elongation at break were 42.24 N/mm² and 3.38, respectively, for the membrane containing 15 wt % zeolite. The experimental results show that both the flux and selectivity increased with increasing zeolite content. The membrane containing 20 wt % zeolite showed the highest separation selectivity (5118) with a substantial flux of 0.121 kg m⁻² h⁻¹ at 35°C and with 10 wt % water in the feed; this suggested that the membranes could be used effectively to break the azeotropic point of the water–IPA mixture, so as to remove a small amount of water from IPA. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of dual-functionalized mixed matrix membrane with amino-GO-Bent/PVDF for efficient separation of CO2/CH4 and CO2/N2

Mixed matrix membranes (MMMs), which combine the characteristics of inorganic nanofillers and organic matrices, have received wide attention because of their good permeability and selective performance for separating CO₂ from industrial waste gases. In this work, the amino-GO-loaded bentonite (amino GO-Bent) was prepared by loading  NH₂ on the GO surface with a large number of functional sites. Firstly, by introducing  NH₂ on the surface of GO and then interacting with bentonite (Bent) organically modified by silane coupling agents through amide bonding. Mixed matrix membranes (MMMs) with an area of 623.7 cm² and homogeneous texture were prepared using amino-GO-Bent as inorganic filler to improve the membrane selectivity for CO₂/N₂ and CO₂/CH₄ separation. The results show that the introduction of amino GO-Bent in MMMs can greatly improve the CO₂ permeability and obtain high CO₂ permeation performance: 2.67945 × 10⁻⁷ cm³ (STP)·cm/s/cm²/cmHg, and the selectivity of CO₂/N₂ and CO₂/CH₄ can reach 307.28 and 325.97, respectively. The two selective values were 14 and 18 times higher than those of pure PVDF membranes, and the performance of MMMs far exceeded the Robeson upper limit in 2008, respectively.     

Spherical hybrid filler BN@Al2O3 via chemical adhesive for enhancing thermal conductivity and processability of silicon rubber

Hexagonal boron nitride (h-BN) is an ideal candidate material for electrical and electronic systems due to its excellent performance. However, the addition of platelet-like h-BN leads to a dramatic increase of viscosity of composites and anisotropic thermal conductivity of composites. Herein, modified h-BN (m-BN) was coated onto spherical α-Al₂O₃ via chemical adhesive, and core-shell structured hybrid spherical filler (m-BN@Al₂O₃) was prepared. Furthermore, the microstructure, rheology, mechanical properties, and thermal conductivity of hybrid filler/polydimethylsiloxane (PDMS) were studied. At 60 vol% filler loading, the thermal conductivity of m-BN@Al₂O₃/PDMS is up to 2.23 W·m⁻¹·K⁻¹, which is 86% higher than that of Al₂O₃/PDMS and the ratio of in-plane diffusivity to through-plane diffusivity decreases from 2.0 to 1.0. At meanwhile, the viscosity of m-BN@Al₂O₃/PDMS is about one fourth of the viscosity of m-BN/Al₂O₃/PDMS. This simple and versatile strategy opens a pavement for enhancing the thermal conductivity of polymer and has great potential in high-frequency communication.     

Fabrication of highly permeable PDMS@ZIF-8/PVDF hollow fiber composite membrane in module for ethanol-water separation

The construction of high-performance MOF-based hollow fiber composite membrane (HFCM) modules is a significant, yet challenging task for the biofuel production industry. In this study, a novel approach was taken to fabricate PDMS@ZIF-8/PVDF HFCMs in modules through a facile ZIF-8 self-crystallization synthesis followed by pressure-assisted PDMS infusion for pervaporation ethanol-water separation. The as-prepared HFCMs exhibited an ultrathin separation layer (thickness, 370 ± 35 nm), which was achieved through precise regulation of the ZIF-8 membrane and defect repair by PDMS infusion. Moreover, the strategy utilized in this study resolved the defect issues arising from MOF agglomeration in conventional composite membranes. Impressively, at the optimal packing density, the prepared membrane demonstrated a remarkable ethanol flux (1.11 kg m⁻² h⁻¹) with an PSI value (26.59 kg m⁻² h⁻¹) and showed promising long-term stability for the pervaporation of 5 wt% ethanol aqueous solution at 40°C.     

