• Title/Summary/Keyword: hydrogenation

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Hydrogenation of Ethyl Acetate to Ethanol over Bimetallic Cu-Zn/SiO2 Catalysts Prepared by Means of Coprecipitation

  • Zhu, Ying-Ming;Shi, Xin Wang Li
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.141-146
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    • 2014
  • A series of bimetallic Cu-Zn/$SiO_2$ catalysts were prepared via thermal decomposition of the as-synthesized $CuZn(OH)_4(H_2SiO_3)_2{\cdot}nH_2O$ hydroxides precursors. This highly dispersed Cu-solid base catalyst is extremely effective for hydrogenation of ethyl acetate to ethanol. The reduction and oxidation features of the precursors prepared by coprecipitation method and catalysts were extensively investigated by TGA, XRD, TPR and $N_2$-adsorption techniques. Catalytic activity by ethyl acetate hydrogenation of reaction temperatures between 120 and $300^{\circ}C$, different catalyst calcination and reduction temperatures, different Cu/Zn loadings have been examined extensively. The relation between the performance for hydrogenation of ethyl acetate and the structure of the Cu-solid base catalysts with Zn loading were discussed. The detected conversion of ethyl acetate reached 81.6% with a 93.8% selectivity of ethanol. This investigation of the Cu-Zn/$SiO_2$ catalyst provides a recently proposed pathway for ethyl acetate hydrogenation reaction to produce ethanol over Cu-solid base catalysts.

Comparison of Adsorption Properties of Adsorbates on Pt(111) and Pt(111)/$\gamma-Al_2O_3$ Surface in the Ethylene Hydrogenation Reaction : MO-Theory

  • 조상준;박상문;박동호;허도성
    • Bulletin of the Korean Chemical Society
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    • v.19 no.7
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    • pp.733-737
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    • 1998
  • Using an atom superposition and electron delocalization molecular orbital (ASED-MO) method, we have compared adsorption properties of adsorbates on the Pt(Ill) surface with the Pt(lll)/γ-Al203 surface in the ethylene hydrogenation reaction. In two-layer thick model systems, the calculated activation energy of the hydrogenation by the surface platinum hydride is equal to the energy by the hydride over supported platinum/γ-alumina. The transition structure on platinum is very close to the structure on the supported platinum/γ-alumina surface. Hydrogenation by the surface hydride on platinum can take place easily because the activation energy is about 0.5 eV less than hydrogenation by ethylidene. On supported platinum/,y-alumina the activation energy of the hydride mechanism is about 0.61 eV less than that of ethylidene mechanism. In one-layer thick model systems, the activation energy of hydrogenation by ethylidene is about 0.13 eV less than the activation energy of hydride reaction. The calculated activation energy by the hydride over the supported platinum y-alumina is 0. 24 eV higher than the platinum surface. We have found from this result that the catalytic properties of one-layer thick model systems have been influenced by the support but the two-layer thick model systems have not been influenced by the support.

Effect of Preparation Conditions on the Hydrogenation Activity and Metal Dispersion of Pt/C and Pd/C Catalysts

  • Jhung, Sung-Hwa;Lee, Jin-Ho;Lee, Jong-Min;Lee, Ji-Hye;Hong, Do-Young;Kim, Myong-Woon;Chang, Jong-San
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.563-568
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    • 2005
  • The Pt/C and Pd/C catalysts were prepared from conventional chloride precursors by adsorption or precipitation-deposition methods. Their activities for hydrogenation reactions of cyclohexene and acetophenone were compared with those of commercial catalysts. The Pt/C and Pd/C catalysts obtained from the adsorption procedure reveal higher hydrogenation activity than commercial catalysts and the catalysts prepared by the precipitation-deposition method. Their improved performances are attributed to the decreased metal crystallite sizes of Pt or Pd formed on the active carbon support upon the adsorption of the precursors probably due to the same negative charges of the chloride precursor and the carbon support. Under the preparation conditions studied, the reduction of the supported catalysts using borohydrides in liquid phase is superior to a gas phase reduction by using hydrogen in the viewpoint of particle size, hydrogenation activity and convenience.

