• Title/Summary/Keyword: selective oxidation reaction

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A Comparison between the Decomposition of Bisphenol A and the Concentration of Hydrogen Peroxide Formed during Ozone/Catalyst Oxidation Process (오존/촉매 산화공정에서 비스페놀 A의 분해와 생성된 과산화수소의 농도 비교)

  • Choi, Jae Won;Lee, Hak Sung
    • Applied Chemistry for Engineering
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    • v.28 no.6
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    • pp.619-625
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    • 2017
  • In this study, the formation of hydroxyl radical and decomposition characteristics of bisphenol A (BPA) was investigated by quantifying hydrogen peroxide formed as a reaction by-product during the formation stage of hydroperoxyl radical. The direct oxidation reaction by ozone only decomposed BPA just like the Criegee mechanism under the condition where radical chain reactions did not occur. Non-selective oxidation reactions occurred under the conditions of pH 6.5 and 9.5 where radical chain reactions do occur, confirming indirectly the formation of hydroxyl radical. The decomposition efficiency of BPA by the added catalysts appeared in the order of $O_3$/PAC ${\geq}$ $O_3/H_2O_2$ > $O_3$/high pH > $O_3$ alone. 0.03~0.08 mM of hydrogen peroxide were continuously measured during the oxidation reactions of ozone/catalyst processes. In the case of $O_3$/high pH process, BPA was completely decomposed in 50 min of the oxidation reaction, but reaction intermediates formed by oxidation reaction were not oxidized sufficiently with 29% of the removal ratio for total organic carbon (TOC, selective oxidation reaction). In the case of $O_3/H_2O_2$ and $O_3$/PAC processes, BPA was completely decomposed in 40 min of the oxidation reaction, and reaction intermediates formed by the oxidation reaction were oxidized with 57% and 66% of removal ratios for TOC, respectively (non-selective oxidation reactions).

N3S-ligated Copper(II) Complex Catalyzed Selective Oxidation of Benzylic Alcohols to Aldehydes under Mild Reaction Conditions

  • Dharmalingam, Sivanesan;Koo, Eunhae;Yoon, Sungho;Park, Gyoosoon
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.715-720
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    • 2014
  • A Cu(II) complex with an three nitrogens and one sulfur coordination environment was synthesized and characterized. Its redox potential was observed at 0.483 V vs. NHE, very similar to that of a Cu-containing fungal enzyme, galactose oxidase, which catalyzes the oxidation of alcohols to corresponding aldehydes with the concomitant reduction of molecular oxygen to water. The Cu(II) complex selectively oxidizes the benzylic alcohols using TEMPO/$O_2$ under mild reaction conditions to corresponding aldehydes without forming any over-oxidation product. Moreover, the catalyst can be recovered and reused multiple times for further oxidation reactions, thus minimizing the waste generation.

PARTIAL OXIDATION OF PROPANE ON NAFION SUPPORTED CATALYTIC MEMBRANE

  • F. Frusteri;C. Espro;F. Arena;F. Arena;E. Passalacqua;A.Patti;A. Parmaliana
    • Proceedings of the Membrane Society of Korea Conference
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    • 1999.07a
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    • pp.55-58
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    • 1999
  • Nafion supported catalytic membranes were found to be active, stable and selective in th partial oxidation of propane to oxygenates with H2O2 under mild condition. Addition of Fe2+ in liquid phase enhances the reaction rate. Reaction proceeds according to a radical mechanism based on th electrophilic activation of propane on superacid sites and subsequent reaction of the activated paraffin with OH radicals. The use of a catalytic membrane, which allow separation of the intermediate products from the liquid phase containing the oxidant, was found to be effective to perform selective partial oxidation of propane with high yields to oxygenated products.

