• Title/Summary/Keyword: ruthenium(Ru) catalyst

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Ruthenium Complex-catalyzed Highly Selective Co-oligomerization of Alkenes

  • Ura, Yasuyuki;Tsujita, Hiroshi;Mitsudo, Take-Aki;Kondo, Teruyuki
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2139-2152
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    • 2007
  • Ruthenium complex-catalyzed reactions often require highly qualified tuning of reaction conditions with substrates to attain high yield and selectivity of the products. In this review, our strategies for achieving characteristic ruthenium complex-catalyzed co-oligomerization of different alkenes are disclosed: 1) The codimerization of 2-norbornenes with acrylic compounds by new ruthenium catalyst systems of RuCl3(tpy)/Zn [tpy = 2,2':6',2''-terpyridine] or [RuCl2(η6-C6H6)]2/Zn in alcohols, 2) A novel synthesis of 2-alkylidenetetrahydrofurans from dihydrofurans and acrylates by zerovalent ruthenium catalysts, such as Ru(η4-cod)(η6-cot) [cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene] and Ru(η6-cot)(η2-dmfm)2 [dmfm = dimethyl fumarate], 3) Regio- and stereoselective synthesis of enamides by Ru(η6-cot)(η2-dmfm)2-catalyzed codimerization of N-vinylamides with alkenes, and 4) Unusual head-to-head dimerization of styrenes and linear codimerization of styrenes with ethylene by Ru(η6-cot)(η2-dmfm)2 catalyst in the presence of primary alcohols.

Synthesis of Ru Incorporated TiO2 and Application to Oxidation of Benzyl Alcohol with Molecular Oxygen (Ru를 도입한 TiO2의 합성과 산소를 이용한 알코올 산화반응 연구)

  • Kim, Youngyeong;Choi, Myong Yong;Kwon, Ki-Young
    • Applied Chemistry for Engineering
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    • v.25 no.6
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    • pp.645-647
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    • 2014
  • We synthesized $TiO_2$ ($Ru_x/TiO_2$) incorporating $TiO_2$ and Ru via an one-step hydrothermal method. The physical properties were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The prepared samples were applied as a catalyst for the oxidation of benzyl alcohol to benzaldehyde using molecular oxygen ($O_2$). Especially, the catalytic activities increased as the contents of ruthenium in $TiO_2$ increased without the formation of any byproducts.

Efficient Oxidative Scission of Alkenes or Alkynes with Heterogeneous Ruthenium Zirconia Catalyst (루테늄 지르코니아 불균일 촉매를 이용한 알켄 또는 알킨의 효과적인 산화절단반응)

  • Irshad, Mobina;Choi, Bong Gill;Kang, Onyu;Hong, Seok Bok;Hwang, Sung Yeon;Heo, Young Min;Kim, Jung Won
    • Applied Chemistry for Engineering
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    • v.27 no.6
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    • pp.659-663
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    • 2016
  • The efficiency of a heterogeneous ruthenium zirconia catalyst ($Ru(OH)_x/ZrO_2$) was demonstrated to the selective oxidative transformation of alkenes or alkynes. The scissions of C-C double bonds to aldehydes and triple bonds to diketones or carboxylic acids were carried out with (diacetoxyiodo)benzene as an oxidant under dichloromethane (5 mL)/water (0.5 mL) solvent system at $30^{\circ}C$ for wide range of substrates. The $Ru(OH)_x/ZrO_2$composite showed higher catalytic activity and selectivity than other ruthenium-based homogeneous or heterogeneous catalysts for the scission reaction. The catalyst exhibited a high mechanical stability, and no leaching of the metal was observed during the reaction. These features ensured the reusability of the catalyst for several times for the oxidative cleavage of unsaturated hydrocarbons.

Microwave-mediated Asymmetric Hydrogen Transfer by SBA-15-supported Ruthenium Catalyst (SBA-15 실리카에 고정화된 ruthenium 촉매를 사용한 Microwave하에서의 비대칭 수소 전달반응)

  • Jin, Myung-Jong;Jun, In-Chul
    • Korean Chemical Engineering Research
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    • v.46 no.4
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    • pp.752-755
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    • 2008
  • Mesoporous SBA-15 silica-supported TsCHDA and TsDPEN ligands have been prepared by reaction of SBA-15 silica with (1R,2R)-N-(trimethoxysilylpropyl-N-sulfonyl)-1,2-cyclohaxanediamine or (1R,2R)-N-(trimethoxysilylpropyl-N-sulfonyl)-1,2-diphenylethylenediamine-1,2-diphenylethylenediamine, respectively. The Ru complexes exhibited excellent catalytic activity and satisfactory enantioselectivity in the asymmetric hydrogen transfer of ketones under microwave conditions. The heterogeneous Ru catalyst was reusable as well as air-stable to allow easy use. Microwave-assisted efficient procedure has been developed for asymmetric hydrogen transfer.

