Rice Bran Lipase Catalyzed Esterification of Palm Oil Fatty Acid Distillate and Glycerol in Organic Solvent

Chong, Fui Chin,Tey, Beng Ti,Dom, Zanariah Mohd,Cheong, Kok Hing,Satiawihardja, Budiatman,Ibrahim, Mohd Nordin,Rahman, Russly Abdul,Biak, Dayang Radiah Awang,Ling, Tau Chuan Korean Society for Biotechnology and Bioengineerin 2007 Biotechnology and Bioprocess Engineering Vol.12 No.3

Rice bran lipase (RBL) was delipidated to enhance its stability in organic solvent and its esterification activity at elevated temperature. The esterification activity of delipidated RBL increased as temperature was increased from 45 to $65^{\circ}C$. The esterification activity of delipidated RBL at $65^{\circ}C$ was about 14 times greater than that of the non-delipidated RBL. As temperature was further increased to $75^{\circ}C$, the non-delipidated RBL lost all esterification activity, whereas the delipidated RBL retained approximately 48% of its esterification activity. The delipidated RBL maintained a relative esterification activity greater than 80% after 16 h of incubation in hexane, whereas the non-delipidated RBL maintained a relative esterification activity of only 50%. A method for production of acylglycerol using delipidated RBL to esterify palm oil fatty acid distillate (PFAD) with glycerol in hexane was successfully developed. The effects of reaction temperatures and type of water removal agents (silica gel and molecular sieve) on the degree of esterification were also examined. A 4 h reaction at $65^{\circ}C$, catalyzed by delipidated RBL and using silica gel as the water removal agent resulted in 53.8% esterification. Thin layer chromatography analysis suggested that the esterified product was primarily comprised of mono- and di-acylglycerols.

바이오디젤 생산을 위한 동물성 오일의 에스테르화 반응

김성민(Sung-Min Kim),김덕근(Deog-Keun Kim),이진석(Jin-Suk Lee),박순철(Soon-Chul Park),이영우(Young-Woo Rhee) 한국청정기술학회 2012 청정기술 Vol.18 No.1

본 연구에서는 동물성 오일로부터 바이오디젤 생산을 위한 에스테르화 반응과 전이에스테르화 반응을 실시하였다. 원료 초기 상태인 동물성 비계로부터 오일을 추출하기 위해 3개의 추출법을 적용하였다. 에스테르화 반응은 불균질계 촉매인 Amberlyst-15와 Amberlyst BD-20 그리고 균질계 촉매인 황산이 사용되었다. 3가지 촉매 중 유리지방산 제거 효율이 가장 높은 촉매는 황산으로 나타났으며 에스테르화 반응에 대한 황산과 메탄올의 최적 투입량 결정을 위해 반응표면분석법(Response Surface Method, RSM)을 적용하였다. 에스테르화 최적 조건 도출 후 유리지방산이 제거된 오일을 이용해 전이에스테르화 반응을 진행하였다. 전이에스테르화 반응 원료의 유리지방산 함량은 1% 이하이며 수분함량은 0.090% 이하였다. 촉매는 KOH, NaOH, NaOCH₃를 이용하였으며 무수메탄올에 녹여 사용하였다. 촉매 종류 및 투입량에 따른 영향을 관찰하기 위해 촉매 투입량을 0.3, 0.6, 0.9 wt%로 사용하였고 메탄올은 26.7 wt%로 고정하였다. 알코올 투입량에 따른 영향 실험은 투입량을 오일대비 4 : 1, 6 : 1, 9 : 1, 12 : 1로 변경하여 실시하였으며 촉매양은 0.8 wt%로 고정하였다. 촉매와 알코올 외 반응변수는 모두 동일하게 적용하였다. 반응온도는 메탄올의 끓는점인 65 ℃로 설정하였고 내부 온도계를 설치해 반응물의 온도를 측정하였다. 촉매 투입량 변경실험 후 KOH의 FAME 전환율이 높은 것을 확인하였다. 메탄올 투입량 변경실험은 오일대비 6 : 1 이상 사용했을 때 전환율이 높았다. 촉매, 메탄올 변경 실험 중 가장 높은 FAME 함량은 96.0%였으며 품질규격인 96.5%에는 미달하였다. FAME 함량증가 및 불순물 제거를 위해 바이오디젤 증류를 실시하였다. 이때 FAME 함량은 98%로 나타났다. In this study, the production of bio-diesel from animal oil by esterification and trans-esterification was investigated. There were three different extraction methods for oil extraction from raw animal fat. Heterogeneous catalysts such as Amberlyst-15 and Amberlyst BD-20 and a homogeneous catalyst such as sulfuric acid were used for esterification. Among three catalysts, the removal efficiency of Free Fatty Acid (FFA) was the highest in sulfuric acid. Response surface method was carried out to find the optimal esterification condition of sulfuric acid and methanol. After the esterification under the optimal condition, this animal fat was used for the trans-esterification. Animal oil used for trans-esterification was below 1% of FFA content and 0.09% of water content. The catalysts for trans-esterification were KOH, NaOH and NaOCH₃. To investigate the effects of catalyst type and amount on transesterification, The amount of catalyst were changed with 0.3, 0.6 and 0.9 wt%. The molar ratio of methanol/oil was changed with 4, 6, 9 and 12. The amount of catalyst was fixed to 0.8 wt%. The KOH catalyst showed the highest FAME conversion for trans- esterification, and the optimal methanol/oil weight ratio was 6. In the experiments of various catalysts and methanol molar ratios, the highest content of FAME is 96%. However, this FAME content was below Korean bio-diesel standard which is 96.5% of FAME content. After distillation, FAME content increased to 98%.

