• Title/Summary/Keyword: methanol oxidation reaction

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Synthesis of Methanol and Formaldehyde by Partial Oxidation of Methane (메탄의 부분산화에 의한 메탄올 및 포름알데히드의 합성)

  • Hahm, Hyun-Sik;Shin, Ki-Seok;Kim, Song-Hyoung;Ahn, Sung-Hwan;Kim, Myung-Soo;Park, Hong-Soo
    • Journal of the Korean Applied Science and Technology
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    • v.23 no.1
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    • pp.63-69
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    • 2006
  • Methanol and formaldehyde were produced directly by the partial oxidation of methane. The catalysts used were mixed oxides of late-transition metals, such as Mn, Fe, Co, Ni and Cu. The reaction was carried out at $450^{\circ}C$, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by XRD, TPD and BET apparatus. Of the catalysts, A-Mn0.2-6, which contains 0.2 mole of Mn and calcined at $600^{\circ}C$, showed the best catalytic activity: 3.7% methane conversion, and 30 and 28% methanol and formaldehyde selectivities, respectively. The catalytic activity was changed with the content of Mn and the calcination temperature. Catalytic activity increased with the specific surface areas of the catalysts. With XRD, it was found that the structure of the catalysts are changed with calcination temperature. Through $O_2-TPD$ experiment, it was found that the catalysts showing good catalytic activity showed $O_2$ desorption peak around $800^{\circ}C$.

Effects of Fe(III) and Cu(II) Ions on the Autoxidation of L-Ascorbic Acid

  • Kim, Mi-Ok
    • Preventive Nutrition and Food Science
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    • v.6 no.2
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    • pp.83-86
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    • 2001
  • The autoxidation reaction of L-ascorbic acid(AsA), and, particularly, the oxidation rates of AsA in the presence of Fe(III) or Cu(II) ions were determined in water and methanol. UV spectral measurement (at 265 nm) and HPLC were used to determine the remaining amounts of AsA in water and methanol, respectively. It was found that, in the presence of metal ions, the autoxidation rate of AsA was significantly affected by the kinds of solvents used, and also by the kinds of metal ions present. Moreover, the first-order rate constants for the oxidation of non-dissociated AsA compared with dissociated-AsA were investigated. It was confirmed that the oxidation of AsA was more accelerated in the dissociated form of AsA than in the non-dissociated form of AsA in either with Fe(III) or Cu(II). It was also found that the Cu(II) at a concentration of 0.1 $\mu$M had a more significant effect on the first-order rate constants for the autoxidation of AsA than Fe(III) at 5 $\mu$M.

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Vanadium(IV)-Catalyzed Oxidation of Dimethylsulfoxide by Hydrogen Peroxide (바나듐(IV) 촉매존재하에서 과산화수소에 의한 디메틸술폭시드의 산화반응)

  • Chang-Su Kim;Sang-Chil Moon;Seung-Hyun Chang
    • Journal of the Korean Chemical Society
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    • v.32 no.6
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    • pp.567-574
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    • 1988
  • Kinetic studies on the vanadium(IV)-catalyzed oxidation of dimethylsulfoxide by hydrogen peroxide in water and aqueous methanol and ethanol show that the reaction is the first order in the concentration of dimethylsulfoxide and hydrogen peroxide, respectively. Activation parameters are also measured for the oxidation of dimethylsulfoxide. It is suggested that the rate determining step is a process involving oxidation of dimethylsulfoxide as the result of nucleophilic attack by the sulfur on the O-O bond of vanadium(V)-peroxide complex.

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The Oxidation of Hydrazobenzene Catalyzed by Cobalt Complexes in Nonaqueous Solvents

  • Kim, Stephen S.B.;Hommer, Roger B.;Cannon, Roderick D.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.2
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    • pp.255-265
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    • 2006
  • The oxidation of hydrazobenzene by molecular oxygen in the polar solvent methanol is catalysed by a Schiff's base complex Co(3MeOsalen) which is a synthetic oxygen carrier. The products are trans-azobenzene and water. The rate of the reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a ternary complex of catalyst, hydrazobenzene and molecular oxygen has been proposed. The kinetic studies show that a ternary complex $CoL{\cdot}H_2AB{\cdot}O_2$ is involved in the rate determining step. The reactions are summarised in a catalytic cycle. The kinetic data suggest that a ternary complex involving Co(3MeOsalen), triphenyl-phosphine and molecular oxygen is catalytically acive species but at higher triphenylphosphine concentrations the catalyst becomes inactive. The destruction of the catalytic activity could be due to the catalyst becoming coordinated with triphenyl phosphine at both z axis sites of the complex e.g. Co (3MeOsalen)$(PPh_3)_2$.

