• Membrane and Water Treatment
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• 제7권2호
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• pp.143-154
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• 2016

Acetic acid can be removed from wastewater by esterification in a membrane reactor. Pervaporation membrane reactor (PVMR) is an alternative process to conventional separation processes. It is an environmentally friendly process. The main advantages of the PVMR are simultaneous water removal and production of an ester economically. In this study, the synthetic wastewater has been used. Esterification reaction of acetic acid with isopropanol has been studied in the presence of tungstosilicic acid hydrate as a catalyst in a batch reactor and in a PVMR. The effects of important operating parameters such as reaction temperature, initial molar ratio of isopropanol to acetic acid and catalyst concentration has been examined. Removal of acetic acid (conversion of acetic acid) was obtained as 85% using a PVMR by removal of water from the reaction mixture.

• Bulletin of the Korean Chemical Society
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• 제34권11호
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• pp.3410-3414
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• 2013

Atom-economical esterification is of great importance in green chemistry. In this work, we demonstrated the catalyst and additive free esterification of alcohols by their reaction with 2-acyl-4,5-dichloropyridazin-3(2H)-ones without solvent at $100^{\circ}C$. Aliphatic and aromatic alcohols were converted into the corresponding esters in good to excellent yields. It is noteworthy that the reaction is solvent-free, atom-economic, easy-workup, and rapid and that the process is inexpensive.

• KSBB Journal
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• 제17권6호
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• pp.543-548
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• 2002

Candida rugosa lipase를 이용하여 효소 농도, 반응온도, 알콜 농도 및 종류 등의 반응조건에 따른 racemic ibuprofen 에스테르화 반응의 초기반응속도, 전환율 그리고 입체 선택성 을 조사하였다. 제조된 S-(+)-ibuprofen alkyl ester는 황산을 촉매로 하는 가수분해반응에 의해 순수한 S-(+)-ibuprofen으로 전환되었다. 에스테르화 반응에서는 반응온도 6$0^{\circ}C$에서 최대 활성을 보였으며, 그 이상의 온도에서는 효소의 활성 저하로 전환율과 enantiomeric excess값이 동시에 현격하게 감소하는 경향을 보였다. 알코올 농도가 증가할수록 알콜의 효소반응 저해제작용으로 인하여 초기반응속도가 감소하는 경향을 보였으며, 최종 전환율은 Ibuprofen와 Alcohol의 몰 비가 1/1에서 최고 값을 나타냈다. 알콜 종류에 따른 알코올 체인 길이가(C$_2$~C$_{10}$) 증가할수록 전환율은 증가하였는데, 특히 알코올 체인길이가 가장 큰 데칸올이 가장 높은 전환율을 보였다. 반응온도가 6$0^{\circ}C$ 이상의 높은 경우를 제외하고 에스테르화 반응 조건에 따라 입체 선택성 즉 enantiomeric excess의 큰 변화는 없었다. 화학적 가수분해 반응은 비교적 짧은 반응시간(3시간)내에 평형반응에 도달하였으며 알코올 체인 길이에 관계없이 거의 95% 이상의 높은 전환율 및 입체 선택성을 나타냈다. Lipase에 의한 ibuprofen 에스테르화 반응의 최적 조건과 화학적인 가수분해 반응을 통해서 racemic ibuprofen으로부터 높은 수율의 S-(+)-ibuprofen을 확보할 수 있었다.

• Bulletin of the Korean Chemical Society
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• 제35권6호
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• pp.1659-1664
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• 2014

A porous metal-organic framework (MOF), MIL-101, was synthesized in the presence of sulfated zirconia (SZ) to produce acidic SZ/MIL-101 composites for the first time. The composites were characterized with XRD, nitrogen adsorption, FT-IR, scanning electron microscope, chemical analysis and so on. The composites (SZ/MIL-101s) were successfully applied in a liquid-phase esterification for a high yield of ester. This catalytic result of SZ/MIL-101, compared with that of pure SZ or MIL-101 (showing a negligible yield of ester), suggests that the SZ in the composite is highly active in the acid catalysis probably because of the well-dispersed active species of SZ. Moreover, the esterification is catalyzed in heterogeneous mode as confirmed by negligible esterification after filtration of the catalyst. Finally, microwaves can be efficiently applied both in the synthesis of the composites and the esterification reaction to accelerate the two processes of synthesis and esterification by about 5 times.

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2361-2367
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• 2010

$TiO_2-ZrO_2$ was prepared with surfactant through a sol-gel method. Catalysts containing 5 - 35% $H_3PO_4$ were prepared using these oxides. Subsequently the catalytic performance of prepared catalysts was determined for liquid phase esterification of aromatic acids. $H_3PO_4/TiO_2-ZrO_2$ has been used as catalyst to synthesize various novel esters by esterification of some aromatic acids with aliphatic alcohols (2-propanol, 1-butanol, iso butanol, 3-pentanol, 1-hexanol, heptanol, cyclo heptanol, octanol and decanol). Under optimized conditions, maximum yields and selectivity (100%) to the corresponding ester, was obtained by using 25 wt % $H_3PO_4/TiO_2-ZrO_2$ as catalyst. The Catalyst can be easily recycled after reaction and can be reused without any significant loss of activity/selectivity performance. No by-product formation, high yields, short reaction times, mild reaction conditions, operational simplicity with reusability of the catalyst are the salient features of the present synthetic protocol. The reaction was carried out under solvent-free condition.

