• Proceedings of the Membrane Society of Korea Conference
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• 1995.04a
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• pp.38-39
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• 1995

최근 자동차 대체 연료로 가솔린에 10% 무수에탄올이 혼합된 Gasohol 사용에 관한 관심이 고조되고 있으며, 이는 Gasohol이 자동차 배기 가스중의 일산화탄소 및 탄화수소 함유량을 감소시켜 대기 오염을 줄일 수 있기 때문이다. Gasohol에 사용되는 무수에탄올의 농도는 99.5% 이상이어야 하며, 이러한 고순도의 에탄올을 제조하기 위해서는 물과 에탄올의 공비 혼합물(95.6% 에탄올)로부터 공비증류, 분자체 흡착, 투과증발과 같은 분리 조작을 이용하여 물을 제거하는 공정이 필요하다. 현재 에탄올 탈수에는 공비증류가 많이 사용되고 있으나 공비증류는 에너지 사용량이 많을 뿐더러 유독한 Entrainer를 첨가하기 때문에 투과증발과 같은 저 에너지 소비형, 환경친화적인 공정으로의 전환이 이루어지고 있다. 에탄올 탈수용 투과증발 플랜트는 전세계 20여개가 가동되고 있으며, 상업화된 플랜트의 대부분은 독일의 Deutsche Carbone사가 제조한 PVA/PAN 투과증발 복합막을 사용하고 있다. 투과증발 시스템은 물에 대한 친화도가 높은 투과증발막 및 모듈, 기타 분리 구동력을 높여주기 위한 Heater, 진공펌프, 냉각기, 열 교환기 등의 주변 설비로 구성되며, 투과증발 시스템 개발을 위해서는 우수한 막/모듈 제조와 아울러 최적 공정 설계 기술 개발이 필수적이라 하겠다.

• Proceedings of the Membrane Society of Korea Conference
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• 1994.10a
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• pp.32-33
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• 1994

Poly(vinyl alcohol)(PVA) membranes crosslinked with Glutaraldehyde (GA) were prepared for the separation of acetic acid-water mixtures. For the preparation of the crosslinked membranes, dry PVA films were immersed for 2 days at 40$\circ$C in reaction solutions which contain different content of GA solution(25% GA in water), aceton and a catalyst, HCl. IR spectroscopy was employed to characterize the crosslinking reaction between hydroxyl groups in PVA and aldehyde groups in GA. Swelling measurements of the crosslinked membranes were carried out in both water and acetic acid to investigate the crosslinking density and swelling behaviour of the membranes.

• Applied Chemistry for Engineering
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• v.3 no.4
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• pp.595-604
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• 1992

Carbonate-type polyurethane resins containing anionic moieties were systhesized from NCO-terminated prepolymer method. Membranes were manufactured from the polymer solution and the separation of aqueous ethanol solution was investigated. To enhance the property of urethane resin, carbonate-type polyol(PTMCG) was used. ${\alpha}^{\prime},{\alpha}^{{\prime}{\prime}}$-dimethylolpropionic acid was used as a chain extender to increase the hydrophilicily of the urethane membrane. The ionization of the pendent carboxylic groups in urethane resin was carried out using trimthylamine. To confirm the formation of anionic groups in urethane resin, IR spectra of model compounds were compared with those of urethane resins. It was confirmed that the concentration of hard segment and hydrogen bond contributed to the property of the concentration of hard segment and hydrogen bond contributed to the property of urethane resin in which the mole ratio of chain extender and polyol was from 3:1 to urethane resin in which the mole ratio of chain extender and polyol was from 3:1 to 5:1. The carbonate-type polyurethane containing pendent carboxylic grop(PU) had Tg of around-$25^{\circ}C$ and Tm, $45^{\circ}C$ measured by DSC. Transition temperatures of one containing pendent anionic group(APU) prepared from the ionization of PU shifted to $8{\sim}10^{\circ}C$ lower temperature region than those of PU. Pervaporation membrane was prepared through the casting method. N, N-dimethylformamide (DMF) were used as a solvent and hexamethylene diisocyanate(HMDl) as a crosslinking agent. Swelling degree increased with ethanol concentration in mixure and the control of the swelling degree of the membrane could be achieved by crossliking. The results of pervaporation were as follows : separation factor, 2.3~9.8 ; flux, $27{\sim}79.5g/m^2hr$. Pervaporation separation capacity could be enhanced by reducing the molecular weight of polyol from 2,000 to 1,000.

