• Title/Summary/Keyword: Oxidative Dehydrogenation

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Catalytic Reactions of Ethanol over $TiO_2$-supported Vanadia Catalysts

  • Jeon, Byung-Wook;Kim, Yu-Kwon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.284-284
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    • 2012
  • In this study, $V_2O_5/TiO_2$ catalyst was measured reactivity of ethanol when vanadia ratio was increasing. First, $V_2O_5/TiO_2$ catalyst was prepared to the increasing vanadia ($VO_x$) ratio as 0.2, 1, 10 wt%. And we were used X-ray diffraction (XRD), then not appear markedly peak to pure vanadia about XRD analysis. So we were decided vanadia that was evenly dispersed on $TiO_2$. Result about temperature-programmed reduction (TPR) analysis was obtained 3 reactions that was dehydrogenationfrom obtained to acetaldehyde, dehydration from obtained to ethylene, condensation from obtained to diethyl ether. If vanadia ratio was increasing in $V_2O_5/TiO_2$, reactions temperature of ethanol was known lower. And condensation into diethyl ether is quenched away with increasing vanadia loading. In addition, competition between reductive dehydration and oxidative dehydrogenation occurs, while the selectivity toward dehydrogenation is favored with increasing vanadia loading.

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Oxidative Dehydrogenation of 1-butene over BiFe0.65MoP0.1 Catalyst: Effect of Phosphorous Precursors (BiFe0.65MoP0.1 촉매 상에서 1-부텐의 산화탈수소화 반응 : 인 전구체의 영향)

  • Park, Jung-Hyun;Youn, Hyun Ki;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.53 no.6
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    • pp.824-830
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    • 2015
  • The influence of phosphorous precursors, $NH_4H_2PO_4$, $(NH_4)_2HPO_4$, $H_3PO_4$, $(C_2H_5)_3PO_4$, and $P_2O_5$, on the catalytic performance of the $BiFe_{0.65}MoP_{0.1}$ catalysts in the oxidative dehydrogenation of 1-butene to 1,3-butadiene was studied. The catalysts were characterized by XRD, $N_2$-sorption, ICP, SEM and TPRO analyses. It was not observed big difference on the physical properties of catalysts in accordance with used different phosphorous precursors, however, the catalytic performance was largely depended on the nature of the phosphorous precursors. Of various precursors, the $BiFe_{0.65}MoP_{0.1}$ oxide catalyst, which was prepared from a phosphoric acid precursor, showed the best catalytic performance. Conversion and yield to butadiene of the catalyst showed 79.5% and 67.7%, respectively, after 14 h on stream. The cation of phosphorous precursors was speculated to affect the lattice structure of the catalysts during catalyst preparation and this difference was influenced on the re-oxidation ability of the catalysts. Based on the results of TPRO, it was proposed that the catalytic performance could be correlated with re-oxidation ability of the catalysts.

Reaction of the Fe(II) Macrocyclic Complexes with Dioxygen : Preparation of New Unsaturated Ring Systems by Oxidative Dehydrogenation Reactions of Fe(II) Macrocyclic Ligands (이가철 거대고리 리간드의 착화합물과 산소 분자간의 반응 : 이가철 거대고리 리간드 착화합물의 산화성 탈수소 반응에 의한 새로운 불포화 고리계의 합성)

  • Myunghyun Paik;Shin-Geol Kang;Kyu Whan Woo
    • Journal of the Korean Chemical Society
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    • v.28 no.6
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    • pp.384-392
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    • 1984
  • Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

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Selective Oxidation of Amines to Imines or Nitriles by Manganese Dioxide in Air (공기 중에서 망간 다이옥사이드에 의한 아민에서 이민 또는 나이트릴로의 선택적 산화 반응)

  • Kim, Yo Han;Hwang, Seung Kyu;Lee, Yoon Sik;Kim, Jung Won
    • Applied Chemistry for Engineering
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    • v.25 no.2
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    • pp.215-221
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    • 2014
  • A simple heterogeneous system has been developed by using base treated manganese dioxide (B-$MnO_2$) for the aerobic oxidation of amines under mild reaction conditions of 1 atm of air and $50^{\circ}C$ in hexane. This system was highly efficient to oxidize various kinds of primary or secondary amines including aliphatic, aromatic, and hetero-atomic ones under the applied reaction conditions. Amines were oxidized to nitriles or diimines by the self-condensation or oxidative dehydrogenation through imine intermediate. The B-$MnO_2$ was reused for at least 5 times without any loss of its catalytic performance and showed its cost effectiveness, easy workup, and easy separation of the products for achieving the protocol of green chemistry.

