Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 10

Pervaporation Related Abstracts

10 Development of Polybenzoxazine Membranes on Al2O3 Support for Water-Ethanol Separation via Pervaporation Technique

Authors: Thanyalak Chaisuwan, Sujitra Wongkasemjit, Chonlada Choedchun, Ni-on Saelim, Panupong Chuntanalerg


Bioethanol is one of the candidates to replace fossil fuels. Membrane technique is one of the attractive processes to produce high purity of ethanol. In this work, polybenzoxazine (PBZ) membrane successfully synthesized from bisphenol-A (BPA), formaldehyde, and two different types of multifunctionalamines: tetraethylenepentamine (tepa), and diethylenetriamine (deta), was evaluated for water-ethanol separation. The membrane thickness was determined by scanning electron microscopy (SEM). Pervaporation technique was carried out to find separation performance. It was found that the optimum PBZ concentration for the preparation of the membranes is 25%. The dipping cycles of PBZ-tepa and PBZ-deta was found to be 4 and 5, giving the total permeation flux of 28.97 and 14.75 g/m2.h, respectively. The separation factor of both membranes was higher than 10,000.

Keywords: Pervaporation, polybenzoxazine, permeation flux, separation factor

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9 Hydrothermal Synthesis of ZIF-7 Crystals and Their Composite ZIF-7/CS Membranes for Water/Ethanol Separation

Authors: Yi-Feng Lin, Kai-Sheng Ji


The pervaporation process for solvent and water separation has attracted research attention due to its lower energy consumption compared with conventional distillation processes. The membranes used for the pervaporation approach should exhibit high flux and separation factors. In this study, the ZIF-7 crystal particles were successfully incorporated into chitosan (CS) membranes to form ZIF-7/CS mixed-matrix membranes. The as-prepared ZIF-7/CS mixed-matrix membranes were used to separate mixtures of water/ethanol at 25℃ in the pervaporation process. The mixed-matrix membranes with different ZIF-7 wt% incorporation showed better separation efficiency than the pristine CS membranes because of the smaller pore size of the mixed-matrix membranes. The separation factor and the flux of the ZIF-7/CS membranes clearly exceed the upper limit of the previously reported CS-based and mixed-matrix membranes.

Keywords: Pervaporation, chitosan, ZIF-7, memberane separation

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8 Prussian Blue/Chitosan Mixed-Matrix Membranes with Improved Separation Performance of Ethanol/Water Mixtures

Authors: Yi-Feng Lin, Ting-YuLiu


Porous Prussian Blue (PB) nanoparticles were successfully incorporated into chitosan (CS) membranes to form PB/CS mixed-matrix membranes (MMMs) and the as-prepared PB/CS MMMs were used to dehydration of ethanol at 25 oC in the pervaporation process. The effect of PB loading in CS matrix on pervaporation performance was investigated. The FESEM, EDS, FTIR and XRD measurements were also used for the characterization of the PB/CS MMMs. The PB/CS membranes with 30 wt% PB loading show the best performance with the permeate flux of 614 g/m2h and the separation factor of 1472. The pervaporation using the PB/CS membranes exhibits outstanding performance as compared with the previously reported CS based membranes and MMMs. The present work demonstrates good pervaporation performance of the PB/CS MMMs for the separation of 90wt% ethanol aqueous solution, moreover, it has an opportunity for dehydration of bioethanol in this system of pervaporation.

Keywords: Pervaporation, chitosan, Prussian blue, mixed-matrix membrane

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7 Preparation of hydrophobic silica membranes supported on alumina hollow fibers for pervaporation applications

Authors: Sadao Araki, Daisuke Gondo, Hideki Yamamoto, Ami Okabe, Akira Ogawa, Yasuhisa Hasegawa, Koichi Sato


Membrane separation draws attention as the energy-saving technology. Pervaporation (PV) uses hydrophobic ceramic membranes to separate organic compounds from industrial wastewaters. PV makes it possible to separate organic compounds from azeotropic mixtures and from aqueous solutions. For the PV separation of low concentrations of organics from aqueous solutions, hydrophobic ceramic membranes are expected to have high separation performance compared with that of conventional hydrophilic membranes. Membrane separation performance is evaluated based on the pervaporation separation index (PSI), which depends on both the separation factor and the permeate flux. Ingenuity is required to increase the PSI such that the permeate flux increases without reducing the separation factor or to increase the separation factor without reducing the flux. A thin separation layer without defects and pinholes is required. In addition, it is known that the flux can be increased without reducing the separation factor by reducing the diffusion resistance of the membrane support. In a previous study, we prepared hydrophobic silica membranes by a molecular templating sol−gel method using cetyltrimethylammonium bromide (CTAB) to form pores suitable for permitting the passage of organic compounds through the membrane. We separated low-concentration organics from aqueous solutions by PV using these membranes. In the present study, hydrophobic silica membranes were prepared on a porous alumina hollow fiber support that is thinner than the previously used alumina support. Ethyl acetate (EA) is used in large industrial quantities, so it was selected as the organic substance to be separated. Hydrophobic silica membranes were prepared by dip-coating porous alumina supports with a -alumina interlayer into a silica sol containing CTAB and vinyltrimethoxysilane (VTMS) as the silica precursor. Membrane thickness increases with the lifting speed of the sol in the dip-coating process. Different thicknesses of the γ-alumina layer were prepared by dip-coating the support into a boehmite sol at different lifting speeds (0.5, 1, 3, and 5 mm s-1). Silica layers were subsequently formed by dip-coating using an immersion time of 60 s and lifting speed of 1 mm s-1. PV measurements of the EA (5 wt.%)/water system were carried out using VTMS hydrophobic silica membranes prepared on -alumina layers of different thicknesses. Water and EA flux showed substantially constant value despite of the change of the lifting speed to form the γ-alumina interlayer. All prepared hydrophobic silica membranes showed the higher PSI compared with the hydrophobic membranes using the previous alumina support of hollow fiber.

