• Membrane Journal
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• v.17 no.2
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• pp.146-160
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• 2007

A parametric study on pervaporation-facilitated esterification was performed by using a practical model based on non-perfect separation through membrane which is not perfectly permselective to water. Thus, membrane selectivity as well as membrane capability to remove water should be taken into account in establishing the simulation model to explain how the membrane separation influence the esterification reaction process. It was shown by simulation that in the reaction systems with non-perfect separation, the permeation of reactants which are acid or/and alcohol retards the reaction by inducing the backward reaction so that reaction conversion curve is located between a reaction system coupled with pervaporation process having a perfect permselectivity to water and a reaction system without pervaporation process. The volume change of reaction system occurs as a result of the permeation through the membrane. The reaction volume change which can be characterized by the reaction ratio of $r_{\Psi}\;to\;r_{{\Psi}=1}$ affects reaction kinetics by concentrating reactants and products, respectively, with different extent with time; reactant-concentrating effect is dominant during the initial stage of reaction, resulting in facilitating the reaction, and then product-concentrating effect is exerted more on reaction, causing to slow down the reaction. When pervaporative dehydration is applied to the reaction system plays an important role in the reaction as well. The effect of timing to impose pervaporation on reaction system affected the reaction kinetics in terms of reaction rate and reaction conversion. A relationship was derived to explain membrane unit capacity and reaction parameters that will be used as a design tool to determine membrane unit capacity at a given reaction conditions or reaction parameters at a membrane unit capacity.

• Membrane Journal
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• v.16 no.2
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• pp.115-122
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• 2006

In this study the membrane preparation and water vapor permeation of the hydrophilic polymer materials, polyaminosiloxane and polyhydroxylsiloxane, used as the coating materials for the preparation of asymmetric flat and hollow fiber membranes were investigated. And the water vapor permeation towards air permeation and their permselectivity were intensively studied for the resulting Resin A/Resin C (coupling agent) and Resin B/Resin C membranes. The water vapor permeability for 3 wt% Resin C introduced into Resin A (Resin A/Resin C) membrane was higher than for 1 and 5 wt% membranes and also water vapor permeability increased with increasing operating temperatures. In addition, at this content of 3 wt% Resin C, the absorption capability became maximum through dynamic equilibrium absorption experiment. Water vapor permeability, 43578 Barrer (1 Barrer = $10^{-10}cm^3(STP){\cdot}cm/cm^2{\cdot}s{\cdot}cmHg$) and 53000 Barrer, and the selectivity of $P(H_2O)P(Air)$, 101.3 and 102.6 were shown at 25 and $35^{\circ}C$, respectively.

• Membrane Journal
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• v.24 no.4
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• pp.285-291
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• 2014

The PTMSP[Poly(1-trimethylsilyl-1-propyne)]-NaY zeolite composite membranes were prepared by adding 0~50 wt% NaY zeolite to PTMSP. In order to investigate the characteristics of these membranes, we used the analytical methods such as FT-IR, $^1H$-NMR, GPC, DSC, TGA, and SEM. Gas permeation experiments were carried out at $23{\sim}26^{\circ}C$, $2kgf/cm^2$, and the permselectivity of $H_2$ and $N_2$ gases through the composite membranes was studied as a function of the NaY zeolite contents. According to TGA measurements, when NaY zeolite was inserted within the PTMSP, thermal stability of PTMSP was enhanced. Based on SEM observation, NaY zeolite was dispersed in the PTMSP-NaY zeolite composite membrane with a size of $1.5{\mu}m$. The permeability of $H_2$ and $N_2$ through the PTMSP-NaY zeolite composite membranes increased as NaY zeolite content increased. On the contrary, the selectivity($H_2/N_2$) of the PTMSP-NaY zeolite composite membranes decreased as zeolite content increased.

• Membrane Journal
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• v.28 no.5
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• pp.351-360
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• 2018

In this study, propylene/propane separation mechanism through NaY zeolite membrane was investigated. As permeation temperature increased, both propylene and propane permeances increased, saturated and decreased again, and a maximum selectivity was shown at around 50 to $60^{\circ}C$. Propane permeance in mixed gas experiment was much smaller than that in single gas experiment, and propylene/propane mixed gas selectivity was much larger than single gas permselectivity. As permeation time increased in transient permeation experiment, propylene permeance initially increased and saturated, while propane permeance decreased and saturated. All the experimental results announced that propylene/propane separation through NaY zeolite membrane was from preferentially adsorbed propylene molecules. The adsorbed propylene molecules efficiently prevented propane molecules from permeating through the membrane, and sufae diffused through the membrane. NaY zeolite capillary membrane prepared in the present study showed a high mixed gas selectivity of 12 and high propylene permeance of 497 GPU for a propylene/propane (89 : 11) mixture at $50^{\circ}C$ and 4 bar. Therefore, it was concluded that NaY zeolite membrane is one of promising membrane materials for propylene/propane separation due to the low cost and high separation performance.