The Hydrogenation Behaviors of V-xAl (x=1, 5wt.%) Composites by Mechanical Alloying (기계적 합금화법으로 제조한 V-xAl (x=1, 5wt.%) 복합재료의 수소화 반응 거동)

  • Kim, Kyeong-Il;Hong, Tae-Whan
    • Journal of Hydrogen and New Energy
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    • v.22 no.4
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    • pp.458-464
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    • 2011
  • Recently, one of the hydrogen production methods has attracted using dense metallic membrane. It has high hydrogen permeation and selectivity which hardly could adopt industrial product because of high cost, hydrogen embrittlment and thermal stability. Meanwhile, vanadium has high hydrogen solubility and it use to instead of Pd-Ag amorphous membrane. Aluminum carried out blocking hydrogen diffusion on grain boundary therefore protecting hydrogen embrittlement. Most of dense metallic membrane is solution diffusion mechanism. The solution diffusion mechanism was very similar hydrogen storing steps such as steps of metal hydride. Thus, V-Al composites were fabricated to use hydrogen induced mechanical alloying. The fabricated V-Al composites were characterized by XRD, SEM, EDS and simultaneous TG/DSC analyses. The hydrogenation behaviors were evaluated using a Sievert's type automatic PCT apparatus. The hydrogenation behaviors of V-Al composites was evaluated too low hydrogen stored capacity and fast hydrogenation kinetics. In PCI results, V-Al composites had low hydrogen solubility, in spite of that, hydrogen kinetics was calculated very fast and hydrogen absorption/desorption contents were same capacity.

Adsorption and Thermal Reduction Mechanism of CO2 on ZnO/Cu Model Catalysts

  • Kim, Yeonwoo;Kim, Sehun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.191.2-191.2
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    • 2014
  • Cu/ZnO/$Al_2O_3$ is widely used methanol synthesis catalyst at elevated pressures P (50 to 100 bar) and temperatures T (473 to 573 K) using $CO_2$, CO, $H_2$ syngas mixture. Although Cu step and planar defects have been regarded as active sites in this catalyst, detailed $CO_2$ hydrogenation procedure has been still unknown and debated as well as initial intermediate. In this study, we investigated the mechanism of $CO_2$ hydrogenation on Cu(111) model surface at P (1 bar) and T (298 to 450 K) using reflection absorption infrared spectroscopy (RAIRS). Two distinct formates by hydrogenation of $CO_2$, on step and on terrace, show different behavior with elevating temperature. The peak intensity of on step formate was continuously decreased above 360 K up to 450K in contrast to the increase of on terrace formate. These phenomena are strong possibilities that the formate is initial intermediate and is desorbed by hydrogenation reaction because thermal desorption temperature of formate (~470 K) is much higher than desorption of on step formate. And the formate production peak of on step site was weakly correlated with CO formation.

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Optical Properties of Hydrogenated Amorphous Chalcogenide Thin Films (수소화 처리된 비정질 칼코게나이드 박막의 광학적 특성)

  • Nam Gi-Yeon;Kim Jun-Hyung;Cho Sung-June;Lee Hyun-Yong
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.19 no.5
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    • pp.450-456
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    • 2006
  • In this paper, we report the changes of morphology, transmittance and photoluminescence (PL) in hydrogenated amorphous $As_{40}Ge_{10}Se_{15}S_{35}$ thin films, thermally deposited at the vapor incidence angles (${\theta}$) of $0^{\circ},\;45^{\circ}\;and\;80^{\circ}$. The hydrogenation was carried out under the condition of a $H_2$ pressure ($P_H$) of 20 atm and an annealing temperature range, $T_{Anneal}$ of $150^{\circ}C{\sim}210^{\circ}C$. A columnar structures with an inclination angle of approximately $65{\sim}70^{\circ}$ was formed in $80^{\circ}$-deposited films and then the columnar was broken after hydrogenation. Transmittance increases with an increase of deposition angle and by the hydrogenation. In particular, a broad PL band on the extended region is observed in obliquely deposited films and it increases during the hydrogenation.

