• Title/Summary/Keyword: Esterification of Free Fatty Acids

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Effects of water on the esterification of oil with high content of free fatty acids (고유리지방산 함량 오일의 바이오디젤 전환 반응에서 수분의 영향)

  • Park, Ji-Yeon;Kim, Deog-Keun;Lee, Jin-Suk
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.248.1-248.1
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    • 2010
  • 수송용 바이오연료로써 바이오디젤의 보급 활성화에 따른 원료인 식물성 기름의 가격 상승 및 수급 불안정성 문제를 해결하고자 그동안 활용되지 않았던 폐유지를 바이오디젤 생산 원료로 사용하여 바이오디젤 생산 단가를 낮추고 원료의 수급 안정성도 확보하려는 시도가 이루어지고 있다. 폐유지의 경우 대부분 유리지방산 함량이 높아 염기 촉매를 적용하는 방법으로는 비누의 생성으로 전환이 힘들며 산 촉매를 적용하여 유리지방산을 에스테르화하는 공정을 필요로 한다. 에스테르화 반응에서는 반응 부산물로 물이 생성되며, 생성된 물은 바이오디젤 생산 반응을 저해하고 역반응을 유도하며 촉매의 활성을 감소시킨다. 본 연구에서는 고유리지방산 함량 오일의 에스테르화 반응에서 수분의 영향을 검토하였다. 산 촉매로 액상 촉매인 황산과 고체 산 촉매인 Amberlyst-15를 사용하였다. 초기 수분 함량이 0, 1, 2, 5, 10, 20%로 증가하였을 때, 지방산 메틸 에스테르 함량이 크게 감소하였으며, 1%의 수분 함량에서도 반응이 크게 저해받는 것으로 나타났다. 따라서 고유리지방산 함량 오일의 에스테르화 반응에서 수분에 의한 저해가 중요한 변수라는 것을 알 수 있다. Amberlyst-15는 황산보다 수분의 영향에 의해 지방산 메틸 에스테르 함량이 빠르게 감소하였다. 이는 다공성의 Amberlyst-15에서 생성된 물이 반응물질들이 active site에 접근하는 것을 방해하였기 때문인 것으로 생각된다. 황산을 사용하였을 경우에는 오일 대 메탄올 몰비를 1:3에서 1:6으로 증가시킴으로써 정반응 속도가 증가하여 수분에 대한 영향이 감소하는 현상이 나타났다. 에스테르화 반응 종료 12시간 후에 바이오디젤과 메탄올 내에 수분 함량을 분석한 결과 12%의 수분이 바이오디젤 층에 존재하며 88%의 수분은 메탄올 층에 존재하였다. 반응 중에 생성된 수분을 제거하기 위해, 에스테르화 반응 30분 후에 물을 포함하는 메탄올과 촉매 층을 새 메탄올과 촉매로 교환하는 2단계 반응을 수행함으로써 지방산 메틸 에스테르 함량을 향상시킬 수 있었다. 반응 초기에는 황산이 Amberlyst-15보다 높은 활성을 보였지만, 시간이 지날수록 두 촉매 사이의 에스테르화 성능 차이는 감소하였다. 따라서 2단계 에스테르화 반응이 수분의 저해작용을 줄이는 한 가지 대안으로 제안될 수 있다. 또한 에스테르화 반응에서 물의 저해 작용을 줄이기 위해 앞으로 투과증발막의 적용 또는 물에 저해작용을 받지 않는 구조의 촉매 사용을 검토할 필요가 있다.