Production of stearidonic acid-rich triacylglycerol via a two-step enzymatic esterification

Kim, Nam Ho,Kim, Heejin,Choi, Nakyung,Kim, Yangha,Kim, Byung Hee,Kim, In-Hwan Elsevier 2019 Food chemistry Vol.270 No.-

<P><B>Abstract</B></P> <P>The aim of this study was to synthesize stearidonic acid (SDA)-rich triacylglycerol (TAG) via a two-step lipase-catalyzed esterification under vacuum. SDA-rich fatty acid, which was prepared from echium oil via <I>Candida rugosa</I> lipase-catalyzed selective esterification, was used as the substrate. Two different immobilized lipases, Novozym 435 from <I>Candida antarctica</I> and Lipozyme TL IM from <I>Thermomyces lanuginosus</I>, were employed for the synthesis of SDA-rich TAG. In the first step, Novozym 435-catalyzed esterification of the SDA-rich fatty acid with glycerol was carried out for 2 h. In the second step, Lipozyme TL IM-catalyzed esterification of the reaction mixture from the first step was performed for an additional 10 h. The optimal reaction conditions for the second step were a temperature of 65 °C, an enzyme loading of 20%, and a vacuum of 0.7 kPa. Consequently, the maximum TAG conversion of ca. 86.4 wt% was obtained after 12 h via a two-step lipase-catalyzed esterification.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Stearidonic acid-rich triacylglycerol was successfully synthesized. </LI> <LI> A two-step enzymatic esterification was carried out under vacuum. </LI> <LI> Novozym 435 from <I>Candida antarctica</I> was used for the first step reaction. </LI> <LI> Lipozyme TL IM from <I>Thermomyces lanuginosus</I> was used for the second step. </LI> </UL> </P>

Esterification of acrylic acid with ethanol using pervaporation membrane reactor

Ghoshna Jyoti,Amit Keshav,Jayapal Anandkumar 한국화학공학회 2017 Korean Journal of Chemical Engineering Vol.34 No.6

Esterification of acrylic acid with ethanol was carried out using an in-situ reactor with an integrated pervaporation assembly (IPAE) made of polyvinyl alcohol (PVA) membrane and was compared with a non-integrated (NIE) system. Effect of reaction temperature (Tr), catalyst loading (CC), molar ratios of reactants (MR) and ratio of effective membrane area to unit volume of reaction mixture (S/Vo) on kinetics of esterification reaction were studied. Conversions achieved in IPAE were found to be distinctly higher than the NIE. The highest conversion of acrylic acid was obtained as 83.3% at Tr=60 oC, MR=3 : 1, CC=2% and S/Vo=14.1m−1. Equilibrium conversion of acrylic acid in NIE was obtained as 55.1% at 60 oC, 1 : 1 in 7 h, while using IPAE conversion enhances to 67.6%. Esterification of acrylic acid and ethanol with presently studied operating parameters provides a new approach to existing literature reported esterification-pervaporation system.