Analysis of hydrogenation effects on Low temperature Poly-Si Thin Film Transistor (저온에서 제작된 다결정 실리콘 박막 트랜지스터의 수소화 효과에 대한 분석)

  • Choi, K.Y.;Kim, Y.S.;Lee, S.K.;Lee, M.C.;Han, M.K.
    • Proceedings of the KIEE Conference
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    • 1993.07b
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    • pp.1289-1291
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    • 1993
  • The hydrogenation effects on characteristics of polycrystalline silicon thin film transistors(poly-Si TFT's) of which the channel length varies from $2.5{\mu}m\;to\;20{\mu}m$ and poly-Si layer thickness is 50, 100, and 150 nm was investigated. After 1 hr hydrogenation annealing by PECVD, the threshold voltage shift decreased dependent on the channel length, but channel width may not alter the threshold voltage shift. In addition to channel length, the active poly-Si layer thickness may be an important parameter on hydrogenation effects, while gate poly-Si thickness may do not influence on the characteristics of TFT's. Considering our experimental results, we propose that channel length and active poly-Si layer thickness may be a key parameters of hydrogenation of poly-Si TFT's.

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Shapes and Deformation of the Hydrogen Absorption Metal (수소저장금속의 형상과 변형)

  • 정영관;박규섭;이근진;김경훈;김세웅
    • Proceedings of the Korean Society of Precision Engineering Conference
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    • 2003.06a
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    • pp.1382-1385
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    • 2003
  • Deformation on shapes of the hydrogen absorption metal in this paper was investigated on hydrogen absorption-desorption cycling. In order to study this problem, the cold rolled palladium plate and the cold extrusion palladium bar as specimens had been used. By using the electrochemical method, the palladium specimens were cyclically hydrogenated in the 0.1 mol H$_2$SO$_4$ electrolyte. As results, it is noted that the thickness of the plate specimen gradually increased in increasing hydrogenation cycles whereas the width and the length decreased. But both the diameter and the length of the bar specimen increased with increasing hydrogenation cycles. Also, grains in the plate specimen were greatly deformed after hydrogenation cycling whereas internal grains in the bar specimen were pulverized. And deterioration of the hydrogen absorption rate of the bar specimen was lager than the plate specimen.

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Effects of Catalyst Promotion on the Selective Hydrogenation of Biphenol Using Various Pd/C Catalysts

  • Cho, Hong-Baek;Hong, Bum-Eui;Park, Jai-Hyun;Ahn, Sung-Hyun;Park, Yeung-Ho
    • Bulletin of the Korean Chemical Society
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    • v.29 no.12
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    • pp.2434-2440
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    • 2008
  • The effect of sodium (Na) promotion was studied in the biphenol (BP) hydrogenation using various Pd/C catalysts. Different amounts of sodium metal were used for promotion with Pd/C and their effects on BP hydrogenation were observed. The promotion order was changed to compare the effect of the position of the promoter in relation to the palladium (Pd) metal on the catalytic activity and yield of the final product, bicyclohexyl-4,4'-diol (BHD). Pd/C catalysts prepared from different methods were also sodium-promoted and the changes of the reaction pathway according to the type of promoted Pd/C catalyst were compared.

Selective Hydrogenation of 1,3-Butadiene over Supported Nickel Catalyst Obtained from Nickel-Zirconia Solid Solution

  • Chang, Jong-San;Ryu, Jae-Oak;Lee, Jong-Min;Park, Sang-Eon;Hong, Do-Young;Jhung, Sung-Hwa
    • Bulletin of the Korean Chemical Society
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    • v.26 no.10
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    • pp.1512-1514
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    • 2005
  • Catalytic properties of Ni-Zr$O_2$ catalysts prepared by coprecipitation have been studied for the gas-phase hydrogenation of 1,3-butadiene to butenes. The coprecipitation method led to the solid solution of Ni-Zr$O_2$, which contains highly resistant Ni species to thermal reduction with H2. Nickel species of the solid solution were highly dispersed in the ZrO2 lattice, so that the reduced catalysts were selective for hydrogenation of 1,3-butadiene to butenes (99.9%) even in the presence of 1-butene.