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Recent Developments and Challenging issues of Solid Catalysts for Biodiesel Production (바이오디젤 생산용 고체 촉매의 개발 동향 및 과제)

  • Lee, Jin-Suk;Park, Soon-Chul
    • Korean Chemical Engineering Research
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    • v.48 no.1
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    • pp.10-15
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    • 2010
  • Intensive works have been carried out to develop more efficient solid catalysts for biodiesel production from various feedstocks including refined oils and waste fats. Among many catalysts, metal oxides and ion exchange resins are the most intensively studied ones. With regard to metal oxide catalysts, major research activities have focused on the identification of the active compounds and their immobilizing methods on the supports. As metal oxide catalysts have strong thermal stability, they may be used in simultaneous transesterification and esterification of waste fats. However, ion exchange resin catalysts were mainly applied in the esterification of the free fatty acids in waste fats because of their lower thermal stability. For both solid catalysts, further works are needed to make them to be used in commercial process. Especially fast deactivation of the solid catalyst would be the most challenging problem.

Effects of High Polyunsaturated Fat Diet on Human Plasma Cholesterol Esterification and Transfer (고 불포화 지방산 식이가 인체 혈청 Cholesterol의 Esterification과 Transfer에 미치는 영향)

  • Lee Myoung Sook
    • Journal of Nutrition and Health
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    • v.26 no.7
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    • pp.819-828
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    • 1993
  • The reaction of lecithin cholesterol acyltransferase(LCAT) and cholesteryl ester transfer protein (CETP) are important in cholesterol esterification and transfer for the reverse cholesterol transport(RCT) system. The purpose of this study were to assess the effects of fatty acid unsaturation on RCT system. After 12 female human subjects consumed a prescribed high saturated fat diet prior to the period, two groups of six subjects were provided with a high PUFA(corn oil) or a high SFA(butter) as major fats in a 40 en % fat diet. Butter feeding increased plasma total-(34%), esterified-(96%), HDL_3$-(23%), LDL-(20%), and VLDL plus LDL(35%) cholesterol while corn oil feeding decreased esterified-(25%), LDL(15%) cholesterol and TG(27%). There were significant differences of fats on total-(p=0.0001), esterified-(p=0.0001), total HDL-(p=0.005), $HDL_2$-(p=0.01)and LDL-(p=0.0001) cholesterol. LCAT activity did not change during the period but highly correlated to apo A-I in HDL which was increased in the corn oil group. The 2.5 fold increased CETP activity in the butter group during the period might be related to changes in plasma VLDL plus LDL cholesterol level which were increased in the butter group.

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Optimization of Pre-treatment of Tropical Crop Oil by Sulfuric Acid and Bio-diesel Production (황산을 이용한 열대작물 오일의 전처리 반응 최적화 및 바이오디젤 생산)

  • Kim, Deog-Keun;Choi, Jong-Doo;Park, Ji-Yeon;Lee, Jin-Suk;Park, Seung-Bin;Park, Soon-Chul
    • Korean Chemical Engineering Research
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    • v.47 no.6
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    • pp.762-767
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    • 2009
  • In this study, the feasibility of using vegetable oil extracted from tropical crop seed as a biodiesel feedstock was investigated by producing biodiesel and analysing the quality parameters as a transport fuel. In order to produce biodiesel efficiently, two step reaction process(pre-treatment and transesterificaion) was required because the tropical crop oil have a high content of free fatty acids. To determine the suitable acid catalyst for the pre-esterification, three kinds of acid catalysts were tested and sulfuric acid was identified as the best catalyst. After constructing the experimental matrix based on RSM and analysing the statistical data, the optimal pre-treatment conditions were determined to be 26.7% of methanol and 0.982% of sulfuric acid. Trans-esterification experiments of the pre-esterified oil based on RSM were carried out, then discovered 1.24% of KOH catalyst and 22.76% of methanol as the optimal trans-esterification conditions. However, the quantity of KOH was higher than the previously established KOH concentration of our team. So, we carried out supplemental experiment to determine the quantity of catalyst and methanol. As a result, the optimal transesterification conditions were determined to be 0.8% of KOH and 16.13% of methanol. After trans-esterification of tropical crop oil, the produced biodiesel could meet the major quality standard specifications; 100.8% of FAME, 0.45 mgKOH/g of acid value, 0.00% of water, 0.04% of total glycerol, $4.041mm^2/s$ of kinematic viscosity(at $40^{\circ}C$).

