• Title/Summary/Keyword: alcohol oxidation

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Kinetic Study on the Oxidation Reaction of Substituted Benzyl Alcohols by Cr(VI)-Heterocyclic Complex (2,2'-Bipyridinium Dichromate) (크롬(VI)-헤테로고리 착물(2,2'-Bipyridinium Dichromate)에 의한 치환 벤질 알코올류의 산화반응에 대한 속도론적 연구)

  • Kim, Young Sik;Park, Young Cho
    • Applied Chemistry for Engineering
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    • v.23 no.2
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    • pp.241-246
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    • 2012
  • Cr(VI)-heterocyclic complex (2,2'-bipyridinium dichromate) was synthesized by the reaction between of 2,2'-bipyridine and chromium trioxide in $H_2O$, and characterized by IR and ICP. The oxidation of benzyl alcohol using 2,2'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant, in the order: cyclohexene < chloroform < acetone < N,N-dimethylformamide. In the presence of DMF solvent with acidic catalyst such as $H_2SO_4$ solution, 2,2'-bipyridinium dichromate oxidized the benzyl alcohol and its derivatives (p-$p-OCH_3$, $m-CH_3$, H, $m-OCH_3$, m-Cl, $m-NO_2$). Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant was -0.66 (303 K). The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using 2,4'-Bipyridinium Dichromate (2,4'-Bipyridinium Dichromate를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Kim, Young Sik;Park, Young Cho
    • Applied Chemistry for Engineering
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    • v.22 no.6
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    • pp.718-722
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    • 2011
  • 2,4'-Bipyridinium dichromate [$(C_{10}H_8N_2H)_2Cr_2O_7$] was synthesized by the reaction of 2,4'-bipyridinie with chromium trioxide in $H_2O$. The structure was characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase in the order of the dielectric constant (${\varepsilon}$), in the order : cyclohexene < chloroform < acetone < N,N'-dimethylformamide. In the presence of hydrochloric acid, 2,4'-bipyridinium dichromate effectively oxidized benzyl alcohol and its derivatives ($p-CH_3$, H, m-Br, $m-NO_2$) in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant (${\rho}$) was -0.65 at 303 K. The observed experimental data was used to rationalize the hydride ion transfer in the rate-determining step.

The Effects of TEMPO, NaBr and Temperature on the Selective Oxidation of Primary Alcohol Groups in Corn Starch (TEMPO와 NaBr 의 농도 및 온도가 옥수수 전분의 선택적 산화반응에 미치는 영향)

  • Suh, Dong-Soon;Chang, Pahn-Shick;Kim, Kwang-Ok
    • Korean Journal of Food Science and Technology
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    • v.33 no.1
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    • pp.40-44
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    • 2001
  • The effects of TEMPO and NaBr concentration, and temperature on the selective oxidation of primary alcohol groups in corn starch were examined. Reaction time decreased with the increased levels of TEMPO, NaBr and temperature up to 1.7 mM and 100 mM per 100 mM anhydroglucose unit(AGU) and $14^{\circ}C$, respectively, and did not change appreciably at the higher levels. Yield decreased with the increased NaBr levels and was not affected TEMPO level and the temperature. NaBr level and temperature showed negative effects on the selectivity. But the selectivity was not affected by NaBr level and temperature until 100 mM/100 mM AGU and $6^{\circ}C$. TEMPO had no effect on the selectivity significantly.

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Kinetics and Mechanism of the Oxidation of Alcohols by C9H7NHCrO3Cl (C9H7NHCrO3Cl에 의한 알코올류의 산화반응에서 속도론과 메카니즘)

  • Park, Young-Cho;Kim, Young-Sik;Kim, Soo-Jong
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.8
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    • pp.378-384
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    • 2018
  • $C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.