Hydropurification of Crude Terephthalic Acid over PdRu/Carbon Composite Catalyst (PdRu/Carbon Composite 촉매를 이용한 테레프탈산의 수소화 정제)

  • Jhung, Sung-Hwa;Park, Youn-Seok
    • Journal of the Korean Chemical Society
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    • v.46 no.1
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    • pp.57-63
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    • 2002
  • The hydropurification reaction of CTA (crude terephthalic acid) was carried out with hydrogen over PdRu/CCM (carbon-carbonaceous composite material) catalyst in a batch reactor at high temperature. The first order kinetics of hydropurification is confirmed with the linear dependence of ln(4-CBA; 4-carboxybenzaldehyde) with reaction time. The reaction condition studied is thought to represent the hydropurification well because of the linear dependence of catalytic activity on the catalyst weight. The p-toluic acid (p-tol) in solid and liquid increases with the conversion of reaction or the decrease of 4-CBA. However, the benzoic acid (BA) concentration does not depend much on the conversion. The AT (alkali transmittance) does not depend on the 4-CBA when the concentration is higher than about 0.2% which shows the 4-CBA, in itself, does not cause the coloring effect. The AT of PTA depends inversely with the concentration of 4-CBA when the 4-CBA is less than about 0.15%. This may show the coloring materials are removed in parallel with the hydrogenation of 4-CBA. The (0.3%Pd-0.2%Ru)/CCM shows larger residual catalytic activity than a commercial catalyst, 0.5%Pd/C, after using in a commercial reactor even though the former has smaller fresh activity than the latter. The palladium and ruthenium in PdRu/CCM show the synergetic effect in activity when the ruthenium concentration is about $0.2{\sim}0.35$ wt%. It may be supposed that the PdRu/CCM catalyst can be a promising candidate to replace the commercial Pd/C catalyst.

The Change in Interfacial and Mechanical Properties for Glass Fiber/p-DCPD Composites with Degree of Ruthenium Catalyst Activation (루테늄촉매 활성정도에 따른 유리섬유/폴리다이사이클로펜타다이엔 복합재료의 기계 및 계면물성 변화)

  • Shin, Pyeong-Su;Kim, Jong-Hyun;Baek, Yeong-Min;Park, Ha-Seung;Kwon, Dong-Jun;Park, Joung-Man
    • Journal of Adhesion and Interface
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    • v.19 no.1
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    • pp.13-18
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    • 2018
  • At ruthenium (Ru) catalyst was exposed from the atmosphere, the degree of catalyst activation decreased. The change of catalyst activity with the number of days of exposure to air for the Ru catalyst was confirmed using the surface tension method quantitatively. Mechanical properties and surfactant change after polymerization by DCPD using Ru catalyst for each air exposure day was evaluated. The Ru catalyst mixed with a dilution agent was exposed in the air and color was monitored for each day. Surface tension was measured using Wilhelmy and PTFE and associated with different catalyst activities. Heat was measured in real time during polymerizing DCPD with Ru catalyst. After polymerization, tensile strength was measured for p-DCPD and the change of material property was measured. Interfacial properties were also evaluated via microdroplet pull-out tests between glass fiber and p-DCPD. The surface tension was stable until the 4 days (33 dyne/cm) whereas the surface energy increased at the 10 days (34 dyne/cm), which could be correlated with oxidation of the catalyst. Tensile property and interfacial shear strength (IFSS) was also stable until the 4 days (tensile strength: 38 MPa and IFSS: 26 MPa) whereas the mechanical property decrease at 10 days (tensile strength: 15 MPa and IFSS: 3 MPa) dramatically.

