• Applied Chemistry for Engineering
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• v.18 no.6
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• pp.643-649
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• 2007

Lipase-catalyzed esterification of structural butanol isomers and n-butyric acid was investigated in supercritical carbon dioxide. The experiments were performed in a high pressure cell for 5 hrs with a stirring rate of 150 rpm at 323.15 K and 130 bar. The Candida Antarctica lipase B (CALB) was used in whole system as a catalyst. The experimental results were analyzed by GC-FID using a INNOWax capillary column. The conversion yield and the tendency of the esterification in supercritical carbon dioxide were compared with estimated results by molecular dynamics simulation. Based on the Ping-Pong Bi-Bi mechanism with competitive inhibition, each step of the reaction was optimized; using this result the transition state was predicted. Conformational preference of isomers was also analyzed using molecular dynamics simulations. This kind of approach will be further extended to the prediction of enzyme-catalyzed reactions using computers.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.18 no.10
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• pp.136-152
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• 2017

The thermodynamic models, PC-SAFT (Perturbed-Chain Statistical Associated Fluid Theory) state equation and the Two-model approach liquid activity coefficient model NRTL (Non Random Two Liquid) + Henry + Peng-Robinson, for modeling the Rectisol process using methanol aqueous solution as the $CO_2$ removal solvent were compared. In addition, to determine the new binary interaction parameters of the PC-SAFT state equations and the Henry's constant of the two-model approach, absorption equilibrium experiments between carbon dioxide and methanol at 273.25K and 262.35K were carried out and regression analysis was performed. The accuracy of the newly determined parameters was verified through the regression results of the experimental data. These model equations and validated parameters were used to model the carbon dioxide removal process. In the case of using the two-model approach, the methanol solvent flow rate required to remove 99.00% of $CO_2$ was estimated to be approximately 43.72% higher, the cooling water consumption in the distillation tower was 39.22% higher, and the steam consumption was 43.09% higher than that using PC-SAFT EOS. In conclusion, the Rectisol process operating under high pressure was designed to be larger than that using the PC-SAFT state equation when modeled using the liquid activity coefficient model equation with Henry's relation. For this reason, if the quantity of low-solubility gas components dissolved in a liquid at a constant temperature is proportional to the partial pressure of the gas phase, the carbon dioxide with high solubility in methanol does not predict the absorption characteristics between methanol and carbon dioxide.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.3
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• pp.305-312
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• 2011

The use of a separator to control stack temperature in a molten carbonate fuel cell was studied by numerical simulation using a computational fluid dynamics code. The stack model assumed steady-state and constant-load operation of a co-flow stack with an external reformer at atmospheric pressure. Representing a conventional cell type, separators with two flow paths, one each for the anode and cathode gas, were simulated under conditions in which the cathode gas was composed of either air and carbon dioxide (case I) or oxygen and carbon dioxide (case II). The results showed that the average cell potential in case II was higher than that in case I due to the higher partial pressures of oxygen and carbon dioxide in the cathode gas. This result indicates that the amount of heat released during the electrochemical reactions was less for case II than for case I under the same load. However, simulated results showed that the maximum stack temperature in case I was lower than that in case II due to a reduction in the total flow rate of the cathode gas. To control the stack temperature and retain a high cell potential, we proposed the use of a separator with three flow paths (case III); two flow paths for the electrodes and a path in the center of the separator for the flow of nitrogen for cooling. The simulated results for case III showed that the average cell potential was similar to that in case II, indicating that the amount of heat released in the stack was similar to that in case II, and that the maximum stack temperature was the lowest of the three cases due to the nitrogen gas flow in the center of the separator. In summary, the simulated results showed that the use of a separator with three flow paths enabled temperature control in a co-flow stack with an external reformer at atmospheric pressure.

• Applied Chemistry for Engineering
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• v.10 no.1
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• pp.129-134
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• 1999

This study is related to the investigation of the direct incorporation of $CO_2$ to polymer using quaternary ammonium salt catalysts. Quaternary ammonium salts showed good catalytic activity of $CO_2$ fixation in the synthesis of poly[(1,3-dioxolane-2-oxo-4-yl)methyl methacrylate] [poly(DOMA)] by the direct incorporation of $CO_2$ to poly(glycidyl methacrylate)[poly(GMA)]. Among the salts tested, the ones with higher alkyl chain length and with more nucleophilic counter anion showed higher catalytic activity. The yield of carbon dioxide addition increased with the reaction temperature. Kinetic study was carried out by measuring the variation of $CO_2$, pressure in a high pressure batch reactor. The reaction rate was first order to the concentration of poly(GMA) and $CO_2$, respectively. The rate constant was $0.69L/mol{\cdot}h$ and Henry's constant of $CO_2$ in DMSO at $80^{\circ}C$ was $6.8{\times}10^{-4}mol/L{\cdot}KPa$.