Oxidation of Ethanol in the Gas Phase with Alcohol Oxidase and Alcohol Dehydrogenase (Alcohol Oxidase와 Alcohol Dehydrogenase를 이용한 기상에서의 Ethanol의 산화반응)

  • 박현규;장호남김동옥
    • KSBB Journal
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    • v.9 no.3
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    • pp.239-245
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    • 1994
  • The effects of reaction temperature and the level of hydration(water activity) were studied for gas phase reactions of alcohol oxidase and alcohol dehydrogenase immobilized on DEAE-cellulose and controlled pore glass(CPG). Optimum reaction temperature zone of gas phase reaction was similar to that of aqueous phase reaction. The activity of alcohol oxidase increased dramatically and the stability decreased when the water activity was increased from 0.3 to 0.8. The apparent activation energies of the gas phase reaction decreased approaching the values obtained in the aqueous phase reaction as the water activity increased. In the both cases of alcohol oxidase and alcohol dehydrogenase, the rate constants of the gas phase reaction were lower than those of aqueous phase reaction by two orders of magnitude and these results could be correlated to the vapor-liquid equilibrium data of the substrate, ethanol.

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A PRACTICAL METHOD FOR THE DISPOSAL OF RADIOACTIVE ORGANIC WASTE

  • Kim, Kil-Jeong;Shon, Jong-Sik;Ryu, Woo-Seog
    • Nuclear Engineering and Technology
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    • v.39 no.6
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    • pp.731-736
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    • 2007
  • Radioactive organic wastes containing acetone, alcohol, and particularly tributyl phosphate (TBP)/dodecane contaminated with uranium are extracted from the PUREX process and the decontamination of related equipment. An evaporation method that utilizes existing DU oxidation apparatuses and ventilation systems and a typical muffle furnace installed with an aspirating system are adopted. A separation method using phosphoric acid especially for the TBP/dodecane waste is also studied and evaluated. The results show that a simple evaporation process is utilizable for wastes containing acetone or alcohol with a lower boiling point. A modified muffle furnace is more appropriate to dispose directly of organic wastes having a higher boiling point, such as TBP/dodecane, without generating a condensed waste solution. It is recommended that, when the uranium concentration of TBP/dodecane waste is much higher than stipulated levels, separation technology should be applied to remove uranium from the mixture. Each type of solvent after separation can then be considered disposable below the regulatory limit in the modified furnace discussed in this study.

Biotransformation of Tranylcypromine in Rat Liver Microsomes

  • Kang, Gun-Il;Hong, Suk-Kil
    • Archives of Pharmacal Research
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    • v.11 no.4
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    • pp.292-300
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    • 1988
  • Metabolism of tranylcypromine (TCP) in rat liver microsomes was studied in vitro using fortified microsomal preparations. As well as unlabeled TCP, two deuterium labeled analogs, TCP-phenyl-$d_{5}$ and TCP-cyclopropyl-$d_{2}$ were used and GC/MS employed which was then metabolized to cinnamaldehyde and hydrocinnamyl alcohol. Schiff bases of TCP with hydrocinnamaldehyde and acetaldehyde were detected and possibility of the metabolic formation of N-ethylidene TCP was proposed. In addition, acetophenone (benzoylacetic acid), benzaldehyde, benzoic acid, and benzyl alcohol were detected as the metabolites. Chemical decomposition studies suggested that parts of the oxidized products might be derived by air oxidation processes. A potential metabolite assumed to be N-ethylidene-1, 2-dihydroxy-3-phenylpropanamine oxide was also detected.