Tar Reforming for Biomass Gasification by Ru/$Al_2O_3$ catalyst (Ru/$Al_2O_3$ 촉매를 이용한 바이오매스 타르 개질 특성)

  • Park, Yeong-Su;Kim, Woo-Hyun;Keel, Sang-In;Yun, Jin-Han;Min, Tai-Jin;Roh, Seon-Ah
    • 한국신재생에너지학회:학술대회논문집
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    • 2008.05a
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    • pp.247-250
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    • 2008
  • Biomass gasification is a promising technology for producing a fuel gas which is useful for power generation systems. In biomass gasification processes, tar formation often causes some problems such as pipeline plugging. Thus, proper tar treatment is necessary. So far, nickel (Ni)-based catalysts have been intensively studied for the catalytic tar removal. However, the deactivation of Ni-based catalysts takes place because of coke deposition and sintering of Ni metal particles. To overcome these problems, we have been using ruthenium (Ru)-based catalyst for tar removal. It is reported by Okada et al., that a Ru/$Al_2O_3$ catalyst is very effective for preventing the carbon deposition during the steam reforming of hydrocarbons. Also, this catalyst is more active than the Ni-based catalyst at a low steam to carbon ratio (S/C). Benzene was used for the tar model compound because it is the main constituent of biomass tar and also because it represents a stable aromatic structure apparent in tar formed in biomass gasification processes. The steam reforming process transforms hydrocarbons into gaseous mixtures constituted of carbon dioxide ($CO_2$), carbon monoxide (CO), methane ($CH_4$) and hydrogen ($H_2$).

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Decomposition of Eco-friendly Liquid Propellants over Ruthenium/Al2O3/metal foam Catalysts (Ru/Al2O3/메탈폼 촉매를 이용한 친환경 액체추진제 분해)

  • Yoo, Dalsan;Jeon, Jong-Ki
    • Clean Technology
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    • v.25 no.3
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    • pp.256-262
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    • 2019
  • Hydroxylammonium nitrate (HAN)-based liquid propellants are attracting attention as environmentally friendly propellants because they are not carcinogens and the combustion gases have little toxicity. The catalyst used to decompose the HAN-based liquid propellant in a thruster must have both low temperature activity and high heat resistance. The objective of this study is to prepare an Ru/alumina/metal foam catalyst by supporting alumina slurry on the surface of NiCrAl metal foam using a washing coating method and then to support a ruthenium precursor thereon. The decomposition activity of a HAN aqueous solution of the Ru/alumina/metal foam catalyst was evaluated. The effect of the number of repetitive coatings of alumina slurry on the physical properties of the alumina/metal foam was analyzed. As the number of alumina wash coatings increased, mesopores with a diameter of about 7 nm were well-developed, thereby increasing the surface area and pore volume. It was optimal to repeat the wash coating alumina on the metal foam 12 times to maximize the surface area and pore volume of the alumina/metal foam. Mesopores were also well developed on the surface of the Ru/alumina/metal foam catalyst. It was found that the metal form itself without the active metal and alumina can promote the decomposition reaction of the HAN aqueous solution. In the case of the Ru/alumina/metal foam-550 catalyst, the decomposition onset temperature was significantly lowered compared with that of the thermal decomposition reaction, and ${\Delta}P$ could be greatly increased in the decomposition of the HAN aqueous solution. However, when the catalyst was calcined at $1,200^{\circ}C$, the catalytic activity was lowered inevitably because the surface area and pore volume of the catalyst were drastically reduced and Ru was sintered. Further research is needed to improve the heat resistance of Ru/alumina/metal foam catalysts.

Development of Monolithic Catalyst System with Co-Ru-Zr for CO2 (dry) Reforming of Methane : Enhanced Coke Tolerance

  • Kim, Hyojin;You, Young-Woo;Heo, Iljeong;Chang, Tae-Sun;Hong, Ji Sook;Lee, Ki Bong;Suh, Jeong Kwon
    • Clean Technology
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    • v.23 no.3
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    • pp.314-324
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    • 2017
  • To verify the viability of Co, Ru and Zr-based catalyst for $CO_2$ (dry) reforming reaction, catalysts were fabricated using cordierite, silicon carbide and rota monolithic substrates, and they were compared with the conventional $Co-Ru-Zr/SiO_2$ catalyst in terms of performance and durability. Cordierite monolith was showed high activity with the least amount of active component. In addition, when Cordierite monolith was coated with Co-Ru-Zr in various ways, most excellent performance was showed at a precursor solution coating method. In particular, when 0.9 wt% Co-Ru-Zr/Cordierite was used for reaction, it was observed that 95% $CO_2$ conversion was maintained for 300 h at $900^{\circ}C$.