• Title/Summary/Keyword: Bio-Hydrogenation

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Highly Enantioselective Rh-catalyzed Transfer Hydrogenation of α-Functionalized Arylketones

  • Lee, Do-Min;Kwak, Se-Hun;Lee, Kee-In
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1317-1324
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    • 2009
  • Asymmetric transfer hydrogenation of α-functionalized arylketones has been studied. The chiral Rh-catalyst effectively performed in transfer hydrogenation of $\alpha$-mesyloxyketones with an azeotropic mixture of formic acid/triethylamine to produce optically active 1-arylethandiols with excellent enantioselectivity.

Biosynthesis of Conjugated Linoleic Acid and Its Incorporation into Ruminant's Products

  • Song, Man K.;Kennelly, John J.
    • Asian-Australasian Journal of Animal Sciences
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    • v.16 no.2
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    • pp.306-314
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    • 2003
  • Bio-hydrogenation of $C_{18}$-unsaturated fatty acids released from the hydrolysis of dietary lipids in the rumen, in general, occurs rapidly but the range of hydrogenation is quite large, depending on the degree of unsaturation of fatty acids, the configuration of unsaturated fatty acids, microbial type and the experimental condition. Conjugated linoleic acid (CLA) is incompletely hydrogenated products by rumen microorganisms in ruminant animals. It has been shown to have numerous potential benefits for human health and the richest dietary sources of CLA are bovine milk and milk products. The cis-9, trans-11 is the predominant CLA isomer in bovine products and other isomers can be formed with double bonds in positions 8/10, 10/12, or 11/13. The term CLA refers to this whole group of 18 carbon conjugated fatty acids. Alpha-linolenic acid goes through a similar bio-hydrogenation process producing trans-11 $C_{18:1}$ and $C_{18:0}$, but may not appear to produce CLA as an intermediate. Although the CLA has been mostly derived from the dietary $C_{18:2}$ alternative pathway may be existed due to the extreme microbial diversity in the reticulo-rumen. Regardless of the origin of CLA, manipulation of the bio-hydrogenation process remains the key to increasing CLA in milk and beef by dietary means, by increasing rumen production of CLA. Although the effect of oil supplementation on changes in fatty acid composition in milk seems to be clear its effect on beef is still controversial. Thus further studies are required to enrich the CLA in beef under various dietary and feeding conditions.

Ru-NiOx nanohybrids on TiO2 support prepared by impregnation-reduction method for efficient hydrogenation of lactose to lactitol

  • Mishra, Dinesh Kumar;Dabbawala, Aasif A.;Truong, Cong Chien;Alhassan, Saeed M.;Jegal, Jonggeon;Hwang, Jin Soo
    • Journal of Industrial and Engineering Chemistry
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    • v.68
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    • pp.325-334
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    • 2018
  • Lactose is a reducing disaccharide consisting of two different monosaccharides such as galactose and glucose. The hydrogenation of lactose to lactitol is a formidable challenge because it is a complex process and several side products are formed. In this work, we synthesized Ru-Ni bimetallic nanohybrids as efficient catalysts for selective lactose hydrogenation to give selective lactitol. Ru-Ni bimetallic nanohybrids with $Ru-NiO_x$ (x = 1, 5, and 10 wt%) are prepared by impregnating Ru and Ni salts precursors with $TiO_2$ used as support material. Ru-Ni bimetallic nanohybrids (represented as $5Ru-5NiO/TiO_2$) catalyst is found to exhibit the remarkably high selectivity of lactitol (99.4%) and turnover frequency i.e. ($374h^{-1}$). In contrast, monometallic $Ru/TiO_2$ catalyst shows poor performance with ($TOF=251h^{-1}$). The detailed characterizations confirmed a strong interaction between Ru and NiO species, demonstrating a synergistic effect on the improvement on lactitol selectivity. The impregnation-reduction method for the preparation of bimetallic $Ru-NiO/TiO_2$ catalyst promoted Ru nanoparticles dispersed on NiO and intensified the interaction between Ru and NiO species. $Ru-NiO/TiO_2$ efficiently catalyzed the hydrogenation of lactose to lactitol with high yield/selectivity at almost complete conversion of lactose at $120^{\circ}C$ and 55 bar of hydrogen ($H_2$) pressure. Moreover, $Ru-NiO/TiO_2$ catalyst could also be easily recovered and reused up to four runs without notable change in original activity.