Development of mixed matrix membranes for controlled release of ibuprofen

In this work was studied the effect of different zeolite topologies on the release of ibuprofen from mixed matrix membranes (MMMs). The main parameters investigated were: zeolite concentration, its hydrophilic/hydrophobic character, and drug loading. About the different investigated systems, the PDMS NaX (I) membrane seems to be the most promising for its application as transdermal device. The release data were fitted with different mathematical models (zero order, first order, Higuchi, Bhaskar, and Korsemeyer‐Peppas) to give a possible explanation of the release mechanism of the drug from MMMs. The release data of the drug from pure PDMS membranes (PDMS IBU) were fitted by the Higuchi model (R² pari a 0.97). In the case of MMMs, the correlation coefficients are very far from the unit value except for the PDMS NaX (I) system that obeys to the Korsmeyer–Peppas (0.98) and Bashkar (0.99) models. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of zeolite addition on ethanol production from glucose by Saccharomyces bayanus

Zeolite NaY at 5 g dm⁻³ concentration, was selected to improve the production of ethanol fermentation by Saccharomyces bayanus from high glucose concentration media. The highest ethanol productivity (3·07 g dm⁻³ h⁻¹) was obtained from a 220 g dm⁻³ initial glucose concentration, while the highest ethanol concentration (130 g dm⁻³) was obtained from a 350 g dm⁻³ glucose medium. The zeolite is believed to have acted as a pH regulator, maintaining the pH value around 3·7–3·8. Under these conditions cellular viability was preserved and metabolic activity was maintained. Thus all the glucose was consumed, and high ethanol productivity and concentration were obtained. Therefore, the addition of zeolite improved ethanol production from high concentrations of glucose by Saccharomyces bayanus. © 1998 Society of Chemical Industry     

Regulatable pervaporation performance of Zn-MOFs/polydimethylsiloxane mixed matrix pervaporation membranes

Pervaporation (PV) is an emerging separation technique for liquid mixture. Mixed matrix membranes (MMMs) often demonstrate trade-off relationship between separation factor and flux. In this study, by changing the organic linkers (2-methyl imidazolate, imidazole-2-carboxaldehyde, 2-ethyl imidazolate), ZIF-8, ZIF-90 and MAF-6 were prepared and filled in polydimethylsiloxane (PDMS) membranes for dealcoholization of 5% (mass) n-butanol solution, and the membranes properties and pervaporation performances were adjusted. Compared with the pure PDMS membrane, the addition of ZIF-8 resulted in a 9% increase in flux (1136 g·m^-2·h^-1) and a 22.5% increase in separation factor (28.3), displaying anti-trade-off effect. For the MAF-6/PDMS MMMs (2.0% mass loading), the pervaporation separation index (PSI) and separation factor were 32347 g·m^-2·h^-1 and 58.6 respectively (increased by 34% and 154% in contrast with that of the pure PDMS membrane), and the corresponding permeation flux was 552 g·m^-2·h^-1, presenting great potential in the removal butanol from water. It was deduced that the large aperture size combined with moderate hydrophobicity of metal-organic frameworks (MOFs) favor the concurrent increase in permeability and selectivity.     

Pervaporation properties of polyvinyl alcohol/ceramic composite membrane for separation of ethyl acetate/ethanol/water ternary mixtures

In further purification of ethyl acetate (EAC) process, azeotropic distillation or extractive distillation is usually applied. High energy consumption limits the economic profit of the process. In this study, pervaporation separation of EAC/ethanol (EA)/water ternary mixtures using the ceramic-supported polyvinyl alcohol (PVA) composite membrane was investigated to substitute the azeotropic distillation or extractive distillation. Swelling experiments were performed to evaluate the sorption characteristic of the membrane. Flory-Huggins theory was applied to study the interaction between the membrane and the penetrant. The UNIFAC model was adopted to investigate the variation of the penetrant activity in the membrane. The effects of operation temperature, feed water content and feed flow rate on the PV performance of the membrane were systematically investigated. The composite membrane exhibited high PV performance with the total flux of 2.1 kg·m⁻²·h⁻¹ and 94.9 wt% permeate concentration of water (operation condition: feed composition 82.6 wt% EAC, 8.4 wt% EA, 9 wt% water, feed temperature 60 °C, feed flow rate 252 mL· min⁻¹). The PV performance of the membrane varied slightly over a continuous PV experiment period of 110 h. Our results demonstrated that the PVA/ceramic membrane was a potential candidate for the purification of EAC/EA/water ternary mixtures.     

