• Title/Summary/Keyword: zirconium catalyst.

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Zirconium(IV) Chloride - Catalysed Reaction of Indoles: An Expeditious Synthesis of Bis(indolyl)methanes

  • Nagawade, Rahul R.;Shinde, Devanand B.
    • Bulletin of the Korean Chemical Society
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    • v.26 no.12
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    • pp.1962-1964
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    • 2005
  • Zirconium(IV) chloride is found to be an efficient catalyst for the electrophilic addition reaction of indole with aldehydes/ketones to afford the corresponding bis(indolyl methanes in good yields. The remarkable features of this new procedure are high conversions, shorter reaction times, cleaner reaction profiles and simple experimental and work-up procedures.

Mild and Efficient Silylcyanation of Aldehydes Catalyzed by Zirconium Complex

  • Kim, Sung-Soo;Lee, Jun-Tae;Song, Dae-Ho;Lee, Ik-Mo;Park, Sun-Young
    • Bulletin of the Korean Chemical Society
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    • v.26 no.2
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    • pp.265-267
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    • 2005
  • An efficient method of addition of trimethylsilyl cyanide to aldehydes by employing a zirconium complex as the catalyst has been described. A variety of aromatic, aliphatic, cyclic and heterocyclic aldehydes has been converted into corresponding trimethylsilyl ethers in excellent yield within short reaction time.

Intramolecular Hydroaminations of Aminoalkynes Catalyzed by Yttrium Complexes and Aminoallenes Catalyzed by Zirconium Complexes

  • Kim, Hyun-Seok;Livinghouse, T.;SeoMoon, Dong;Lee, Phil-Ho
    • Bulletin of the Korean Chemical Society
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    • v.28 no.7
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    • pp.1127-1134
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    • 2007
  • It was demonstrated that Y[N(TMS)2]3, the neutral yttrium-diamine complex 13 and yttrium-NPS complexes 15 are efficient precatalysts for intramolecular hydroamination of aminoalkynes involving primary amines. Complex 13 and 15 were quantitatively prepared in situ by direct metalation of the ligands 4 and 9 with 1 equiv of Y[N(TMS)2]3 in benzene-d6 at 120 oC for 5 days and 10 days, respectively, via elimination of (TMS)2NH. 5-Exo- and 6-exo-dig intramolecular hydroamination of aminoalkynes using catalyst 12 and 13 proceeded smoothly to give nitrogen-contained cyclic products in good to excellent yields in all cases. In the case of 7- exo-dig intramolecular hydroamination, the desired product was produced in 41% and 48% yields despite the gem-dimethyl effect. However, treatment of catalyst 15 with aminoalkynes (19 and 22) having a methyl substituent at the carbon adjacent to triple bond and 6-exo-dig intramolecular hydroamination of 21 failed to give the desired products. Zirconium-catalyzed intramolecular hydroamination of aminoallenes (25, 27, and 31) with 5 mol% 16 afforded 2-(trans-1-propenyl)pyrrolidine, 2-isopropylenepyrrolidine, and 2-(trans-1- propenyl)piperidine in 96%, 95%, and 93% yield, respectively. However, subjecting 25 to 5 mol% 15 was unsuccessful to produce the desired product.

Preparation of Self-detoxifying Textile for Removal of Chemical Warfare Agents (군사목적의 유해화학물질 제거용 보호복 소재 제조를 위한 섬유 후가공 처리)

  • Kim, Hanil;Choi, Ik-Sung;Park, Seong-Woo;Han, Yo-han;Kim, Sung-Hun;Park, Hyun-Bae;Min, Mun-hong
    • Textile Coloration and Finishing
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    • v.31 no.1
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    • pp.33-41
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    • 2019
  • In this report, nano-sized catalysts were introduced onto fabric surface to eliminate toxic chemicals assisted by physical adsorption. For chemical removal of toxic compounds, a series of zirconium-containing catalysts were synthesized and treated on fabric to catalyze the hydrolysis and oxidation of target molecules. Antimicrobial was also introduced for the research purpose to prove the compatibility of as-synthesized catalysts with other solutions. Zirconium ligated with hydroxyl group and MOF(Metal-Organic Frameworks) were exploited as catalyst for removal of toxic compounds, while zinc complex was used for an antimicrobial to culminate in a chemical shield. Once fabrics were functionalized, fabrics were washed 2 or 5 times for a washing durability test. The amount of catalyst in textile were measured by ICP-MS and weight increasing ratio of fabrics.