Effect of the Level of Carbohydrates on Bio-hydrogenation and CLA Production by Rumen Bacteria When Incubated with Soybean Oil or Flaxseed Oil In vitro (Soybean Oil 및 Flaxseed Oil 첨가 배양시 탄수화물 첨가수준에 의한 반추미생물의 Bio-hydrogenation과 CLA 생성에 미치는 효과)

  • 최성호;임근우;김광림;송만강
    • Journal of Animal Science and Technology
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    • v.48 no.4
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    • pp.521-532
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    • 2006
  • An in vitro study was conducted to examine the effect of addition level of carbohydrates on fermentation characteristics, and bio-hydrogenation of unsaturated fatty acids by mixed rumen bacteria when incubated with soybean oil or flaxseed oil. Four levels(0%, 0.3%, 0.6% and 0.9%, w/v) of the mixed carbohydrates(glucose, cellobiose, soluble starch, 1:1:1, in weight basis) and oil sources(soybean or flaxseed oil, 60mg in 150ml culture solution) were added to the mixed solution of strained rumen fluid with artificial saliva(1:4, v/v), and incubated anaerobically for 12 hours at 39℃. pH and ammonia-N concentration were lower by increasing the substrate levels at all incubation periods(P<0.05~P<0.001). The propionate proportion increased(P<0.001), but acetic acid and butyric acid decreased(P<0.001) with the substrate level at 6 and 12 h incubations. Oil sources did not influence the proportions of individual VFA. At the end of incubation, the proportions of C18:0(P<0.01), C18:1(P<0.001) and trans-11C-18:1(P<0.01) were reduced but those of C18:2(P<0.001) and C18:3(P<0.01) were enhanced by the addition of flaxseed oil compared to addition of soybean oil. The proportions of C18:0 and total CLA were reduced(P<0.01) but those of trans-11-C18: (P<0.05) and C18:2(P<0.01) were increased with the substrate level when incubated with soybean oil or flaxseed oil. There were interactions(P<0.05) in the proportions of C18:1, C18:2 and C18:3(P<0.01) between oil source and substrate level. The proportions of cis-9, trans-11-CLA and trans-10, cis-12-CLA tended to reduce with substrate level, although there was no significant difference between treatments.

Practical Process Development of AMCA from Recyclable Source MFB (재사용이 가능한 MFB로부터 AMCA의 합성 공정 개발)

  • Kim, Jong Cheon;Ryu, Young;Kim, Seok Chan
    • Applied Chemistry for Engineering
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    • v.27 no.5
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    • pp.508-511
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    • 2016
  • A facile synthesis of 4-(aminomethyl)cyclohexanecarboxylic acid (AMCA) from recyclable methyl 4-formylbenzoate (MFB) was described. In particular, we investigated the best process variables such as catalyst, hydrogen pressure, reaction temperature, and reaction time for AMCA conversion from AMBA through hydrogenation reaction. The best conditions were found to be as follows: the catalyst as [5% Pd/C, 5% Pt/C, 5% Rh/C (1 : 1 : 1)] which is a composite catalyst, the pressure as 30 bar, the reaction time as 8 hours and the reaction temperature at $130^{\circ}C$. Under the condition, a 90% yield (purity 99.9%) for the mass production of AMCA was achieved.

A Study on the Bio-Based Polyurethane (바이오 폴리우레탄에 관한 연구)

  • Ko, Jong-Sung;Lee, Jin-Hui;Sung, Ki-Chun
    • Journal of the Korean Applied Science and Technology
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    • v.29 no.3
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    • pp.531-542
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    • 2012
  • The thesis covers the trend of research on bio-based polyurethane which is made from polyols derived mainly from plant oils and isocyanates. Castor oil is a triglyceride of ricinoleic acid containing hydroxyl group. Hydroxylation is done on the unsaturated bonds of the oils by the reactions of epoxidation/ring opening, hydroformylation/hydrogenation, ozonolysis/hydrogenation, and thiol-ene reaction. Polyols from hyperbranch, primary alcohol, polysaccharide have been studied to control the reactivity of the polyol and morphology of the microdomains. Besides, researches cover biodegradable polylactic acid polyol for medical use, fatty acid dimer polyol for the prevention of hydrolysis, and polyol with ionic group for water-borne polyurethane. Bio-based polyurethanes are being used in flexible and rigid foams, coatings, sealants, and elastomers.