Improved Ethanol Production by Saccharomyces cerevisiae with EDTA,Ferrocyanide and Zeolite X Addition to Sugar Beet Molasses

The influence of ethylenediaminetetra acetic acid (EDTA), potassium ferrocyanide and zeolite X on ethanol production from sugar beet molasses by Saccharomyces cerevisiae was studied. For all of the three substances used, the effect was more pronounced when added to the fermentation medium rather than to the growth medium; 1·9 mmol dm⁻³ potassium ferrocyanide caused an increase in the final ethanol concentration of about 16·4% and 47·5% with respect to control culture on addition to growth and fermentation media respectively. The greatest stimulation in product yield was obtained with zeolite X introduced during the fermentation stage; 8·0 g dm⁻³ zeolite X increased ethanol concentration by 53·3%. © 1997 SCI.     

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     

Preparation of PDMS—Silica Nanocomposite Membranes with Silane Coupling for Recovering Ethanol by Pervaporation

In this article, the composite polydimethylsiloxane (PDMS) membranes supported by cellulose-acetate (CA) microfiltration membrane were successfully prepared by adding nano-fumed silica particles modified with a silane coupling reagent, NH₂-C₃H₆-Si(OC₂H₅)₃. The effects of silica content, feed concentration, and feed temperature on the pervaporation performances of the nano-composite PDMS membranes were investigated for recovering ethanol from aqueous solution by pervaporation. It was found that adding the modified silica particles significantly improved the pervaporation performances of the composite membranes. When the silica content in the membrane was 5 wt%, for a 5 wt% ethanol/water mixture at 40°C, the permeation flux of the membrane maintained about 200 g · m^?2 · h^?1 and separation factor reached the maximum value of 19.     

Iron oxide nanoparticles improved biocompatibility and removal of middle molecule uremic toxin of polysulfone hollow fiber membranes

Middle molecule uremic toxins constitute to a quarter of uremic toxins present in human blood. In a condition where these uremic toxins accumulate in bloodstream due to renal failure, blood purification process using a high performance membrane is required. Here, we develop biocompatible mixed matrix membranes (MMMs) made up of polysulfone (PSf) and iron oxide nanoparticles (Fe₂O₃ NPs) with the focus to remove middle molecule uremic toxin effectively. The MMMs were evaluated in terms of their biocompatibility and separation performance. At higher Fe₂O₃ NPs loading, the MMM displayed a huge reduction of protein adsorption and platelet adhesion while maintaining normal blood coagulation time and acceptable complement activation. The optimized MMM exhibited high permeability (110.47 L m⁻² h⁻¹ bar⁻¹), protein retention (99.9%) and demonstrated excellent clearance of urea (82%) and lysozyme (46.7%). The PSf/Fe₂O₃ MMM is proven to have promising attributes for hemodialysis application. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48234.     

Poly(vinyl alcohol)/carboxyl graphene mixed matrix membranes: High-power ultrasonic treatment for enhanced pervaporation performance

High-power ultrasonic treatment was conducted during the mixing process to obtain poly(vinyl alcohol) (PVA)/carboxyl graphene (CG) mixed matrix membranes (MMMs). Results from X-ray photoelectron spectrometer and thermogravimetric analysis confirmed the enhanced esterification reaction. The increased amorphous region and free volume were investigated by wide-angle X-ray diffraction and positron annihilation lifetime spectroscopy. Scanning electron microscope and atomic force microscope measurements suggested that ultrasonic could uniformly disperse CG in PVA polymer matrix. The mechanical properties and hydrophilicity of as-prepared membrane were enhanced due to ultrasonic treatment. The permeation flux and separation factor of PVA/CG-US membrane for 90 wt % ethanol aqueous solution were 0.79 kg m⁻² h⁻¹ and 860, respectively. For methanol (15 wt %)/methyl tert-butyl ether mixture, its permeation flux and separation factor were also increased significantly compared with membranes without ultrasonic treatment. Due to the simplicity of the ultrasonic process and the versatility of the inorganic fillers, this method may contribute to the design of various MMMs and extend the application of these membranes in different uses. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48526.