• Korean Chemical Engineering Research
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• v.49 no.6
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• pp.816-822
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• 2011

Pervaporation is known to be a low energy consumption process since it needs only an electric power to maintain the permeate side in vacuum. Also, the pervaporation is an environmentally clean technology because it does not use the third material such as an entrainer for either an azeotropic distillation or an extractive distillation. In this study, Silicalite-1 particles are hydrothermally synthesized and polydimethylsiloxane(PDMS)-zeolite composite membranes are prepared with a mixture of synthesized Silicalite-1 particles and PDMS-polymer. They are used to separate n-butanol from its aqueous solution. Pervaporation characteristics such as a permeation flux and a separation factor are investigated as a function of the feed concentration and the weight % of Silicalite-1 particles in the membrane. A 1,000 $cm^3$ aqueous solution containing butanol of low mole fraction such as order of 0.001 was used as a feed to the membrane cell while the pressure of the permeation side was kept about 0.2~0.3 torr. When the butanol concentration in the feed solution was 0.015 mole fraction, the flux of n-butanol significantly increased from 14.5 g/ $m^2$/hr to 186.3 g/$m^2$/hr as the Silicalite-1 content increased from 0 wt% to 10 wt%, indicating that the Silicalite-1 molecular sieve improved the membrane permselectivity from 4.8 to 11.8 due to its unique crystalline microporous structure and its strong hydrophobicity. Consequently, the concentration of n-butanol in the permeate substantially increased from 0.07 to 0.15 mole fraction. This composite membrane could be potentially appliable for separation of n-butanol from insitu fermentation broth where n-butanol is produced at a fairly low concentration of 0.015 mole fraction.

• 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 Journal
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• v.31 no.3
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• pp.219-227
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• 2021

Molecularly imprinted membrane (MIM) is a porous polymer membrane incorporating with the molecular recognizing sites. In this study, the supporting P(AN-co-MA) asymmetric membrane was prepared by nonsolvent induced phase separation (NIPS) method. And then, MIM with lysozyme template sites was prepared using the surface imprinting method on the P(AN-co-MA) asymmetric membrane introducing a photoactive iniferter and then photo-grafting. The P(AN-co-MA) asymmetric membrane was modified with 3-chloropropyltrimethoxysilane and dithiocarbamate as a photoactive iniferter. To prepare a lysozyme imprinted membrane, the modified P(AN-co-MA) membrane was copolymerized with acrylamide as a functional momomer, N,N'-methylene bisacrylamide as a crosslinker and lysozyme as a template in the UV irradiation environment. The lysozyme imprinted MIM was analyzed by using SEM, FT-IR and EDS measurements. Its results confirm that all the P(AN-co-MA) membranes have an asymmetric structure and the iniferter group is successfully introduced on the membrane surface. The process parameters were adjusted to obtain MIM having the excellent lysozyme adsorption. The maximum lysozyme adsorption capacity reaches at 2.7 mg/g, which is 13 times higher than that of the non imprinted membrane (NIM). The permselective membrane filtration experiments of ovalbumin to lysozyme show that the P(AN-co-MA) MIM preferentially bounds a greater amount of lysozyme.

• Korean Chemical Engineering Research
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• v.54 no.5
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• pp.653-658
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• 2016

Poly(ether-block-amide)(PEBAX$_{(R)}$) resin is a thermoplastic elastomer combining linear chains of hard-rigid polyamide block interspaced soft-flexible polyether block. It was believed that the hard polyamide block provides the mechanical strength and permselectivity, whereas gas transport occurs primarily through the soft polyether block. The objective of this work was to investigate the gas permeation properties of carbon dioxide and methane for PEBAX$^{(R)}$-1657 membrane, and compare with those obtained for other grade of pure PEBAX$^{(R)}$, PEBAX$^{(R)}$-2533 and PEBAX$^{(R)}$ based hybrid membranes. The hybrid membranes based PEBAX$^{(R)}$ were obtained by a sol-gel process using GPTMS ((3-glycidoxypropyl) trimethoxysilane) as the only inorganic precursor. Molecular structure and morphology of membrane were analyzed by $^{29}Si$-NMR, DSC and SEM. PEBAX$_{(R)}$-2533 membrane exhibited higher gas permeability coefficients than PEBAX$^{(R)}$-1657 membrane. This was explained by the increase of chain mobility. In contrast, ideal separation factor of $CO_2/CH_4$ for PEBAX$^{(R)}$-1657 membrane was higher than PEBAX$^{(R)}$-2533 membrane. It was explained by the decrease of diffusion selectivity caused by increase of chain mobility. For PEBAX$^{(R)}$/GPTMS hybrid membrane, gas permeability coefficients were decreased with reaction time. Gas permeability coefficient of $CH_4$ was more significantly decreased than $CO_2$. It can be explained by the reduction of chain mobility caused by the sol-gel process, and strong affinity of PEO segment with $CO_2$. Comparing with pure PEBAX$^{(R)}$-1657 membrane, ideal separation factor of $CO_2/CH_4$ for PEBAX$^{(R)}$/GPTMS hybrid membrane has decreased to 4.5%, and gas permeability coefficient of $CO_2$ has increased 3.5 times.

