• Korean Chemical Engineering Research
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• 제51권1호
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• pp.58-67
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• 2013

PBT (polybutylene terephthalate)는 저흡수율, 치수 안정성, 내마모성 등 기계적 특성이 우수하며, 전기전자 부품, 자동차 부품, 각종 정밀 부품에 사용된다. DMT (dimethyl terephthalate)와 BD (1,4-butandiol)를 사용하여 PBT의 원료단량체인 BHBT (bis-hydroxybutyle terephthalate)를 생산하는 에스테르 교환 반응 반응에 대해 연구 하였다. 촉매로는 zinc acetate가 사용되었다. 기존의 연구에서는 반응 중 생성 메탄올이 제거되는 반회분식 반응기를 통한 kinetics 연구가 이루어져 역반응이 고려되지 않음에 따른 모델의 부정확함이 있었다. 본 연구에서는 회분식 반응기를 사용하고 반응 중 DMT와 메탄올 양을 정량하여 생성되는 MHBT (methyl hydroxylbutylene terephthalate)와 BHBT를 추정할 수 있도록 하고, 이 반응들에서 역반응들을 고려할 수 있도록 하여 보다 정확한 모델을 제안하였다. 다양한 반응속도 모델을 제시하였고, 이 모델들이 예측한 값들이 실험 데이터와 잘 일치함을 보였다.

• Korean Chemical Engineering Research
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• 제51권1호
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• pp.144-150
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• 2013

본 연구에서는 촉매로 zinc acetate를 사용하였고 dimethyl terephthalate(DMT)와 ethylene glycol(EG)의 에스테르 교환을 통하여 polyethylene terephthalate(PET)의 단량체인 bishydroxyethyl terephthalate(BHET)를 생성하는 반응에 대하여 알아보았다. 기존의 kinetics 연구는 에스테르 교환 반응에서 생성되는 메탄올이 반응계에서 제거되는 반회분식공정을 바탕으로 하여 이때 제거된 메탄올 양을 측정하여 역반응이 무시된 반응 kinetics 모델을 구성하였다. 본 연구에서는 회분식 반응기를 통하여 DMT와 메탄올의 양을 정량하여, 역반응을 고려한 보다 정확한 kinetics 모델을 제안하였고, 제안된 모델의 예측값들이 실험값들과 잘 일치하는 것을 보였다. 또한 모델과 실험값을 분석하여 여러 공정 변수들이 에스테르 교환 반응에 미치는 영향을 조사하였다.

• Advances in environmental research
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• 제1권3호
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• pp.191-199
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• 2012

A kinetic study of the transesterification of soybean oil was conducted using microwaves under various temperatures, power densities, and reaction times. Results show that power density affects the kinetics and yield. The biodiesel yield increased with increasing microwave power density. The non-thermal effects of microwave irradiation on transesterification reactions were evaluated at a constant reaction temperature ($65^{\circ}C$) and power density (0.204 $Wg^{-1}$). Microwave irradiation was found to increase the reaction rates by 3.52-7.06 fold.

• Korean Chemical Engineering Research
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• 제53권2호
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• pp.253-261
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• 2015

DMT(dimethylterephthalate)와 DEG(diethylene glycol)의 에스테르 교환반응을 통하여 BHEET(bis-hydroxyethoxyethyl-terephthalate)을 생성하는 반응에 대하여 조사하였다. BHEET는 polyurethanr foam의 원료인 폴리에스터 폴리올의 단량체이다. DMT를 이용한 기존의 에스테르 교환 반응은 반응 중 생성 MeOH이 제거되는 반회분식 반응기를 사용하였다. 따라서 이러한 kinetics 연구에서는 역반응이 고려되지 않는다. 본 실험에서는 촉매로는 zinc acetate를 사용하였고, 소형 회분식 반응기를 통하여 DMT와 MeOH의 양을 정량하여 생성되는 MHEET와 BHEET를 추정하였다. 이 반응들에서 역반응을 고려한 보다 정확한 반응 kinetics를 조사하였다. 제안된 모델의 예측 값들이 실험값들과 잘 일치함을 보였다.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1471-1473
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• 2004

An efficient dynamic kinetic resolution of racemic ${\beta}$-hydroxyalkylferrocene and 1,1'-bis( ${\beta}$-hydroxyalkyl)-ferrocene derivatives was achieved using lipase/ruthenium-catalyzed transesterification in the presence of an acyl donor. The racemic ${\beta}$-hydroxyalkylferrocene derivatives were successfully transformed to the corresponding chiral acetates of high optical purities in high yields.