A Study on the Coordination Polymerization Using C2-Symmetric Dichloro[rac-ethylenebisindenyl] zirconium(IV)/Methylaluminoxane System (C2-Symmetric Dichloro[rac-ethylenebisindenyl] zirconium(IV)/Methylaluminoxane 시스템을 이용한 배위 중합에 관한 연구)

  • Yang, Dong Jin;Kim, Hyun Ki;Park, No-Hyung;Lee, Jun Chul;Kim, Dong Hyun
    • Elastomers and Composites
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    • v.48 no.1
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    • pp.2-9
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    • 2013
  • We synthesized polyethylene, poly(ethylene-co-1-decene), poly(ethylene-co-p-methylstyrene), and poly(ethylene-ter-1-decene-ter-p-methystyrene) using a rac-$Et(Ind)_2ZrCl_2$ metallocene catalyst and a methylaluminoxane cocatalyst system. The materials were characterized using nuclear magnetic spectroscopy and fourier transform infrared spectroscopy. To identify suitable reaction conditions for terpolymerization, we studied the effects of catalyst content, cocatalyst/catalyst molar ratio, polymerization time, and polymerization temperature. As the catalyst content increased, the catalytic activity and the molecular weight of the terpolymers increased. The catalytic activity sharply increased but little change was observed after a polymerization time of 30 min. The increase in the cocatalyst/catalyst molar ratio resulted in a decrease in the molecular weight of the terpolymers and an increase in the catalytic activity to some degree. The catalytic activity increased with increasing polymerization temperature, while the molecular weight of the terpolymers decreased.

Preparation of Dinuclear, Constrained Geometry Zirconium Complexes with Polymethylene Bridges and an Investigation of Their Polymerization Behavior

  • Noh, Seok-Kyun;Jiang, Wen-Long
    • Macromolecular Research
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    • v.12 no.1
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    • pp.100-106
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    • 2004
  • We have prepared the polymethylene-bridged, dinuciear, half-sandwich constrained geometry catalysts (CGC)[Zr(η$\^$5/:η$^1$-C$\_$9/H$\_$5/SiMe$_2$NCMe$_3$)]$_2$[(CH$_2$)$\_$n/][n=6(9), n=12(10)]by treating 2 equivalents of ZrCl$_4$with the corresponding tetralithium salts of the ligands in toluene. $^1$H and $\^$13/C NMR spectra of the synthesized complexes provide firm evidence for the anticipated dinuciear structure. In $^1$H NMR spectra, two singlets representing the methyl group protons bonded at the Si atom of the CGC are present at 0.88 and 0.64 ppm, which are considerably downfield positions relative to the shifts of 0.02 and 0.05 ppm of the corresponding ligands. To investigate the catalytic behavior of the prepared dinuciear catalysts, we conducted copolymerizations of ethylene and styrene in the presence of MMAO. The prime observation is that the two dinuclear CGCs 9 and 10 are not efficient for copo-lymerization, which definitely distinguishes them from the corresponding titanium-based dinuclear CGC. These species are active catalysts, however, for ethylene homopolymerization; the activity of catalyst 10, which contains a 12-methylene bridge, is larger than that of 9 (6-methylene bridge), which indicates that the presence of the longer bridge between the two active sites contributes more effectively to facilitate the polymerization activity of the dinuciear CGC. The activities increase as the polymerization temperature increases from 40 to 70$^{\circ}C$. On the other hand, the molecular weights of the polyethylenes are reduced when the polymerization temperature is increased. We observe that dinuciear metallocenes having different-length bridges give different polymerization results, which reconfirms the significant role that the nature of the bridging ligand has in controlling the polymerization properties of dinuclear 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 $900^{\circ}C$.

