• Title/Summary/Keyword: Pd catalysts

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Catalytic Oxidation of 1.2-Dichloroethane on Precious Metal Catalysts (귀금속 촉매를 이용한 1.2-Dichloroethane의 산화분해에 관한 연구)

  • Lee, Hae-Wan;Kim, Young-Chai;Moon, Sei-Ki
    • Applied Chemistry for Engineering
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    • v.9 no.4
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    • pp.497-503
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    • 1998
  • The catalytic oxidation of 1.2-dichloroethane was investigated over precious metal supported on alumina using a fixed bed microreactor. Among the catalysts tested, the conversion of 1.2-dichloroethane decreased in the following order : Ru > Pt > Pd $${\sim_=}$$ Rh and Pt was found to be the most active catalyst for the complete oxidation of 1.2-dichloroethane to $CO_2$. Major products containing carbon were vinyl chloride and $Co_2$ at temperature ranging from 200 to $400^{\circ}C$. The presence of vinyl chloride in products suggests that the first step in the oxidation of 1.2-dichloroethane is dehydrochlorination and the second is oxidation of vinyl chloride to $CO_2$. To investigate the effect of HCl on the activity of the complete oxidation, some experiments were conducted by adding HCl to the feed. The presence of HCl increased the conversion of 1.2-dichloroethane below $300^{\circ}C$ owing to the increase of surface acidity, but it didn't affect the conversion above $300^{\circ}C$. The reversible adsorption of HCl onto catalyst surface inhibited the complete oxidation to $CO_2$.

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Chiral [Iminophosphoranyl]ferrocenes: Synthesis, Coordination Chemistry, and Catalytic Application

  • Co, Thanh Thien;Shim, Sang-Chul;Cho, Chan-Sik;Kim, Dong-Uk;Kim, Tae-Jeong
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1359-1365
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    • 2005
  • A series of new chiral [iminophosphoranyl]ferrocenes, {${\eta}^5-C_5H_4-(PPh_2=N-2,6-R_2-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-PPh^2-2-CH(Me)NMe_2$} (1: R = Me, $^iPr$), {${\eta}^5{-C_5H_4-(PPh_2=N-2,6-R_2}^1-C_6H_3)$}Fe{${\eta}^5-C_5H_3-1-(PPh_2=N-2,6-R_2-C_6H_3)-2-CH(Me)R_2$} (2: $R^1\;=\;Me,\;^iPr;\;R^2\;=\;NMe_2$, OMe), and $({\eta}^5-C_5H_5)Fe${${\eta}^5-C_5H_4-1-PR_2-2-CH(Me)N=PPh_3$} (3:R = Ph, $C_6H_{11}$) have been prepared from the reaction of [1,1'-diphenylphosphino-2-(N,N-dimethylamino) ethyl]ferrocene with arylazides (1 & 2) and the reaction of phosphine dichlorides ($R_3PCl_{2}$) with [1,1'-diphenylphosphino-2-aminoethyl]ferrocene (3), respectively. They form palladium complexes of the type $[Pd(C_3H_5)(L)]BF_4$ (4-6: L = 1-3), where the ligand (L) adopts an ${\eta}^2-N,N\;(2)\;or\;{\eta}^2$-P,N (3) as expected. In the case of 1, a potential terdentate, an ${\eta}^2$-P,N mode is realized with the exclusion of the –=NAr group from the coordination sphere. Complexes 4-6 were employed as catalysts for allylic alkylation of 1,3-diphenylallyl acetate leading to an almost stoichiometric product yield with modest enantiomeric excess (up to 74% ee). Rh(I)-complexes incorporating 1-3 were also prepared in situ for allylic alkylation of cinnamyl acetate as a probe for both regio- and enantioselectivities of the reaction. The reaction exhibited high regiocontrol in favor of a linear achiral isomer regardless of the ligand employed.