• Korean Chemical Engineering Research
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• 제56권2호
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• pp.275-280
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• 2018

Methyl ester derived from coconut oil is very interesting to study since it contains free-fatty acid with chemical structure of medium carbon chain ($C_{12}-C_{14}$), so the methyl ester obtained from its part can be a biodiesel and another partially into biokerosene. The use of heterogeneous catalysts in the production of methyl ester requires severe conditions (high pressure and high temperature), while at low temperature and atmospheric conditions, yield of methyl ester is relatively very low. By using microwave irradiation trans-esterification reaction with heterogeneous catalysts, it is expected to be much faster and can give higher yields. Therefore, we studied the production of methyl ester from coconut oil using CaO catalyst assisted by microwave. Our aim was to find a kinetic model of methyl ester production through a transesterification process from coconut oil assisted by microwave using heterogeneous CaO catalyst. The experimental apparatus consisted of a batch reactor placed in a microwave oven equipped with a condenser, stirrer and temperature controllers. Batch process was conducted at atmospheric pressure with a variation of CaO catalyst concentration (0.5; 1.0; 1.5; 2.0, 2.5%) and microwave power (100, 264 and 400 W). In general, the production process of methyl esters by heterogeneous catalyst will obtain three layers, wherein the first layer is the product of methyl ester, the second layer is glycerol and the third layer is the catalyst. The experimental results show that the yield of methyl ester increases along with the increase of microwave power, catalyst concentration and reaction time. Kinetic model of methyl ester production can be represented by the following equation: $-r_{TG}=1.7{\cdot}10^6{_e}{\frac{-43.86}{RT}}C_{TG}$.

• 한국응용과학기술학회지
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• 제25권4호
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• pp.418-428
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• 2008

Transesterification of fat of Tra catfish with methanol in the presence of the KOH catalyst yields fatty acid methyl esters (FAME) and glycerol (GL). The effects of the reaction temperature and reaction time on rate constants and kinetic order were investigated. Three regions were observed. In the initial stage, the immiscibility of the Tra fat and methanol limited the reaction rate, hence this region was controlled by the mass transfer. Subsequent to this region, produced FAME like a co-solvent made the reaction mixture homogeneous, therefore the conversion rate increased rapidly so it was controlled by the kinetic parameters of the reaction until the equilibrium was approached in the final slow region. A second-order kinetic mechanism was proposed involving second regions for the forward reaction. The rate determining step for the overall KOH catalyzed-methanolysis of Tra fat was the conversion of triglycerides (TG) to diglycerides (DG). This rate constant was increased from 0.003 to $0.019min^{-1}$ when the reaction temperature was increased from 35 to $60^{\circ}C$. Its calculated activation energy was 14.379 ($kcal.mol^{-1}$).

• Korean Chemical Engineering Research
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• 제56권3호
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• pp.416-420
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• 2018

A comprehensive kinetic study has been conducted on dimethyl carbonate synthesis by transesterification reaction of ethylene carbonate with methanol. An alkali base metal (KOH) was used as catalyst in the synthesis of DMC, and its catalytic ability was investigated in terms of kinetics. The experiment was performed in a batch reactor at atmospheric pressure. The reaction orders, the activation energy and the rate constants were determined for both forward and backward reactions. The reaction order for forward and backward reactions was 0.87 and 2.15, and the activation energy was 12.73 and 29.28 kJ/mol, respectively. Using the general factor analysis in the design of experiments, we analyzed the main effects and interactions according to the MeOH/EC, reaction temperature and KOH concentration. DMC yield with various reaction conditions was presented for all ranges using surface and contour plot. Furthermore, the optimal conditions for DMC yield were determined using response surface method.

• 폴리머
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• 제29권1호
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• pp.41-47
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• 2005

디메틸 테레프탈레이트(DMT)와 1,3-프로판디올(PDO)을 175~190 $^{\circ}C$ 사이의 일정 온도에서 티타늄부톡사이드(TBO) 촉매를 사용하여 에스테르교환반응 속도에 대해서 조사하였다. 에스테르교환반응 정도는 반응기 밖으로 유출되어 나오는 메탄올의 양으로 결정하였으며, 메탄올의 수득률은 반응온도, PDO/DMT의 몰비 및 촉매농도가 증가할수록 증가하였다. 반응차수는 DMT, PDO 및 촉매의 농도에 대해 각각 1차 반응이며, 총괄차수는 3차 반응이었다. 반응속도상수로 계산된 활성화에너지는 26.93 kcal/mole 이었으며, 생성된 비스(2-히드록시트리메틸)테레프탈레이트(BHTMT)의 용융온도는 85.2 $^{\circ}C$, 용융열은 141.3 J/g 이었다.

• Bulletin of the Korean Chemical Society
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• 제27권5호
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• pp.755-758
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• 2006