• Membrane Journal
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• v.5 no.2
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• pp.74-80
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• 1995

Asymmetric poly(vinyl alcohol) (PVA) membranes were prepared by varying the precipitation conditions of the phase inversion technique, and the influences of precipitation conditions on the water uptake of the membrane were investigate. The degree of water uptake of the membrane increased and reached a certain maximum value, as the precipitation time increased. However, it decreded after that. As the precipition temperauure became lower, the degree of water uptake increased more or less. The addition of a nonionic surfactant to the precipitaon solution was effective reducing the precipitation time by lowering the surface tension of the precipitation solution, but ig didn't change the maximum value of its own degree of water uptake. In addition, the relationship between the degree of water uptake and the separation characteristics and mechanical properies of the membrane were investigated. The selectivity factor of the membrane for pervaperation separation decreased, but the permeate flux increased, respectively, with increasing the degree of water uptake. The tensile strength and elongation of the membrane, respectively, increased to a maximum value with increasing the degree of water uptake, and then decreased abtuptly.

• Membrane Journal
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• v.8 no.4
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• pp.235-242
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• 1998

Pervaporation separation of methyl tert-butyl ether (MTBE) and methanol (MeOH) mixture, of which the former compound is well known as the octane booster was carried out. Poly(vinyl alcohol) (PVA) membranes crosslinked with poly(acrylic acid) which have been successfully applied on the water-alcohol mixtures were used in this study. The PVA/PAA ratio in the crosslinked membranes was 95/5, 90/10, 85/15, 80/20, and 75/25 by weight. The operating temperatures were 30, 40, and 50$\circ$C, and the compositions of MTBE and MeOH to be separated were 95/5, 90/10, and 80/20 (MTBE/MeOH) solutions. PVA/PAA=85/15 membrane showed the separation factor $\alpha_{MeOH/MTBE}$=4000 and the permeation rate of 10.1 g/m$^2$hr for MTBE/MeOH=80/20 solution at 50$\circ$. When the same membrane was used, the separation factor and permeation rate for MTBE/MeOH=90/10 solution at 40$\circ$C were $\alpha_{MeOH/MTBE}$=6000 and 8.5 g/m$^2$hr, respectively. Also, the hydrophilic/hydrophobic balance of the membranes would take an important role in the relationships between the membranes and separation performances in terms of the flux and the separation factor.

• Proceedings of the Membrane Society of Korea Conference
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• 1997.10a
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• pp.83-84
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• 1997

1. INTRODUCTION : Polyimides containing siloxane moiety(poly(imide siloxane), or polysiloxaneimide) have been synthesized because of their some merits over polyimide itseft. Polyimides have excellent thermal and mechanical properties but their poor solubility and processibility in their fullly imidized form give disadvantages in applications. Incorporation of siloxane units make it possible to increase solubility and processibility, and also impart impact resistance, low moisture uptake, low dielectric constant, thermo-oxidative resistance, good adhesion properties to substrate and etc.. Incorporation methods of siloxane groups into the polyimide was mainly copolymerization or terpolymerization between oligomeric dimethylsiloxane and aromatic dianhydride. A few methods of introducing siloxane units in functional groups of polyimide was reported. In our laboratory poly(amideimide siloxane) and poly(imide siloxane) were prepared and the study about their thermal kinetics was performed. In separation membrane area, polysiloxaneimides was utilized in pervaporation and gas separation. Polyimides in gas separation show high selectivity and very low permeability, and introduction of siloxane segments increase permeability with low decrease in selectivity. We aimed to introduce silicone segments into poly(amic acid) state and synthesize polymer partially imidized, and also show the gas separation characteristics of the synthesized polymer.