A Study on the Hydrogenation of CO2 Using Cu/ZnO/Cr2O3/Al2O3 Catalysts (Cu/ZnO/Cr2O3/Al2O3 촉매를 이용한 이산화탄소의 수소화 연구)

  • Sim, Kyu-Sung;Han, Sang-Do;Kim, Jong-Won;Kim, Youn-Soon;Myoung, Kwang-Sik;Park, Ki Bae
    • Transactions of the Korean hydrogen and new energy society
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    • v.7 no.2
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    • pp.147-155
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    • 1996
  • The aim of this study is the development of technologies of methanol production from carbon dioxide by catalytic hydrogenation. Experiments about carbon dioxide hydrogenation by catalyst mixed with CuO, ZnO, $Cr_2O_3$ and $Al_2O_3$ were conducted to find optimum catalyst and reaction condition. Reactions were carried out at atmospheric and high pressures between 200 to $350^{\circ}C$. High yield of methanol was obtained with $Cu/ZnO/Cr_2O/Cr_2O_3/Al_2O_3$ catalyst at $250^{\circ}C$ and above 30 atmospheric pressure. There was not any increament of hydrogenation reactivity for the catalysts which was made by the addition of Pd to $Cu/ZnO/Cr_2O/Cr_2O_3/Al_2O_3$.

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A Method for Suppression of Active Metal Leaching during the Direct Synthesis of H2O2 by Using Polyelectrolyte Multilayers (고분자 전해질 다층박막을 이용한 과산화수소 직접제조 반응 중 활성금속 용출 억제 방법)

  • Chung, Young-Min
    • Korean Chemical Engineering Research
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    • v.53 no.2
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    • pp.262-268
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    • 2015
  • In this study, two types of catalysts were prepared via conventional metal supporting method and encapsulation of metal nanoparticles in the polyelectrolyte multilayers constructed on support. The resulting catalysts were applied to the direct synthesis of hydrogen peroxide, and the effect of catalyst preparation method on the catalyst life as well as hydrogen peroxide productivity was investigated. The catalytic activity was strongly dependent upon the acid strength of support regardless of the catalyst preparation methods and HBEA (SAR=25) with strong acidity was superior to other supports to promote the reaction. In the case of metal supported catalyst, while hydrogen peroxide productivity was higher than that of polyelectrolyte multilayered counterpart, the reaction performance was sharply decreased during catalyst recycling due to the metal leaching. On the other hand, construction of polyelectrolyte multilayers on support weakened the influence of acid support on the reaction medium and therefore resulted in the decrease of catalytic activity and the increase of hydrogen peroxide decomposition as well. It is noted, however, that the catalytic activity was maintained after 5 recycles, which suggests that the introduction of polyelectrolyte multilayers on the support is very effective to suppress the unfavorable metal leaching phenomenon during a reaction.

Optimization of Operating Parameters and Components for Water Electrolysis Using Anion Exchange Membrane (음이온 교환막 알칼리 수전해를 위한 운전 조건 및 구성요소의 최적화)

  • Jang, Myeong Je;Won, Mi So;Lee, Kyu Hwan;Choi, Sung Mook
    • Journal of the Korean institute of surface engineering
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    • v.49 no.2
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    • pp.159-165
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    • 2016
  • The hydrogen has been recognized as a clean, nonpolluting and unlimited energy source that can solve fossil fuel depletion and environmental pollution problems at the same time. Water electrolysis has been the most attractive technology in a way to produce hydrogen because it does not emit any pollutants compared to other method such as natural gas steam reforming and coal gasification etc. In order to improve efficiency and durability of the water electrolysis, comprehensive studies for highly active and stable electrocatalysts have been performed. The platinum group metal (PGM; Pt, Ru, Pd, Rh, etc.) electrocatalysts indicated a higher activity and stability compared with other transition metals in harsh condition such as acid solution. It is necessary to develop inexpensive non-noble metal catalysts such as transition metal oxides because the PGM catalysts is expensive materials with insufficient it's reserves. The optimization of operating parameter and the components is also important factor to develop an efficient water electrolysis cell. In this study, we optimized the operating parameter and components such as the type of AEM and density of gas diffusion layer (GDL) and the temperature/concentration of the electrolyte solution for the anion exchange membrane water electrolysis cell (AEMWEC) with the transition metal oxide alloy anode and cathode electrocatalysts. The maximum current density was $345.8mA/cm^2$ with parameter and component optimization.