Structural and rheological properties of pectic polysaccharide extracted from <i>Ulmus davidiana</i> esterified by succinic acid

Choi, Yu-Ra,Lee, Yun-Kyung,Chang, Yoon Hyuk Elsevier 2018 INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES Vol.120 No.1

<P><B>Abstract</B></P> <P>The present study was carried out to investigate the physicochemical and structural properties of pectic polysaccharide extracted from <I>Ulmus davidiana</I> (UDP) and to determine the physicochemical, structural, and rheological properties of esterified UDP with succinic acid (ES-UDP). The results indicated that UDP had high amounts of galacturonic acids and various neutral sugars, such as galactose, rhamnose, and glucose. UDP was identified as a low methoxyl pectin, consisting of 1,4-linked α-<SMALL>D</SMALL>-Gal<I>p</I>A (the main backbone chain), supported by the results of Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction, and 1D Nuclear magnetic resonance (NMR) spectroscopy. In the FT-IR and XRD, no difference was detected between UPD and ES-UDPs. However, <SUP>1</SUP>H and <SUP>13</SUP>C NMR spectra revealed that the new ester bonds were formed between a hydroxyl group of UDP and a carboxyl group of succinic acid during esterification. In the steady shear rheological analysis, the consistency index (K) of ES-UDP was significantly higher than that of UDP and increased significantly with increasing concentration of succinic acid. In the dynamic rheological analysis, the tan <I>δ</I> values of all ES-UDP solutions were significantly lower than those of the UDP solution.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Pectic polysaccharides from <I>Ulmus davidiana</I> were obtained by hot water extraction. </LI> <LI> Esterification of UDP was produced by esterification with succinic acid. </LI> <LI> Esterification affected structural and physicochemical properties of UDP. </LI> <LI> Esterification of UDP had higher rheological properties compared to UDP. </LI> </UL> </P>

Facile Utilization of Carbon Dioxide for the Esterification of Potassium Lactate to Butyl Lactate

Ali Awad,Macchindra Gulabrao Chandgude,Young Kyu Hwang 한국환경에너지공학회 2023 한국열환경공학회 학술대회지 Vol.2023 No.2

The utilization of C아 is crucial for the sustainable growth of human society. Herein, we demonstrate the direct esterification of potassium lactate (KL) ,vith butanol and pressurized CO₂ to butyl lactate (BL). The pressurized C아 reacts with water to form carbonic acid, which promotes esterification. In a single batch reaction, 17% butyl lactate was obtained which was increased to 36% through two consecutive esterification cycles. Finally, the complete conversion of potassium lactate to butyl lactate was achieved using a very small amount of sulfuric acid (H₂SO₄). The proposed integrated process requires approximately 63% less mineral acid compared to the conventional lactate separation and purification processes. The effect of reaction parameters, mcluding reaction temperature, reaction time, CO₂ pressure and moisture content for the esterification of potassium lactate were explored.

Synthesis of <i>trans</i>-10,<i>cis</i>-12 conjugated linoleic acid-enriched triacylglycerols via two-step lipase-catalyzed esterification

Kang, Ingu,Bang, Hyo-Jeong,Kim, In-Hwan,Choi, Hee-Don,Kim, Byung Hee Elsevier 2015 FOOD SCIENCE AND TECHNOLOGY -ZURICH- Vol.62 No.1