• Membrane Journal
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• v.6 no.4
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• pp.227-235
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• 1996

poly(acrylic acid)(PAA)-poly(vinyl alcohol)(PVA) membranes have been prepared by crosslinking reaction between the carboxylic acid groups of PAA and the hydroxylic groups of PVA. In the measurements of the swelling and preferential sorption of the membranes, sorption behaviors of the membranes in pure water, pure acetic acid and a mixture of them have been investigated, respectively. From the measurements of the preferential sorption in 90wt% acetic acid of aqueous mixture, the sorption of water component was found to be more enhanced at high PAA content in the membrane than that of acetic acid component due to the interaction of water with acetic acid. The sorption behavior and the degree of crosslinking influenced competitively the permeation behavior of permeants. Permeation behavior of perrecants through the membranes was analyzed by using permeation activation energies which had been obtained from the Arrhenius plots of fluxes.

• Applied Chemistry for Engineering
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• v.10 no.4
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• pp.515-522
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• 1999

Asymmetric polyetherimide membrane were prepared by phase inversion method, and the effects of NaOH concentration and reaction time on the morphology change of the polyetherimide membranes were studied. The morphology of skin layers varied from dense structure to sphere structure with increasing concentration of modification solution. The thickness of dense layer increased with increasing reaction time. However, when either the concentration of modifying solution was very high or the reaction time was very long, the dense layers of the asymmetric membrane were disappeared. From these results, it was found that the surface morphology of the asymmetric polyetherimide membranes depended strongly on the modification conditions such as concentration of modification solution and reaction time. These results might be explained by the hydrolysis reaction of polyetherimide into polyamic acid by the NaOH solution.

• Membrane Journal
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• v.9 no.2
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• pp.97-106
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• 1999

A and 2SM-5 type zeoli tic crystal films were synthesized on porous supports from the reaction mixture of 1.9 ${SiO}_2$1.5 $Na_20-Al_2O_3-40$ $H_20$ and $Si0_2$-0.l3 $Na_2O$-52 $H_20$-O.l2 TPAOH composition, respectively. The zeolite films were characterized by XRD and SEM. The 2SM -5 crystals grown on the porous matrix were very closely bound together. It was so difficult to obtain the perfectly intergrown crystals in the case of A-type zeolite and this crystal was transformed into P-type zeolite membrane with a prolonged reaction time. The densely intergrown A type zeolite crystal membrane could be also synthesized by the hydrothermal treatment at 100$^{\cirt}C$ after pressing the reaction mixture without addition of water. The pervaporation performance of the synthesized porous inorganic membranes was investigated for alcohol and water mixtures. A-type zeolite membrane crystallized as a thin film showed the selective \'Jermeability of water from the mixtures through the molecular sieving activity of micropores.

• Membrane Journal
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• v.11 no.3
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• pp.133-139
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• 2001

The hydorgen ions in PVA/SSA membranes were substituted with monovalent metal ions, $Li^{+}$, $Na^{+}$, $K^{+}$, divalent metal ion forms, $Mg^{2+}$, $Ca^{2+}$, $Ba^{2+}$, trivalent metal ion forms, $Al^{+}$. The effect of exchange with metal ions was investigated through the swelling measurement and pervaporative experiments for water-ethanol and water-methanol mixtures at various operating conditions. In addition, ESCA analysis was carried out to study the substitution of the metal ions in membranes. The swelling ratio decerased in the sequence of $Li^{+}$, $Na^{+}$, $K^{+}$ and this might be due to the 'salting-out` effect while the swelling ratios for divalnet and trivalent ion-substituted membranes were affected by the combined effect of salting-out, electrostatic crosslinking and extent of metal ion substitution. For the pervaporation performance, PVA/SSA-$H^{+}$membrane showed the lowest flux and highest separation factor for all aqueous ethanol solutions. The typical results of the flux, 59 g/$m^{2}$hr and the separation factor, 44 were obtained at $50^{\circ}C$ for 90% ethanol aqueous mixture. For water-methanol solutions, the PVA/SSA membranes substituted with monovalent PVA/SSA membranes substituted with divalent and tribalent metal ions, both `salting-out` and electrostatic effects affected the pervaporative results.