Keywords: Pervaporation, hydrophobic, silica, membrane separation

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6 Modeling Sorption and Permeation in the Separation of Benzene/ Cyclohexane Mixtures through Styrene-Butadiene Rubber Crosslinked Membranes

Authors: Hassiba Benguergoura, Kamal Chanane, Sâad Moulay


Pervaporation (PV), a membrane-based separation technology, has gained much attention because of its energy saving capability and low-cost, especially for separation of azeotropic or close-boiling liquid mixtures. There are two crucial issues for industrial application of pervaporation process. The first is developing membrane material and tailoring membrane structure to obtain high pervaporation performances. The second is modeling pervaporation transport to better understand of the above-mentioned structure–pervaporation relationship. Many models were proposed to predict the mass transfer process, among them, solution-diffusion model is most widely used in describing pervaporation transport including preferential sorption, diffusion and evaporation steps. For modeling pervaporation transport, the permeation flux, which depends on the solubility and diffusivity of components in the membrane, should be obtained first. Traditionally, the solubility was calculated according to the Flory–Huggins theory. Separation of the benzene (Bz)/cyclohexane (Cx) mixture is industrially significant. Numerous papers have been focused on the Bz/Cx system to assess the PV properties of membrane materials. Membranes with both high permeability and selectivity are desirable for practical application. Several new polymers have been prepared to get both high permeability and selectivity. Styrene-butadiene rubbers (SBR), dense membranes cross-linked by chloromethylation were used in the separation of benzene/cyclohexane mixtures. The impact of chloromethylation reaction as a new method of cross-linking SBR on the pervaporation performance have been reported. In contrast to the vulcanization with sulfur, the cross-linking takes places on styrene units of polymeric chains via a methylene bridge. The partial pervaporative (PV) fluxes of benzene/cyclohexane mixtures in styrene-butadiene rubber (SBR) were predicted using Fick's first law. The predicted partial fluxes and the PV separation factor agreed well with the experimental data by integrating Fick's law over the benzene concentration. The effects of feed concentration and operating temperature on the predicted permeation flux by this proposed model are investigated. The predicted permeation fluxes are in good agreement with experimental data at lower benzene concentration in feed, but at higher benzene concentration, the model overestimated permeation flux. The predicted and experimental permeation fluxes all increase with operating temperature increasing. Solvent sorption levels for benzene/ cyclohexane mixtures in a SBR membrane were determined experimentally. The results showed that the solvent sorption levels were strongly affected by the feed composition. The Flory- Huggins equation generates higher R-square coefficient for the sorption selectivity.

Keywords: Benzene, Pervaporation, Sorption Modeling, SBR, permeation, cyclohexane

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5 Modelling of Pervaporation Separation of Butanol from Aqueous Solutions Using Polydimethylsiloxane Mixed Matrix Membranes

Authors: Arian Ebneyamini, Hoda Azimi, Jules Thibaults, F. Handan Tezel


In this study, a modification of Hennepe model for pervaporation separation of butanol from aqueous solutions using Polydimethylsiloxane (PDMS) mixed matrix membranes has been introduced and validated by experimental data. The model was compared to the original Hennepe model and few other models which are applicable for membrane gas separation processes such as Maxwell, Lewis Nielson and Pal. Theoretical modifications for non-ideal interface morphology have been offered to predict the permeability in case of interface void, interface rigidification and pore-blockage. The model was in a good agreement with experimental data.

Keywords: Modeling, Pervaporation, PDMS, mixed matrix membranes, butanol

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4 Pervaporation of Dimethyl Carbonate / Methanol / Water Mixtures Using Zeolite Membranes

Authors: Dong-Ho Lee, Young Cheol Park, Jong-Ho Moon, Hyunuk Kim, Jong-Seop Lee, Jae-deok Jeon, Hyung-Keun Lee


A novel membrane reactor process for DMC synthesis from carbon dioxide has been developing in Korea Institute of Energy Research. The scheme of direct synthesis of DMC from CO₂ and Methanol is 'CO₂ + 2MeOH ↔ DMC + H₂O'. Among them, reactants are CO₂ and MeOH, product is DMC, and byproduct is H₂O (water). According to Le Chatelier’s principle, removing byproduct (water) can shift the reaction equilibrium to the right (DMC production). The main purpose of this process is removing water during the reaction. For efficient in situ water removal (dehydration) and DMC separation, zeolite 4A membranes with very small pore diameter and hydrophilicity were introduced. In this study, pervaporation performances of binary and ternary DMC / methanol / water mixtures were evaluated.