• Biotechnology and Bioprocess Engineering:BBE
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• 제7권2호
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• pp.76-84
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• 2002

On-line conversion estimation of enzymatic esterification reactions in solvent-free media was investigated. In principle, conversion to ester can be determined from the amount of water produced by the reaction, because water is formed as a by-product in a stoichiometric manner. In this study, we estimated the water production rate only from some measurements of relative humidity and water balances without using any analytical methods. In order to test the performance of the on-line conversion estimation, the lipase-catalyzed esterification of n-capric acid and n-decal alcohol in solvent-free media was performed whilst controlling water activity at various values. The reaction conversions estimated on-line were similar to those determined by offline gas chromatographic analysis. However, when the water activity was controlled at higher values, discrepancies between the estimated conversion values and the measured values became significant. The deviation was found to be due to the inaccurate measurement of the water content in the reaction medium during the initial stages of the reaction. Using a digital filter, we were able to improve the accuracy of the on-line conversion estimation method considerably. Despite the simplicity of this method, the on-line estimated conversions were in good agreement with the off-line measured values.

• 공업화학
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• 제33권4호
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• pp.440-443
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• 2022

만성 췌장염 치료제로 가장 널리 사용되고 있는 camostat mesylate 합성의 key step에 대한 연구를 수행하였다. Camostat mesylate는 두 중간체인 GBA (4-guanidinobenzoic acid hydrochloride)와 DOHA [2-(dimethylamino)-2-oxoethyl-2-(4-hydroxyphenyl)acetate]의 esterification 반응을 통해서 합성되는데, 기존의 esterification 방법 적용 시에는 낮은 수율과 고가의 시약으로 인한 문제점이 제기되어 왔다. 이런 문제점을 극복하고자 본 연구에서 Vilsmeier-Haack 반응을 이용하여 GBA의 acid 작용기를 activating하여 DOHA와 coupling하여 80%의 높은 수율로 Camostat mesylate를 제조할 수 있는 새로운 경제적인 합성법을 개발하였다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 추계학술대회 초록집
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• pp.108.2-108.2
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• 2011

This presentation shows energy-efficiency of microwave-accelerated esterification of free fatty acid with a heterogeneous catalyst by net microwave power measurement. In the reaction condition of 5wt% sulfated zirconia and 1:20 molar ratio of oil to methanol at $60^{\circ}C$ and atmospheric pressure, more than 90% conversion of the esterification was achieved in 20 minutes by microwave heating, while it took about 130 minutes by conventional heating. Electric energy consumption for the microwave heating in this accelerated esterification was only 67% of estimated minimum heat energy demand because of significantly reduced reaction time.

• Bulletin of the Korean Chemical Society
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• 제15권6호
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• pp.448-452
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• 1994

2-Hydroxymethyl-2,5-dihydrothiophene 1,1-dioxide (1) was prepared from thiophene-2-carboxylic acid by consecutive reactions involving the Birch reduction, esterification, reduction with lithium aluminum hydride, and oxidation with Oxone$^{\circledR}$. The esterification of alcohol 1 with various unsaturated carboxylic acids provided the precursors 8 for the intramolecular Diels-Alder reaction. The cheletropic expulsion of sulfur dioxide from the esters 8 followed by intramolecular Diels-Alder reaction furnished bicyclic ${\gamma}$-and ${\delta}$-lactones.

• Korean Chemical Engineering Research
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• 제52권3호
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• pp.395-401
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• 2014

본 연구에서는 고온($230{\sim}290^{\circ}C$)의 무촉매 조건에서 이루어지는 팜 지방산 디스틸레이트(PFAD)의 에스테르화 반응에 대해 수학적 모델링을 통해 그 반응 특성을 분석하였다. '무촉매 에스테르화 반응'에 대해 균일계(homogeneous) 2차 가역 반응으로 가정하였고 액상 내에서 동시적, 경쟁적으로 발생하고 있는 물과 메탄올의 증발과 반응을 모두 고려하기 위해 '반응 유효 인자'(reaction effectiveness factor, ${\eta}$)를 도입하였다. 각 반응물 및 생성물의 농도에 대하여 실험을 통해 측정한 값과 반응모델에 의한 예측값 사이의 차이를 최소화하는 반응속도 상수와 물질전달 계수를 구하기 위해 비선형 계획법(nonlinear programming)을 수행하였다. 이를 통해 얻은 반응의 활성화 에너지는 43.98 kJ/mol이다.