A Study of Combustion Reaction of Methane by Pd Catalyst - Effects of Support Size & Calcination Temperature - (팔라듐 촉매의 메탄의 연소반응에 관한 연구 -담체의 크기와 소성온도에 따른 효과-)

  • Lee Taeck Hong
    • Journal of the Korean Institute of Gas
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    • v.8 no.3 s.24
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    • pp.52-56
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    • 2004
  • Pd catalyst have been used in hydrogenation, oxidation, and low temperature combustion reaction. Recently, it is candidated as a possible reagents in the partial oxidation of methanol reformers of the fuel cell. Pd catalysts, even though it is very precious and expensive, catalytic functioning is good, but it still need to be improved in the matter of durability and low catalytic activity after calcination. In this study, we synthesize the improved Pd catalyst and study their chemical functioning.

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Synthesis of Pt-Sn/Carbon Electrodes by Reduction Method for Direct Methanol Fuel Cell (환원법에 의한 직접 메탄올 연료전지(DMFC)용 Pt-Sn/Carbon 전극제조)

  • Jung, So-Mi;Shin, Ju-Kyung;Kim, Kwan-Sung;Baeck, Sung-Hyeon;Tak, Yong-Sug
    • Applied Chemistry for Engineering
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    • v.21 no.5
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    • pp.537-541
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    • 2010
  • Pt-Sn with various ratios was supported on carbon black after pretreatment in an acidic solution by a reduction method. The Pt/Sn ratio was controlled by varying the concentration of each component in the solution, and the influence of the composition on the electrocatalytic activities was investigated. The crystallinity of the synthesized materials was investigated by XRD (X-ray Diffraction), and the oxidation states of both the platinum and tin were determined by XPS (X-ray Photoelectron Spectroscopy). SEM (Scanning Electron Microscopy)-EDS (Energy Dispersive Spectroscopy) was utilized to examine the morphology and composition of the synthesized electrode, and the particle size of the Pt-Sn was analyzed by TEM (Transmission Electron Microscopy). The electrocatalytic activity for oxygen reduction was evaluated in a 0.5 M $H_2SO_4$ solution using a rotating disk electrode system. The activity and stability were found to be strongly dependent on the electrode composition (Pt/Sn ratio). The catalytic activity and stability for methanol oxidation were also measured using cyclic voltammetry (CV) in a mixture of 0.5 M $H_2SO_4$ and 0.5 M $CH_3OH$ aqueous solution. The addition of proper amount of Sn was found to significantly improve both catalytic activity and stability for methanol oxidation.

Synthesis of TiO2 Composited Nitrogen-doped Carbon Supports for High-Performance Methanol Oxidation Activity (고성능 메탄올 산화 반응을 위한 이산화 티타늄 복합화된 질소 도핑 탄소 지지체의 합성)

  • Jo, Hyun-Gi;Ahn, Hyo-Jin
    • Korean Journal of Materials Research
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    • v.30 no.1
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    • pp.14-21
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    • 2020
  • Carbon supports for dispersed platinum (Pt) electrocatalysts in direct methanol fuel cells (DMFCs) are being continuously developed to improve electrochemical performance and catalyst stability. However, carbon supports still require solutions to reduce costs and improve catalyst efficiency. In this study, we prepare well-dispersed Pt electrocatalysts by introducing titanium dioxide (TiO2) into biomass based nitrogen-doped carbon supports. In order to obtain optimized electrochemical performance, different amounts of TiO2 component are controlled by three types (Pt/TNC-2 wt%, Pt/TNC-4 wt%, and Pt/TNC-6 wt%). Especially, the anodic current density of Pt/TNC-4 wt% is 707.0 mA g-1pt, which is about 1.65 times higher than that of commercial Pt/C (429.1 mA g-1pt); Pt/TNC-4wt% also exhibits excellent catalytic stability, with a retention rate of 91 %. This novel support provides electrochemical performance improvement including several advantages of improved anodic current density and catalyst stability due to the well-dispersed Pt nanoparticles on the support by the introduction of TiO2 component and nitrogen doping in carbon. Therefore, Pt/TNC-4 wt% may be electrocatalyst a promising catalyst as an anode for high-performance DMFCs.