• KSBB Journal
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• v.21 no.3
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• pp.194-198
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• 2006

Dried raw Ascidians(Halocynthia roretzi) shells harvested from fish farms in southern coast area in Korea were used to extract ${\beta}$-carotene using supercritical carbon dioxide($SCO_2$) and with ethanol as a co-solvent at the range of temperatures and pressures, from 25 to $65^{\circ}C$ and 100 to 350 bar respectively. The size of the dried Ascidians shells was around $850{\mu}m$. The system used this study was a semi-batch flow type high pressure unit. The efficiency of ${\beta}$-carotene extraction using $SCO_2$ with and without co-solvent, ethanol, influenced to pressure and temperature changes. The highest solubility of ${\beta}$-carotene in $SCO_2$ was 1.35 mg/g for ${\beta}$-carotene at $35^{\circ}C$ and 350 bar. With addition of 2(v/v%) ethanol the recovery of ${\beta}$-carotene was 93%. As a result of using n-hexane and methanol for rinse, at $35^{\circ}C$ and 350 bar the amount of ${\beta}$-carotene by methanol rinse was 5 times higher than that of n-hexane rinse.

• Clean Technology
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• v.23 no.4
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• pp.357-363
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• 2017

In this study, the supercritical carbon dioxide ($scCO_2$)/ n-butyl acetate (n-BA) co-solvent system was employed to remove an unexposed negative photoresist (PR) from the surface of a silicon wafer. In addition, the selectivity of the $scCO_2$/n-BA co-solvent system was confirmed for the unexposed and exposed negative PR. Optimum conditions for removal of the unexposed PR were obtained from various conditions such as pressure, temperature and n-BA ratio. The n-BA was highly soluble in $scCO_2$ without cloud point and phase separation in mostly experimental conditions. However, the $scCO_2$/n-BA co-solvent was phase separated at 100 bar, above $80^{\circ}C$. The unexposed and exposed PR was swelled in $scCO_2$ solvent at all experimental conditions. The complete removal of unexposed PR was achieved from the reaction condition of 160 bar, 10 min, $40^{\circ}C$ and 75 wt% n-BA in $scCO_2$, as measured by ellipsometry. The exposed photoresist showed high stability in the $scCO_2$/n-BA co-solvent system, which indicated that the $scCO_2$/n-BA co-solvent system has high selectivity for the PR removal in photo lithograph process. The $scCO_2$/n-BA co-solvent system not only prevent swelling of exposed PR, but also provide efficient and powful performance to removal unexposed PR.

• Journal of Institute of Control, Robotics and Systems
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• v.12 no.12
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• pp.1184-1190
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• 2006

Most chemical companies try to maximize their energy efficiencies due to high oil price and reinforcement of environmental regulation. An individual factory continuously has tried to reduce energy consumption or carbon dioxide discharge for high profit. Nevertheless, it is found that waste heat is disposed with forms of low or medium pressure steams. It can be improved by the aspect of entire industrial complex. Therefore, we have developed a steam network optimization method using Steam Networking Matrices(SNMs) in this research. Results from an illustrative example show that energy consumption can be reduced by optimizing steam exchange networks.

• Transactions of the Korean hydrogen and new energy society
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• v.7 no.2
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• pp.147-155
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• 1996

The aim of this study is the development of technologies of methanol production from carbon dioxide by catalytic hydrogenation. Experiments about carbon dioxide hydrogenation by catalyst mixed with CuO, ZnO, $Cr_2O_3$ and $Al_2O_3$ were conducted to find optimum catalyst and reaction condition. Reactions were carried out at atmospheric and high pressures between 200 to $350^{\circ}C$. High yield of methanol was obtained with $Cu/ZnO/Cr_2O/Cr_2O_3/Al_2O_3$ catalyst at $250^{\circ}C$ and above 30 atmospheric pressure. There was not any increament of hydrogenation reactivity for the catalysts which was made by the addition of Pd to $Cu/ZnO/Cr_2O/Cr_2O_3/Al_2O_3$.

• Polymer(Korea)
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• v.35 no.5
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• pp.458-466
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• 2011

In the mixed system of supercritical carbon dioxide/organic solvents, poly(vinyl alcohol)(PVA) film of high degree of hydrolysis could be dyed with a dichroic dye of C. I. direct black 22(DB22) and as a result, high durability was obtained. Especially, as a dye dispersant in a supercritical fluid phase, a mixed solvent system of ethylene glycol: dimethyl sulfoxide=4 : 6 weight ratio was investigated. Then the optimum pressure for dyeing could be reduced down to 200 bar. Using this supercritical fluid system, the maximum dyeing appeared as the transmittance of less than 1% and the waste amount was reduced to the level of 1/10. After 500% drawing of this PVA film, both the polarizing efficiency of 94% and the single piece transmittance of 30% were obtained. The limitation of DB22 and further improvements were also discussed.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.377-382
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• 2014

Micro-/macroporous carbons (MMCs) were prepared using a hollow mesoporous silica capsule (HMSC) as a sacrificial hard template. The carbonization process after the infiltration of furfuryl alcohol into the template-free HMSC material afforded MMC materials in high yield. The hard template HMSC could be removed by HF etching without deteriorating the structure of MMC. The MMC materials were fully characterized by SEM, TEM, PXRD, XPS, and Raman spectroscopy. The replication processes were so successful that MMCs exhibited a hollow capsular structure with multimodal microporosity. Detailed textural properties of MMC materials were investigated by volumetric $N_2$ adsorption-desorption analysis at 77 K. To explore the gas sorption abilities of MMCs for other gases, $H_2$ and $CO_2$ sorption analyses were also performed at various temperatures. The multimodal MMC materials were found to be good sorbents for both $H_2$ and $CO_2$ at low pressure.