Development and validation of diffusion based CFD model for modelling of hydrogen and carbon monoxide recombination in passive autocatalytic recombiner

  • Bhuvaneshwar Gera;Vishnu Verma;Jayanta Chattopadhyay
    • Nuclear Engineering and Technology
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    • v.55 no.9
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    • pp.3194-3201
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    • 2023
  • In water-cooled power reactor, hydrogen is generated in case of steam zirconium reaction during severe accident condition and later on in addition to hydrogen; CO is also generated during molten corium concrete interaction after reactor pressure vessel failure. Passive Autocatalytic Recombiners (PARs) are provided in the containment for hydrogen management. The performance of the PARs in presence of hydrogen and carbon monoxide along with air has been evaluated. Depending on the conditions, CO may either react with oxygen to form carbon dioxide (CO2) or act as catalyst poison, reducing the catalyst activity and hence the hydrogen conversion efficiency. CFD analysis has been carried out to determine the effect of CO on catalyst plate temperature for 2 & 4% v/v H2 and 1-4% v/v CO with air at the recombiner inlet for a reported experiment. The results of CFD simulations have been compared with the reported experimental data for the model validation. The reaction at the recombiner plate is modelled based on diffusion theory. The developed CFD model has been used to predict the maximum catalyst temperature and outlet species concentration for different inlet velocity and temperatures of the mixture gas. The obtained results were used to fit a correlation for obtaining removal rate of carbon monoxide inside PAR as a function of inlet velocity and concentrations.

Ethylene Polymerization Using (n-BuCp)$_{2}ZrCl_{2}$ Catalyst Activated with a Cross-linked MAO-Supported Cocatalyst

  • Yoon, Keun-Byoung
    • Macromolecular Research
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    • v.12 no.4
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    • pp.336-341
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    • 2004
  • A new type of cross-linked methylaluminoxane (MAO)-supported cocatalyst has been prepared by the reaction of a soluble MAO and a cross-liking agent such as an aromatic diamine compound. The cross-linked MAO-supported cocatalyst was used for the polymerization of ethylene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride, (n-BuCp)$_2$ZrCl$_2$. The catalyst activity of (n-BuCp)$_2$ZrCl$_2$ cocatalyzed with the new supported cocatalyst was higher than that of the commercial silica-supported MAO (SMAO) cocatalyst. The molecular weight and the bulk density of the polyethylene produced by using the new supported cocatalyst were slightly higher than those of polyethylene synthesized using commercial SMAO. The resulting polyethylene particles possess spherical morphologies with very few fine particles.

How to Eliminate CO, CO2 and CH4 in H2 & Inert Gas -Possibility of Fuel Cell Application- (수소와 불활성 가스 중 일산화탄소, 이산화탄소, 메탄 제거에 관한 연구 -연료전지에의 적용 가능성-)

  • Lee, Taek-Hong;Cheon, Young-Ki
    • Journal of Hydrogen and New Energy
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    • v.15 no.3
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    • pp.220-227
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    • 2004
  • The purpose of this paper is, based on the theoretical background of the principle of gas purification and absorption, and the absorbing ability of metals, to syudy the efficiency of gas purification of inorganic gases using Zr alloys, so as to contribute to the IT industry. To produce and distribute gas with high purity and ultra-high purity, different types of gas purifier are currently being used: distillation type, getter type, catalyst type, absorption at low-temperature type, and membrane separation equipment. From the different purification methods mentioned above, the getter type gas purifier is capable of not only high performance and capacity but also P.O.U(Point Of Use) method. The key of the getter type gas purifier is its efficiency of gas purification, which is the subject chosen for this study.