Study on the Selective CO Oxidation Using $La_xCe_{1-x}Co_yCu_{1-y}O_{3-{\alpha}}$ Perovskite Catalysts ($La_xCe_{1-x}Co_yCu_{1-y}O_{3-{\alpha}}$ Perovskite촉매의 선택적 CO 산화반응에 관한 연구)

  • Kang, Dae-Kyu;Lee, Young-Il;Sohn, Jung-Min
    • Transactions of the Korean hydrogen and new energy society
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    • v.18 no.1
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    • pp.32-39
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    • 2007
  • CO oxidation and selective CO oxidation of $La_xCe_{1-x}Co_yCu_{1-y}O_{3-{\alpha}}$ perovskite(x=1, 0.9, 0.7. 0.5; y=1, 0.9, 0.7, 0.5) were investigated. For CO oxidation, catalytic activities were studied according to different preparation conditions such as pH and calcination temperature. The influence of the change of the $O_2$ concentration for selective CO oxidation was studied, too. The substitution of Ce for La improved the catalytic activity for CO oxidation and selective CO oxidation and best activity was observed for $La_{0.7}Ce_{0.3}CoO_3$ prepared at pH 11 and calcined at $600^{\circ}C$. The temperature of 90% CO conversion for CO oxidation using $La_{0.7}Ce_{0.3}CoO_3$ was $230^{\circ}C$. In contrast to the enhancement effect by Ce substitution, the partial substitution of Cu for Co in $LaCo_yCu_{1-y}O_{3-{\alpha}}$ decreased catalytic activities for CO oxidation reaction compared to that using $LaCoO_3$. For selective CO oxidation, the best CO conversion was 66% at $230^{\circ}C$ for $La_{0.7}Ce_{0.3}CoO_3$. The CO conversion of $La_{0.7}Ce_{0.3}CoO_3$ was greatly increased from 66% to 91% as increasing $O_2$ concentration from 1% to 2%.

An Environmentally Benign Synthesis of 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane Tribromide and Its Application as an Efficient and Selective Reagent for Oxidation of Sulfides to Sulfoxides in Solution and Solvent-free Conditions

  • Pourmousavi, S.A.;Salehi, P.
    • Bulletin of the Korean Chemical Society
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    • v.29 no.7
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    • pp.1332-1334
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    • 2008
  • Stable crystalline 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane tribromide (BABOT), can be readily synthesized from the reaction of the corresponding bromide with $HNO_3$ and aqueous KBr. Selective Oxidation of a variety of dialkyl and alkyl Aryl sulfides to the corresponding sulfoxides in high yield was achieved by this reagent in solution ($CH_3CN/H_2O$) and solvent free conditions. The reaction proceeds under neutral and mild conditions and can be carried out easily at room temperature with regeneration of BABOT. In this method purification of products is straightforward and no over oxidation to sulfone was noted.

Selective Oxidation of Olefins Catalyzed by Polymer-anchored Nickel(II) Complex in Water Medium

  • Islam, Manirul;Hossain, Dildar;Mondal, Paramita;Roy, Anupam Singha;Mondal, Sanchita;Mobarak, Manir
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3765-3770
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    • 2010
  • Selective oxidation of olefins has been carried out in water medium with tert-butylhydroperoxide (TBHP, 70% aqueous) as an oxidant using polymer-anchored Ni(II) complex as a catalyst. Several parameters were varied to optimize the reaction conditions. Under the optimized reaction conditions olefins gave selectively allylic oxidation products. The present polymer anchored Ni(II) complex can be recycled five times without any appreciable loss in catalytic activity.

Metalloporphyrin-Catalyzed Chemoselective Oxidation of Sulfides with Polyvinylpyrrolidone-Supported Hydrogen Peroxide: Simple Catalytic System for Selective Oxidation of Sulfides to Sulfoxides

  • Zakavi, Saeed;Abasi, Azam;Pourali, Ali Reza;Talebzadeh, Sadegh
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.35-38
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    • 2012
  • Room temperature oxidation of organic sulfides with polyvinylpyrrolidone-supported hydrogen peroxide (PVP-$H_2O_2$) in the presence of Mn(III) complexes of meso-tetraphenylporphyrin, Mn(TPP)X (X = OCN, SCN, OAc, Cl) and imidazole (ImH) leads to the highly chemoselective (ca. 90%) oxidation of sulfides to the corresponding sulfoxide. The efficiency of reaction has been shown to be influenced by different reaction parameters such as the nature of counterion (X) and solvent as well as the molar ratio of reactants. Using Mn(TPP)OCN and ImH in 1:15 molar ratio and acetone as the solvent leads to the efficient oxidation of different sulfides.