Keywords: Water, methanol, Pervaporation, dimehtyl carbonate, zeolite membrane

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3 Ultrathin Tin-Silicalite 1 Zeolite Membrane in Ester Solvent Recovery

Authors: Eng Toon Saw, Kun Liang Ang, Wei He, Xuecheng Dong, Seeram Ramakrishna


Ester solvents are widely used in pharmaceutical, printing and flavor industry due to their good miscibility, low toxicity, and high volatility. Through pervaporation, these ester solvents can be recovered from industrial wastewater. While metal-doped silicalite 1 zeolite membranes are commonly used in organic solvent recovery in the pervaporation process, these ceramic membranes suffer from low membrane permeation flux, mainly due to the high thickness of the metal-doped zeolite membrane. Herein, a simple method of fabricating an ultrathin tin-silicalite 1 membrane supported on alumina tube is reported. This ultrathin membrane is able to achieve high permeation flux and separation factor for an ester in a diluted aqueous solution. Nanosized tin-Silicalite 1 seeds which are smaller than 500nm has been formed through hydrothermal synthesis. The sn-Silicalite 1 seeds were then seeded onto alumina tube through dip coating, and the tin-Silicalite 1 membrane was then formed by hydrothermal synthesis in an autoclave through secondary growth method. Multiple membrane synthesis factors such as seed size, ceramic substrate surface pore size selection, and secondary growth conditions were studied for their effects on zeolite membrane growth. The microstructure, morphology and the membrane thickness of tin-Silicalite 1 zeolite membrane were examined. The membrane separation performance and stability will also be reported.

Keywords: Pervaporation, ceramic membrane, solvent recovery, Sn-MFI zeolite

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2 Layer by Layer Coating of Zinc Oxide/Metal Organic Framework Nanocomposite on Ceramic Support for Solvent/Solvent Separation Using Pervaporation Method

Authors: Seeram Ramakrishna, S. A. A. Nabeela Nasreen, S. Sundarrajan, S. A. Syed Nizar


Metal-organic frameworks (MOFs) have attracted considerable interest due to its diverse pore size tunability, fascinating topologies and extensive uses in fields such as catalysis, membrane separation, chemical sensing, etc. Zeolitic imidazolate frameworks (ZIFs) are a class of MOF with porous crystals containing extended three-dimensional structures of tetrahedral metal ions (e.g., Zn) bridged by Imidazolate (Im). Selected ZIFs are used to separate solvent/solvent mixtures. A layer by layer formation of the nanocomposite of Zinc oxide (ZnO) and ZIF on a ceramic support using a solvothermal method was engaged and tested for target solvent/solvent separation. Metal oxide layer was characterized by XRD, SEM, and TEM to confirm the smooth and continuous coating for the separation process. The chemical composition of ZIF films was studied by using X-Ray absorption near-edge structure (XANES) spectroscopy. The obtained ceramic tube with metal oxide and ZIF layer coating were tested for its packing density, thickness, distribution of seed layers and variation of permeation rate of solvent mixture (isopropyl alcohol (IPA)/methyl isobutyl ketone (MIBK). Pervaporation technique was used for the separation to achieve a high permeation rate with separation ratio of > 99.5% of the solvent mixture.

Keywords: Pervaporation, Membrane, metal oxide, solvothermal, ZIF

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1 Effect of Temperature on Pervaporation Performance of Ag-Poly Vinyl Alcohol Nanocomposite Membranes

Authors: Asmaa Selim, Peter Mizsey


Bio-ethanol is considered of higher potential as a green renewable energy source owing to its environmental benefits and its high efficiency. In the present study, silver nanoparticles were in-situ generated in a poly (vinyl alcohol) in order to improve its potentials for pervaporation of ethanol-water mixture using solution-casting. Effect of silver content on the pervaporation separation index and the enrichment factor of the membrane at 15 percentage mass water at 40ᵒC was reported. Pervaporation data for nanocomposite membranes showed around 100% increase in the water permeance values while the intrinsic selectivity decreased. The water permeances of origin crosslinked PVA membrane, and the 2.5% silver loaded PVA membrane are 26.65 and 70.45 (g/m².kPa.h) respectively. The values of total flux and water flux are closed to each other, indicating that membranes could be effectively used to break the azeotropic point of ethanol-water. Effect of temperature on the pervaporation performance, permeation parameter and diffusion coefficient of both water and ethanol was discussed. The negative heat of sorption ∆Hs values calculated on the basis of the estimated Arrhenius activation energy values indicating that the sorption process was controlled by Langmuir’s mode. The overall results showed that the membrane containing 0.5 mass percentage of Ag salt exhibited excellent PV performance.

Keywords: nanocomposite, Silver Nanoparticles, Pervaporation, diffusion coefficient, bio-ethanol, poly (vinyl alcohol)

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