A Study on Heterogeneous Catalysts for Transesterification of Nepalese Jatropha Oil (네팔산 Jatropha 오일의 전이에스테르화 반응용 불균일계 촉매 연구)

  • Youngbin Kim;Seunghee Lee;Minseok Sim;Yehee Kim;Rajendra Joshi;Jong-Ki Jeon
    • Clean Technology
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    • v.30 no.1
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    • pp.47-54
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    • 2024
  • Jatropha oil extracted from the seeds of Nepalese Jatropha curcas, a non-edible crop, was used as a raw material and converted to biodiesel through a two-step process consisting of an esterification reaction and a transesterification reaction. Amberlyst-15 catalyst was applied to the esterification reaction between the free fatty acids contained in the Jatropha oil and methanol. The acid value of the Jatropha oil could be lowered from 11.0 to 0.26 mgKOH/g through esterification. Biodiesel was synthesized through a transesterification reaction between Jatropha oil with an acid value of 0.26 mgKOH/g and methanol over NaOH/γ-Al2O3 catalysts. As the loading amount of NaOH increased from 3 to 25 wt%, the specific surface area decreased from 129 to 28 m2/g and the pore volume decreased from 0.249 to 0.129 cm3/g. The amount and intensity of base sites over the NaOH/γ-Al2O3 catalysts increased simultaneously with the NaOH loading amount. It was confirmed that the optimal NaOH loading amount for the NaOH/γ-Al2O3 catalyst was 12 wt%. The optimal temperature for the transesterification reaction of Jatropha oil using the NaOH/γ-Al2O3 catalyst was selected to be 65 ℃. In the transesterification reaction of Jatropha oil using the NaOH/γ-Al2O3 catalyst, the reaction rate was affected by external diffusion limitation when the stirring speed was below 150 RPM, however the external diffusion limitation was negligible at higher stirring speeds.

Biodiesel production using lipase producing bacteria isolated from button mushroom bed (양송이 배지에서 유래한 Lipase 생산균을 이용한 바이오디젤 생산)

  • Kim, Heon-Hee;Kim, Chan-Kyum;Han, Chang-Hoon;Lee, Chan-Jung;Kong, Won-Sik;Yoon, Min-Ho
    • Journal of Mushroom
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    • v.13 no.1
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    • pp.56-62
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    • 2015
  • A lipase producing bacterium was isolated from button mushroom bed, which showing high clear zone on agar media containing Tributyrin as the substrate. The strain was identified as Burkholderia cepacia by analysis of 16S rDNA gene sequence. Crude lipase (CL) was partially purified from 70% ammonium sulfate precipitation using the culture filtrate of B. cepacia. Immobilized lipases were prepared by cross-linking method with CL from B. cepacia and Novozyme lipase (NL) onto silanized Silica-gel as support. Residual activitiy of the immobilized CL (ICL) and immobilized NL (INL) was maintained upto 61% and 72%, respectively. Biodiesel (Fatty acid methyl ester, FAME) was recovered by transesterification and methanolysis of Canola oil using NaOH, CL and ICL as the catalysts to compare the composition of fatty acids and the yield of FAME. Total FAME content was NaOH $781mg\;L^{-1}$, CL $681mg\;L^{-1}$ and ICL $596mg\;L^{-1}$, in which the highest levels of FAME was observed to 50% oleic acid (C18:1) and 22% stearic acid (C18:0). In addition, the unsaturated FAME (C18:1, C18:2) decreased, while saturated FAME (C16:0, C18:0) increased according to increasing the reaction times with both CL and ICL, supporting CL possess both transesterification and interesterification activity. When reusability of ICL and INL was estimated by using the continuous reaction of 4 cycles, the activity of ICL and INL was respectively maintained 66% and 79% until the fourth reaction.