Reaction Mechanism and Support Effect for the Gas-Phase Oxidation of o-Xylene (자일렌의 기상 산화반응에서의 반응 메카니즘과 담체영향)

  • Lee, Gun-Dae;Lee, Ho-In
    • Applied Chemistry for Engineering
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    • v.2 no.2
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    • pp.155-164
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    • 1991
  • The reaction mechanism and the effects of the oxidation state of vanadium oxide and of support on catalytic activity for the oxidation of o-xylene were investigated. The oxidation of o-xylene simultaneously proceeded through the consecutive and parallel mechanisms. The high valence of vanadium favored selective oxidation to phthalic anhydride, while the low valence caused complete oxidation of phthalic anhydride to CO and $CO_2$. Crystalline $V_2O_5$ showed better selectivity for partial oxidation rather than amorphous one.

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Characteristics of Exhaust Emission Reduction of Heavy Duty Diesel Engine by Oxidation Catalyst - Reactor Test - (산화촉매에 의한 대형디젤엔진의 배출가스 정화 특성 - Reactor 실험을 중심으로 -)

  • Jo, Gang-Rae;Kim, Yong-U;Kim, Hui-Gang
    • Journal of Korean Society for Atmospheric Environment
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    • v.14 no.4
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    • pp.313-320
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    • 1998
  • The most desirable diesel oxidation catalyst (DOC) should have the properties of oxidibing CO and HC effectively at low exhaust gas temperature while minimizing the formation of sulfate at high exhaust gas temperature. Precious metals such as platinum and palladium have been known to be sufficiently active for oxidizing CO and HC and also to have high activity for the oxidation of sulfur dioxide (SO2) to sulfor trioxide (SO3). There is a need to develop a highly selective catalyst which can promote the oxidation of CO and HC efficiently, but, on the other hand, suppress the oxidation of SO2. One approach to solve this problem is to load a base metal such as vanadium in Pt-based catalyst to suppress sulfate formation. In this study, a Pt-V catalyst was prepared by impregnating platinum and vanadium onto a Ti-Si wash coated catalyst in a laboratory reactor by changing the formulations and reaction temperatures.

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An Experimental and Modeling Study on the Oxidation Kinetics of Nitric Oxide over Platinum-based Catalysts (백금계 촉매상에서 산화질소(NO)의 산화반응속도에 관한 실험 및 모델링 연구)

  • Kim, Young-Deuk;Jeong, Soo-Jin;Kim, Woo-Seung
    • Transactions of the Korean Society of Automotive Engineers
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    • v.20 no.5
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    • pp.71-80
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    • 2012
  • To improve the $NO_X$ conversion over a SCR (selective catalytic reduction) catalyst, the DOC (diesel oxidation catalyst) is usually placed upstream of the SCR catalyst to enhance the fast SCR reaction ($4NH_3+2NO+2NO_2{\rightarrow}4N_2+6H_2O$) using equimolar amounts of NO and $NO_2$. Here, a ratio of $NO_2/NO_X$ above 50% should be avoided, because the reaction with $NO_2$ only ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$) is slower than the standard SCR reaction ($4NH_3+4NO+O_2{\rightarrow}4N_2+6H_2O$). In order to accurately predict the performance characteristics of SCR catalysts, it is therefore desired to develop a more simple and reliable mathematical and kinetic models on the oxidation kinetics of nitric oxide over a DOC. In the present work, the prediction accuracy and limit of three different chemical reaction kinetics models are presented to describe the chemicophysical characteristics and conversion performance of DOCs. Steady-state experiments with DOCs mounted on a light-duty four-cylinder 2.0-L turbocharged diesel engine then are performed, using an engine-dynamometer system to calibrate the kinetic parameters such as activation energies and preexponential factors of heterogeneous reactions. The reaction kinetics for NO oxidation over Pt-based catalysts is determined in conjunction with a transient one-dimensional (1D) heterogeneous plug flow reactor (PFR) model with diesel exhaust gas temperatures in the range of 115~$525^{\circ}C$ and space velocities in the range of $(0.4{\sim}6.5){\times}10^5\;h^{-1}$.