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Nitrogen removal performance of anammox process with PVA-SA gel bead crosslinked with sodium sulfate as a biomass carrier

  • Tuyen, N.V.;Ryu, J.H.;Yae, J.B.;Kim, H.G.;Hong, S.W.;Ahn, D.H.
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.326-332
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    • 2018
  • In this study,the result shows that polyvinyl alcohol-sodium alginate (PVA-SA) gel bead crosslinked with sodium sulfate are better among the different methods by comparing the relative mechanical strength, mechanical strength swelling and expansion coefficient of beads in water. Subsequently, anammox biomass entrapment by PVA-SA gel was introduced into continuous stirred tank reactor (CSTR). After 24 operation days, the nitrogen removal efficiency achieved 60%, while the nitrogen loading rate (NLR) was $0.14kgN/m^3/d$ and the experiment data indicated that PVA-SA gel bead crosslinked with sodium sulfate can be used to initiate anammox process. Furthermore, it is an alternative for culturing anammox in a long-term operation.

Oxidation of Isopropyl Alcohol in Air by a Catalytic Plasma Reactor System (촉매-플라즈마 반응 시스템을 이용한 아이소프로필 알코올 산화)

  • Jo, Jin Oh;Mok, Young Sun
    • Applied Chemistry for Engineering
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    • v.25 no.5
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    • pp.531-537
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    • 2014
  • A catalytic plasma reactor was employed for the oxidation of isopropyl alcohol (IPA) classified as a volatile organic compound (VOC). Copper oxide (Cu : 0.5% (w/w)) supported on a multichannel porous ceramic consisting of ${\alpha}-Al_2O_3$ was used as a catalyst, which was directly exposed to the plasma created in it. The effects of discharge voltage and reaction temperature on the concentrations of IPA and its byproducts were examined to understand the behavior of the catalytic plasma reactor. Without thermal insulation, the reactor temperature increased up to $120^{\circ}C$ at an applied voltage of 17 kV (discharge power : 28 W), and the IPA at a flow rate of $1L\;min^{-1}$ ($O_2$ : 10% (v/v); IPA : 1000 ppm) was completely removed. At temperatures below $120^{\circ}C$, however, besides the desirable product $CO_2$, several unwanted byproducts such as acetone, formaldehyde and CO were also formed from IPA. On the other hand, when the reactor was thermally insulated, the plasma discharge increased the temperature up to $265^{\circ}C$ under the same condition and most of IPA was oxidized to $CO_2$. Without loading CuO on the ceramic support, the plasma discharge in the thermally insulated reactor produced nearly equal amounts of $CO_2$ and CO. On comparison, with the catalyst alone (temperature : $265^{\circ}C$), more than 70% of the removed IPA was simply converted into another type of VOC (acetone), indicating that the catalyst assisted by the plasma is more effective in the oxidation of IPA than that of the catalyst-alone process.

Preparation of Pd/TiO2 Catalyst Using Room Temperature Ionic Liquids for Aerobic Benzyl Alcohol Oxidation (상온 이온성액체를 이용한 호기성 벤질 알코올 산화반응용 Pd/TiO2 촉매 제조)

  • Cho, Tae Jun;Yoo, Kye Sang
    • Applied Chemistry for Engineering
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    • v.26 no.3
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    • pp.351-355
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    • 2015
  • $Pd/TiO_2$ catalysts for aerobic benzyl alcohol oxidation were synthesized and eight different room temperature ionic liquids were used to control the palladium properties as active sites. $Pd/TiO_2$ particles were also calcined at 300, 400 and $500^{\circ}C$ to obtain an optimum catalyst. As the calcination temperature increased, the surface area and pore volume of catalyst decreased, but negligible changes were observed for the pore size of catalyst. However, the structural properties of catalyst varied with respect to the type of ionic liquids. Under identical reaction conditions, different catalytic activities were obtained depending upon the calcination temperature and type of ionic liquids. Mostly, the catalyst calcined at $400^{\circ}C$ showed higher catalytic activity than those at other temperatures. However, the catalyst prepared with 1-octyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium trifluoromethanesulfonate showed good catalytic performance after calcination at $300^{\circ}C$. Among the catalyst, $Pd/TiO_2$ prepared with 1-octyl-3-methylimidazolium tetrafluoroborate and calcined at $400^{\circ}C$ showed the highest catalytic activity.