Reaction Characteristics of Oxidation Catalysts for HCCI Engine (HCCI 엔진용 산화촉매의 반응특성)

  • Park, Sung-Yong;Kim, Hwa-Nam;Choi, Byung-Chul
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.34 no.2
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    • pp.165-171
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    • 2010
  • The Homogeneous Charge Compression Ignition (HCCI) engine concept allows for both NOx and particulate matter to be reduced simultaneously, and it is a promising way to meet the next environmental challenges. Unfortunately, HCCI combustion often increases CO and HC emissions. The development of oxidation catalyst (OC) requires high conversion efficiency for CO and HC at low temperature. Conventional oxidation catalyst technologies may not be able to convert these emissions because of the saturation of active catalytic sites. The OC used in this study was 600 cpsi cordierite. Three kinds of OC with different amounts of Pt and Pd were used. The influence of the space velocity (SV), $H_2O$ and $O_2$ concentration was also studied. All types of OCs were found to have over 90% CO conversion efficiencies at $170^{\circ}C$. When in the presence of water vapor, CO conversion was increased, but $C_3H_8$ conversion was decreased. The performance of the OC was not influenced by initial the HC concentration. The 2Pt/Pd catalyst was better in terms of thermal aging than the Pt-only catalyst. The $LOT_{50}$ of both fresh and aged OC was increased with increasing SV and with the presence of $H_2O$.

Physical and Chemical Characteristics of Waste Automotive Catalysts (자동차 폐촉매의 물리 화학적 특성)

  • Seo, Seong-Gyu;Moon, Joung-Sun
    • Journal of Korean Society of Environmental Engineers
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    • v.22 no.5
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    • pp.819-825
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    • 2000
  • The physico-chemical characteristics and the combustion activities of a waste automotive catalyst were carried out in this study. The physico-chemical characteristics of waste automotive catalyst was examined by EA(Elemental analysis), ICP-AES (Inductively coupled plasma-atomic emission spectrophotometer), and XRD(X-ray diffraction) analysis. Carbon deposit amount was higher in front brick than rear brick of catalyst, and increased with mileage. The content of Pt. Pd and Rh in waste automotive catalyst was different from the car manufacturing company. The combustion activities of waste automotive catalyst were investigated for acetaldehyde as a model VOC in a fixed bed reactor at atmospheric pressure. The catalytic activity of rear brick for acetaldehyde combustion was better than front brick of waste automotive catalyst. The catalytic activity of waste automotive catalyst for acetaldehyde combustion decreased with mileage. The linear relationship between catalytic activity and mileage was negative and has a very excellent correlation. Finally, the waste automotive catalyst has a good catalytic activity for acetaldehyde combustion. and can be used to control of small emission source.

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Regioselective Oxidation of Lauric Acid by CYP119, an Orphan Cytochrome P450 from Sulfolobus acidocaldarius