Effect of C18-polyunsaturated Fatty Acids on Their Direct Incorporation into the Rumen Bacterial Lipids and CLA Production In vitro

  • Choi, S.H.;Song, M.K.
    • Asian-Australasian Journal of Animal Sciences
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    • v.18 no.4
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    • pp.512-515
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    • 2005
  • An in vitro study was conducted to determine the effect of C18-polyunsaturated fatty acid on direct incorporation into the rumen bacteria, bio-hydrogenation and production of CLA in vitro. Sixty milligrams of linoleic acid ($C_{18:2}$) or linolenic acid ($C_{18:3}$) were absorbed into the 0.5 g cellulose powder was added to the 150 ml culture solution consisting of 120 ml McDougall's buffer and 30 ml strained rumen fluid. Four uCi of 1-$^{14}C_{18:2}$ or 1-$^{14}C_{18:3}$ (1 uCi/15 mg each fatty acid) were also added to the corresponding fatty acids to estimate the direct incorporation into the bacterial lipids. The culture solution was then incubated anaerobically in a culture jar with stirrer at 39$^{\circ}C$ for 12 h. Ammonia concentration and pH of the culture solution were slightly influenced by the fatty acids. Amount of fatty acid incorporated into the bacteria was 1.20 mg and 0.43 mg/30 ml rumen fluid for $C_{18:2}$ and $C_{18:3}$, respectively during 12 h incubation. Slightly increased CLA (sum of cis-9, trans-11 and cis-10, trans-12 $C_{18:2}$) was obtained from the $C_{18:3}$ addition compared to that from $C_{18:2}$ after 12 h incubation in vitro.

Hydrotreating for Stabilization of Bio-oil Mixture over Ni-based Bimetallic Catalysts (Ni계 이원금속 촉매에 의한 혼합 바이오오일의 안정화를 위한 수소첨가 반응)

  • Lee, Seong Chan;Zuo, Hao;Woo, Hee Chul
    • Clean Technology
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    • v.27 no.1
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    • pp.69-78
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    • 2021
  • Vegetable oils, such as palm oil and cashew nut shell liquid (CNSL), are used as major raw materials for bio-diesel in transportation and bio-heavy oil in power generation in South Korea. However, due to the high unsaturation degree caused by hydrocarbon double bonds and a high content of oxygen originating from the presence of carboxylic acid, the range of applications as fuel oil is limited. In this study, hydrotreating to saturate unsaturated hydrocarbons and remove oxygen in mixed bio-oil containing 1/1 v/v% palm oil and CNSL on monometallic catalysts (Ni and Cu) and bimetallic catalysts (Ni-Zn, Ni-Fe, Ni-Cu Ni-Co, Ni-Pd, and Ni-Pt) was perform under mild conditions (T = 250 ~ 400 ℃, P = 5 ~ 80 bar and LHSV = 1 h-1). The addition of noble metals and transition metals to Ni showed synergistic effects to improve both hydrogenation (HYD) and hydrodeoxygenation (HDO) activities. The most promising catalyst was Ni-Cu/��-Al2O3, and in the wide range of the Ni/Cu atomic ratio of 9/1~1/4, the conversion for HYD and HDO reactions of the catalysts were 90-93% and 95-99%, respectively. The tendency to exhibit almost constant reaction activity in these catalysts of different Ni/Cu atomic ratios implies a typical structure-insensitive reaction. The refined bio-oil produced by hydrotreating (HDY and HDO) had significantly lower iodine value, acid value, and kinetic viscosity than the raw bio-oil and the higher heating value (HHV) was increased by about 10%.

A Study on the Fuel Characteristics of Hydrotreated Biodiesel(HBD) for Alternative Diesel Fuel (경유 대체연료로서 수첨 바이오디젤의 연료적 특성 연구)

  • Kim, Jae-Kon;Jeon, Cheol-Hwan;Yim, Eui-Soon;Jung, Choong-Sub
    • Journal of the Korean Applied Science and Technology
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    • v.28 no.4
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    • pp.508-516
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    • 2011
  • Hydrotreated biodiesel(HBD) is paraffinic bio-based liquid, with the chemical structure $C_nH_{2n+2}$, originating from vegetable oil(the process can also be applied to animal fat). The oil or fat is treated in a number of process, the most important being hydrogenation, in order to create a bio-based liquid diesel fuel. During the hydrogenation, oxygen is removed from the triglyceride and converted into water. Propane is formed as a by product and can be combusted and used for energy production. HBD can be used in conventional diesel engines, pure or blended with conventional diesel, due to its similar physical properties to diesel. This study reports the quality characteristics with chemical and physical properties as an alternative diesel fuel. Especially, HBD showed higher cetane value and number than FAME, and it is consisted of $C_{15}$ - $C_{18}$ n-paraffinic compounds. We also describes quality characteristics of HBD blends(2, 5, 10, 20, 30, 40, 50 vol%) in automotive diesel. HBD blends(max. 20 vol%) were the limit by the Korean specification due to poor low temperature characteristics.