Antioxidant Activity of Various Solvent Extracts from Freeze Dried Kimchi (김치 용매 추출물의 항산화성)

  • 이영옥;최홍식
    • Journal of Life Science
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    • v.6 no.1
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    • pp.66-71
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    • 1996
  • Antioxidative activity of various solvent extracts from freeze dried Kimchi was studied during the oxidation process of linoleic acid mixture system. The aqueous model systems were used for the evaluation of antioxidative activity of solvent extracts during the oxidative reaction at 37$^{\circ}C$ by the determination of peroxide value. The linoleic acid mixture for the aqueous model systems was consisted of linoleic acid (64.6%), oleic acid(27.4%), and other acids in ethanolic phosphate buffer (pH 7.0). Water and methanol extracts of Kimchi had a considerable antioxidative activity with the inhibition of peroxides formation during the autoxidation of linoleic acid mixture in aqueous model systems. Antioxidative activity of 75% methanol extract of 7 day-fermented-Kimchi was relatively higher than that of others, however lower than alpa-tocopherol and butylated hydroxyanisol. The antioxidative effect of 75% methanol extract of 7 day-fermented-Kimchi was increased by the its concentration from 0.5% to 2.5% in the oxidation reactions of aqueous model systems.

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Synthesis and Characterization of Tetrathiafulvalene (TTF) and 7,7,8,8-Tetracyanoquinodimethane (TCNQ) Compounds with PdX2(X=CI, NO3and Hexafluoroacetylacetonate)

  • Kim, Young-Inn;Jeong, Chan-Kyou;Lee, Yong-Min;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1754-1758
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    • 2002
  • Tetrathiafulvalene(TTF) reacts with $PdCl_2,Pd(NO_3)_2$ and $Pd(hfacac)_2$(hexafluoroacetylacetonate) in ethanol to give $(TTF)_{1.5}PdCl_2$ (1a), $(TTF)_3Pd(NO_3)_2$ (1b) and $(TTF)_4Pd(hfacas)_2$ nd (1c), respectively. $PdCl(TCNQ)_{2.5}{\cdot}CH_3OH(2a)$was obtained from the reaction of $PdCl_2$ with LiTCNQ in methanol via the partial replacement of $Cl^-$ in $PdCl_2$ by $TCNQ^-$anion, whereas the total substitution of the labile $NO_3^-$ in $Pd(NO_3)_2$ yielded pd(TCNQ)·$CH_3OH$ (2b). $Pd(hfacac)_2(TCNQ)_2\cdot3CH_3OH$ (2c) was obtained from $Pd(hfacac)_2$ and LiTCNQ in methanol. The prepared compounds were characterized by spectroscopic (IR, UV, XPS) methods and magnetic (EPR, magnetic susceptibility) studies. The powdered electrical conductivities (${\sigma}_{rt}$) of the prepared compounds at room temperature were about~$10^{-7}S{\cdot}cm^{-1}$. The effective magnetic moments were lass than the spin-only value of one unpaired electron and no EPR signals from Pd metal ions were observed in any of the compounds, indicating that the Pd ions were diamagnetic and the magnetic moments arose from$(TTF)_n$ or $(TCNQ)_n$ moieties. The experimental evidences revealed that the charge transfer had occurred form $(TTF)_n$ moiety to the central Pd metal ion in 1a, 1b and 1c. Thus the TTF donors were ions in 2a and 2b were diamagnetic Pd(II) oxidation state. In contrast, the Pd metal ion was oxidized to Pd(IV) state in 2c as a result of an addition of $TCNQ^-$anion to $Pd(hfacac)_2$ in methanol. The oxidation states of the Pd metal ions were confirmed using the x-ray photoelectron spectroscopy.

Non-Enzymatic Browning Reactions in Dried Alaska Pollak Stored at Different Water Activities (마른명태 저장중(貯藏中)의 수분활성(水分活性)과 갈변반응(褐變反應))

  • Kim, Mu-Nam;Choi, Ho-Yeon;Lee, Kang-Ho
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.2 no.1
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    • pp.41-47
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    • 1973
  • In the present work, the quality stability of sun-dried Alaska pollack, Theragra chalcogramma, was discussed in the aspects of non-enzymatic discoloration as a function of relative humidity during storage at room temperature$(20^{\circ}C)$. Frozen Alaska pollack was dressed, filleted, dried for 48 hours in the open air, and finally stored in cylindrical acrylic chambers which contained saturated specific salt solutions proposed by Rockland(1960) for humidity control. The color development of the product was analyzed by spectrophotometry at 10 day-intervals during the storage. Lipid oxidation was measured as TBA value at wavelength of 538nm. And browning pigments were extracted, divided into two fractions and measured at 460nm: one was chloroform-methanol (2:1 v/v)soluble fraction attributed to lipid oxidation, and the other was water dialyzed fraction caused by so called Maillard reaction. The TBA value showed a maximum on 30 day storage, hereafter, intended to decrease gradually. On the other hand, the rate of brown pigment development in water dialyzed fractions as well as in chloroform-methanol soluble fractions was lower at 34 to 45%RH than at any other case, and propagation of lipid oxidation was also diminished at the same levels of humidity. From the facts described previously, it is recognized that storage at 34 to 45%RH provides higher quality stability for sun-dried Alaska pollack.

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