  • Lim, Young-Ran;Eun, Chang-Yong;Park, Hyoung-Goo;Han, Song-Hee;Han, Jung-Soo;Cho, Kyoung-Sang;Chun, Young-Jin;Kim, Dong-Hak
    • Journal of Microbiology and Biotechnology
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    • v.20 no.3
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    • pp.574-578
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    • 2010
  • Archaebacteria Sulfolobus acidocaldarius contains the highly thermophilic cytochrome P450 enzyme (CYP119). CYP119 possesses stable enzymatic activity at up to $85^{\circ}C$. However, this enzyme is still considered as an orphan P450 without known physiological function with endogenous or xenobiotic substrates. We characterized the regioselectivity of lauric acid by CYP119 using the auxiliary redox partner proteins putidaredoxin (Pd) and putidaredoxin reductase (PdR). Purified CYP119 protein showed a tight binding affinity to lauric acid ($K_d=1.1{\pm}0.1{\mu}M$) and dominantly hydroxylated (${\omega}-1$) position of lauric acid. We determined the steady-state kinetic parameters; $k_{cat}$ was 10.8 $min^{-1}$ and $K_m$, was 12 ${\mu}M$. The increased ratio to $\omega$-hydroxylated production of lauric acid catalyzed by CYP119 was observed with increase in the reaction temperature. These studies suggested that the regioselectivity of CYP119 provide the critical clue for the physiological enzyme function in this thermophilic archaebacteria. In addition, regioselectivity control of CYP119 without altering its thermostability can lead to the development of novel CYP119-based catalysts through protein engineering.

Fabrication of catalytic combustible gas sensor for hydrocarbon gas detection (탄화수소계 가스 감지용 접촉연소식 가스센서의 제조)

  • Park, Hyo-Derk;Lee, Jae-Suk;Kim, Kun-Nyun;Park, Jong-Wan;Shin, Sang-Mo
    • Journal of Sensor Science and Technology
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    • v.3 no.3
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    • pp.9-15
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    • 1994
  • Catalytic combustible gas sensors were fabricated by using ${\gamma}-Al_{2}O_{3}$ with large surface area and noble metal catalysts. The optimum conditions for ${\gamma}-Al_{2}O_{3}$ fabrication were investigated by DT/TGA and XRD analyses and it was found that fabricated ${\gamma}-Al_{2}O_{3}$ had superior value as surface area of $215.5m^{2}/g$. Gas sensors were manufactured and tested to inflammable gases by using Pt coil as a heater and temperature sensing part, fine ${\gamma}-Al_{2}O_{3}$ powder as a bead material and Pt, Pd noble metal powder as a catalyst. From the results, fabricated sensor showed good sensitivity to LPG and LNG of 20mV/l000ppm, 6.5mV/l000ppm respectively.

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Effects of Diffusion Layer (DL) and ORR Catalyst (MORR) on the Performance of MORR/IrO2/DL Electrodes for PEM-Type Unitized Regenerative Fuel Cells

  • Choe, Seunghoe;Lee, Byung-Seok;Jang, Jong Hyun
    • Journal of Electrochemical Science and Technology
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    • v.8 no.1
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    • pp.7-14
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    • 2017
  • This study aims to examine the influences of substrates/diffusion layers (DL) and oxygen reduction reaction catalysts ($M_{ORR}$) on the performance of $M_{ORR}/IrO_2$/DL-type bifunctional oxygen electrodes for use in polymer electrolyte membrane (PEM)-type unitized regenerative fuel cells (URFC). The $M_{ORR}/IrO_2$/DL electrodes were prepared via two sequential steps: anodic electrodeposition of $IrO_2$ on various DLs and fabrication of $M_{ORR}$ layers (Pt, Pd, and Pt-Ru) by spraying on $IrO_2/DL$. Experiments using different DLs, with Pt as the $M_{ORR}$, revealed that the roughness factor of the DL mainly determined the electrode performance for both water electrolyzer (WE) and fuel cell (FC) operations, while the contributions of porosity and substrate material were insignificant. When Pt-Ru was utilized as the $M_{ORR}$ instead of Pt, WE performance was enhanced and the electrode performance was assessed by analyzing round-trip efficiencies (${\varepsilon}_{RT}$) at current densities of 0.2 and $0.4A/cm^2$. As a result, using Pt-Ru instead of Pt alone provided better ${\varepsilon}_{RT}$ at both current densities, while Pd resulted in very low ${\varepsilon}_{RT}$. Improved efficiency was related to the additional catalytic action by Ru toward ORR during WE operation.