<P><B>Abstract</B></P> <P>This study aimed to synthesize <I>trans</I>-10,<I>cis</I>-12 conjugated linoleic acid (<I>t</I>10,<I>c</I>12-CLA)-enriched triacylglycerols (TAGs) with potential anti-obesity effects via a two-step lipase-catalyzed reaction. Commercial CLA isomer mixtures, containing 33.3?g/100?g <I>t</I>10,<I>c</I>12-CLA, were esterified with dodecan-1-ol to selectively enrich the <I>t</I>10,<I>c</I>12-CLA in a free fatty acid (FFA) fraction. The reaction was performed in a recirculating packed bed reactor using <I>Candida rugosa</I> lipase (immobilized on Immobead 150) as the biocatalyst. An FFA fraction containing 54.7?g/100?g <I>t</I>10,<I>c</I>12-CLA was produced in a yield of 21.8?g/100?g initial <I>t</I>10,<I>c</I>12-CLA under the optimal conditions, i.e., temperature, 20?°C; CLA mixtures-to-dodecan-1-ol molar ratio, 1:1; water content, zero (no added water); reaction time, 36?h. A <I>t</I>10,<I>c</I>12-CLA-enriched FFA fraction was esterified with glycerol to prepare <I>t</I>10,<I>c</I>12-CLA-enriched TAGs. The reaction was performed in a stirred batch reactor using <I>Candida antarctica</I> lipase B (immobilized on macroporous acrylic resin) as the biocatalyst. The optimal combination of temperature, glycerol-to-FFA fraction molar ratio, enzyme loading, reaction time, and vacuum level was 60?°C, 1:3, 10?g/100?g (based on total substrates), 12?h, and 0.4?kPa, respectively. Under these conditions, the TAG content reached 93.7?g/100?g and <I>t</I>10,<I>c</I>12-CLA was evenly distributed throughout the glycerol backbone of the TAG.</P> <P><B>Highlights</B></P> <P> <UL> <LI> <I>t</I>10,<I>c</I>12-CLA enrichment was performed in a recirculating packed bed reactor. </LI> <LI> <I>t</I>10,<I>c</I>12-CLA enrichment was achieved via <I>C.?rugosa</I> lipase-catalyzed esterification. </LI> <LI> The yield of <I>t</I>10,<I>c</I>12-CLA was 21.8?g/100?g initial <I>t</I>10,<I>c</I>12-CLA. </LI> <LI> No added water is needed for the <I>C.?rugosa</I> lipase-catalyzed esterification. </LI> <LI> <I>t</I>10,<I>c</I>12-CLA-enriched TAGs was synthesized via Novozym 435-catalyzed esterification. </LI> </UL> </P>

Synthesis of sulfonated catalyst from bituminous coal to catalyze esterification for biodiesel production with promoted mechanism analysis

Tang Xincheng,Niu Shengli,Zhao Shuang,Zhang Xiangyu,Li Ximing,Yu Hewei,Lu Chunmei,Han Kuihua 한국공업화학회 2019 Journal of Industrial and Engineering Chemistry Vol.77 No.-

The carbon-based heterogeneous acid catalyst is synthesized from bituminous coal through the partialcarbonization and sulfonation method and applied to catalyze the esterification of oleic acid withmethanol for biodiesel production. Various characterization methods are used to explain catalyticfeatures and molecular simulation is conducted to analyze the promoted mechanism of acid catalyst inesterification. Carbon catalyst, prepared by partially carbonized at 350 C and sulfonated at 105 C,catalyzes esterification with biodiesel yield of 98.70%. Transition state analysis implies that acid catalystreduces the activation energy through providing proton to promote esterification.

Enantioselective Esterification of Ibuprofen by a Novel Thermophilic Biocatalyst: APE1547

Zhao Dan-tong,Xun Er-na,Wang Jia-xin,Wang Ren,Wei Xiao-fei,Wang Lei,Wang Zhi 한국생물공학회 2011 Biotechnology and Bioprocess Engineering Vol.16 No.4

The enantioselective esterification of ibuprofen catalyzed by a novel thermophilic esterase (APE1547)from the archaeon Aeropyrum pernix K1 was successfully conducted in organic solvents. The effects of acyl acceptor,substrate ratio, organic solvent, temperature, and water activity were investigated. Under optimum conditions, the highest enantioselectivity (E = 38.1) was obtained with a higher enzyme activity (216.5 μmol/g/h). Celites were added into the reaction mixture to remove the water produced in the esterification. The reaction achieved its equilibrium in approximately 96 h with a conversion of 57 and 99%(ee) of the un-reacted (S)-ibuprofen obtained.

염화지방산을 이용한 리그닌의 esterification 및 특성 평가

이은아,박지수,박찬우,( Azelia Wulan Cindradewi ),한송이,권구중,김석주,이승환 한국공업화학회 2020 한국공업화학회 연구논문 초록집 Vol.2020 No.-

신갈나무로부터 이온성 액체를 이용하여 추출한 리그닌에 지방산을 이용하여 esterification을 실시하였다. 리그닌에 tetrahydrofuran, N,N-dimethylformamide, pyridine을 첨가하여 질소 가스 하에서 30분간 용해시켰다. 세 종류의 탄소 체인의 길이가 다른 염화지방산(octanoyl chloride (OC), lauroyl chloride (LC), palmitoyl chloride (PC))을 리그닌의 수산기 대비 0.5 당량의 조건으로 첨가하여 교반하며 60°C에서 48시간 반응을 실시하였다. FT-IR과 1H NMR 분석 결과 C-H 피크가 현저히 증가한 것을 통해 리그닌의 esterification을 확인하였다. GPC 분석을 통해 리그닌의 esterification 후 분자량의 증가를 확인 하였다.