• Proceedings of the Membrane Society of Korea Conference
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• 1999.07a
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• pp.39-42
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• 1999

Perfluoropolymers represent the ultimate resistance to hostile chemical environments and high service temperature, attributed to the presence of fluorine in the polymer backbone, i.e. to the high bond energy of C-F and C-C bonds of fluorocarbons. Copolymers of Tetrafluoroethylene (TEE) and 2, 2, 4Trifluoro-5Trifluorometoxy- 1, 3Dioxole (TTD), commercially known as HYFLON AD, are amorphous perfluoropolymers with glass transition temperature (Tg)higher than room temperature, showing a thermal decomposition temperature exceeding 40$0^{\circ}C$. These polymer systems are highly soluble in fluorinated solvents, with low solution viscosities. This property allows the preparation of self-supported and composite membranes with desired membrane thickness. Symmetric and asymmetric perfluoropolymer membranes, made with HYFLON AD, have been prepared and evaluated. Porous and not porous symmetric membranes have been obtained by solvent evaporation with various processing conditions. Asymmetric membranes have been prepared by th wet phase inversion method. Measure of contact angle to distilled water have been carried out. Figure 1 compares experimental results with those of other commercial membranes. Contact angles of about 120$^{\circ}$for our amorphous perfluoropolymer membranes demonstrate that they posses a high hydrophobic character. Measure of contact angles to hexandecane have been also carried out to evaluate the organophobic character. Rsults are reported in Figure 2. The observed strong organophobicity leads to excellent fouling resistance and inertness. Porous membranes with pore size between 30 and 80 nanometers have shown no permeation to water at pressures as high as 10 bars. However high permeation to gases, such as O2, N2 and CO2, and no selectivities were observed. Considering the porous structure of the membrane, this behavior was expected. In consideration of the above properties, possible useful uses in th field of gas- liquid separations are envisaged for these membranes. A particularly promising application is in the field of membrane contactors, equipments in which membranes are used to improve mass transfer coefficients in respect to traditional extraction and absorption processes. Gas permeation properties have been evaluated for asymmetric membranes and composite symmetric ones. Experimental permselectivity values, obtained at different pressure differences, to various single gases are reported in Tab. 1, 2 and 3. Experimental data have been compared with literature data obtained with membranes made with different amorphous perfluoropolymer systems, such as copolymers of Perfluoro2, 2dimethyl dioxole (PDD) and Tetrafluorethylene, commercialized by the Du Pont Company with the trade name of Teflon AF. An interesting linear relationship between permeability and the glass transition temperature of the polymer constituting the membrane has been observed. Results are descussed in terms of polymer chain structure, which affects the presence of voids at molecular scale and their size distribution. Molecular Dyanmics studies are in progress in order to support the understanding of these results. A modified Theodoru- Suter method provided by the Amorphous Cell module of InsightII/Discover was used to determine the chain packing. A completely amorphous polymer box of about 3.5 nm was considered. Last but not least the use of amorphous perfluoropolymer membranes appears to be ideal when separation processes have to be performed in hostile environments, i.e. high temperatures and aggressive non-aqueous media, such as chemicals and solvents. In these cases Hyflon AD membranes can exploit the outstanding resistance of perfluoropolymers.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.1
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• pp.47-53
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• 2011

$SF_6$ (Sulfur hexafluoride) possesses high GWP (Global Warming Potential) as sepcified by the IPCC (Intergonvernmental Panel of Climate Change). Recently, the recovery-separtion of $SF_6$ research area, including permeation properties studies using various membrane's materials and the practical operation of recovery-separtion using membrane of waste $SF_6$ gas is in the initial state. The separation efficiency of a single $SF_6$ and waste $SF_6$ mixture was evaluated using a PSF (polysulfone), PC (tetra-bromo polycarbonate) and PI (polyimide) hollow fiber membranes. According to the results of single gases permeation properties, PI membrane has the highest permselectivity of $N_2$ gas in $N_2/SF_6$ gas. Under the condition of P=0.5 MPa, the highest concentration of recovered $SF_6$ is 95.6 vol % in the separation experiment of $SF_6/N_2$ mixture gas by PC membrane. Under the operation pressure of P=0.3 MPa at a fixed retentate flow rate fixed of 150 cc/min, the maximum recovery efficiency of $SF_6$ is up to 97.8% by PSF membrane. From the results above, it is thought that the separation and recovery technique of $SF_6$ gas using membrane will be used as the representative eco-technology in the $SF_6$ gas treatment in the future.