Membrane reactors in gas phase oxidations

  • Bottino, A.;Capannelli, G.;Comite, A.;Felice, R.Di
    • Proceedings of the Membrane Society of Korea Conference
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    • 2003.07a
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    • pp.33-36
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    • 2003
  • This research was aimed at developing new catalytic membrane reactors to be used for : i) partial oxidation of toluene (to benzaldehyde and benzoic acid) ii) oxidative dehydrogenation of propane iii) complete oxidation of propane and toluene. The reactor is particularly useful for the optimisation and the industrial development of heterogeneous catalytic processes, particularly for those processes where it is necessary to control the reactants stoichiometry in the reaction zone. This control limits consecutive reactions, thus obtaining high selectivity with industrially interesting conversions. This presentation will concentrate on the partial oxidation of toluene.

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Oxidative Dehydrogenation of n-Butenes over BiFe0.65MoP0.1 Oxide Catalysts Prepared with Various Synthesis Method (다양한 합성 방법으로 제조된 BiFe0.65MoP0.1 산화물 촉매 상에서 n-부텐의 산화탈수소화 반응)

  • Park, Jung-Hyun;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.53 no.3
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    • pp.391-396
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    • 2015
  • To investigate the effect of the catalyst synthesis method on the oxidative dehydrogenation (ODH) of nbutenes, $BiFe_{0.65}MoP_{0.1}$ oxide catalysts were prepared with various synthesis methods such as co-precipitation, citric acid method, hydrothermal method, and surfactant templated method. The catalysts were characterized by X-ray Diffraction (XRD), $N_2$ sorption, and $NH_3/1$-butene-temperature programmed desorption ($NH_3/1$-butene-TPD) to correlate with catalytic activity in ODH reaction. Among the catalysts studied here, $BiFe_{0.65}MoP_{0.1}$ oxide catalyst prepared with co-precipitation method marked the highest activity showing 1-butene conversion, 79.5%, butadiene selectivity, 85.1% and yield, 67.7% after reaction for 14 h. From the result of $NH_3$-TPD, the catalytic activity is closely related to the acidity of the $BiFe_{0.65}MoP_{0.1}$-x oxide catalyst and acidity of the $BiFe_{0.65}MoP_{0.1}$ oxde catalyst prepared with co-precipitation method was higher than that of other catalysts. In addition, combined with the 1-butene TPD, the higher catalytic activity is closely related to the amount of weakly adsorbed intermediate (< $200^{\circ}C$) and the desorbing temperature of strongly adsorbed intermediates (> $200^{\circ}C$).

Studies on the Selective Oxidation of Niobium Containing Mixed Metal Oxide Catalysts (니오비움 함유 복합 금속산화물 촉매의 선택산화반응에 관한 연구)

  • Kim, Young-Chul;Kim, Hyeong-Ju;Moon, Dong-Ju
    • Applied Chemistry for Engineering
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    • v.9 no.1
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    • pp.129-134
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    • 1998
  • Conversion of propane to acrylonitrile via ammoxidation was studied using physically mixed catalysts composed of $Nb_2O_5(10{\sim}30wt%)$ and $V_{0.4}Mo_1Te_{0.1}$. Catalytic activities of ammoxidation were improved by adding strong acidic niobium oxide to $V_{0.4}Mo_1Te_{0.1}$, the selectivities to acrylonitrile+propylene being remained constant. The maximum activity was obtained at the mixing ratio 25wt% niobium oxide in $Nb_2O_5-V_{0.4}Mo_1Te_{0.1}$. Niobium oxide was found to be a selective catalyst for the oxidative dehydrogenation of propane.

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