• Title/Summary/Keyword: 불균일 촉매화반응

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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.

Synthesis of Conjugated Linoleic Acid Methylester using Heterogeneous Catalysts (불균일계 촉매에 의한 공액 리놀레산 메틸에스테르의 합성)

  • Yuk, Jeong-Suk;Lee, Sang-Jun;Kim, Nam-Kyun;Kim, Young-Wun;Yoon, Byeong-Tae
    • Applied Chemistry for Engineering
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    • v.24 no.3
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    • pp.291-298
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    • 2013
  • Conjugated linoleic acid methylester was synthesized through isomerization of linoleic acid methylester by using heterogeneous catalysts. As for heterogeneous catalysts, Ni supported zeolite type catalysts were used. H zoelite Y (HY) were ion exchanged with KCl aqueous solution to synthesize K zeolite Y (KY), and with impregnation method, Ni supported zeolite catalysts were synthesized. Catalysts were used after pre-treatment by using hydrogen. HY catalysts showed a high conversion at low temperatures; but a low selectivity for conjugation reaction. KY catalysts showed a low conversion at low temperatures; but a similar conversion with HY catalysts at high temperatures while a high selectivity at low temperatures. As a result, 4 wt% Ni/KY720 recorded the high conjugation yield of 63.4% at 220.

Application of Chiral Ligands Heterogenized over Solid Supports on Enantioselective Catalysis (고체 담체에 고정화된 키랄리간드의 비대칭 촉매반응에의 응용)

  • Lee, Kwang-Yeon;Kawthekar, Rahul B.;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.17 no.6
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    • pp.565-574
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    • 2006
  • The trend towards the application of single enantiomers of chiral compounds is undoubtedly increasing. Among the various methods to obtain one single enantio-riched compound selectively, enantioselective catalysis is the most attractive method. Especially, it is important to increase the activity, selectivity and lifetime of usually expensive chiral catalysts with a minute quantity in the enantioselective synthesis. Immobilization of active homogeneous catalysts is a fashionable topic in asymmetric catalysis, providing the inherent advantage of easy separation and better handling properties. Many different ways have been investigated to improve the enantioselectivity of products and to recycle the catalysts. This review mainly focused on the present scope and limitations of different types of enantioselective heterogeneous catalysts.

Catalytic Activity of Metal-phthalocyanine Bonded on Polymer for Decomposition of Hydrogen Peroxide (고분자에 결합된 금속-프탈로시아닌의 과산화수소수 분해반응에 대한 촉매활성)

  • KimKong Soo 김공수;Yong Chul Chun;Young Woo Lee;Sang Ho Lee
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.662-668
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    • 1989
  • The decomposition reaction of hydrogen peroxide was carried out by using metal-4,4',4",4"'-tetraaminophthalocyanine [Mt-$PcNH_2$, Mt = Fe(III), Co(II)] supported on poly (styrene-co-methacrylic acid), in heterogeneous aqueous system. These catalysts showed a catalse-like activity and Fe(III)-$PcNH_2$ supported on the copolymer was particularly effective for the decomposition of hydrogen peroxide. It was found that the rate of decomposition increased smoothly in the higher pH region and catalytic reaction was interfered by adding $CN^-,\;CNS^-,\;{C_2O_4}^{-2},\;I^-$ ions. The kinetics of the catalytic reaction was also investigated and the reaction proceeds according to the Michaelis-Menten type mechanism.

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Knoevenagel Reaction in Water Catalyzed by Mesoporous Silica Materials Synthesized from Industrial Waste Coal Fly Ash (석탄회 산업폐기물로부터 제조한 메조다공성 실리카소재를 촉매로 사용하는 Knoevenagel 수용액 반응)

  • Dhokte, Aashish O.;Khillare, Santosh L.;Lande, Machhindra K.;Arbad, Balasaheb R.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.430-435
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    • 2011
  • Coal fly ash of thermal power plants converted into mesoporous materials MCM-41. The synthesized material was characterized by XRD, FT-IR, SEM, and EDS techniques. The catalytic activity of prepared material was studied for the synthesis of 5-arylindene malononitriles via Knoevenagel condensation of aromatic aldehydes and malonontrile is described. The features of present method are easy handling, stability, reusability, and eco-friendliness of catalyst, high yields, short reaction time, simple experimental and work up procedure.

Synthesis of Palladium Nanoparticles Encapsulated in Phosphine Ligand-Grafted Mesoporous Silicas and Their Application to Suzuki Cross-Coupling Reaction (팔라듐 나노입자가 담지된 메조포러스 실리카의 제조와 이를 이용한 Suzuki Cross-Coupling 반응의 적용연구)

  • Kim, Sang-Wook;Joo, Jin
    • Clean Technology
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    • v.17 no.1
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    • pp.13-18
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    • 2011
  • Phosphine ligand-grafted mesoporous silica materials with large pores were prepared for the ligand-modified heterogeneous Pd nanocatalysts. New heterogeneous catalytic system was developed using palladium nanoparticles encapsulated in phosphine ligand-grafted mesoporous silica. The catalyst showed good catalytic activities for Suzuki cross-coupling using bromobenzene derivatives due to excellent phosphine ligand effects. Catalytic results showed nanoparticie catalysts can be recycled twice with decreased yields.

Inhibition of Side Reactions Forming Dimers of Diols in the Selective Hydrogenation of Methacryl Aldehyde (메타아크릴 알데히드의 선택적 수소화에서 2가 알코올의 이합체 형성 부반응 억제효과)

  • Kook-Seung Shin;Mi-Sun Cha;Kyoung-Ku Kang;Chang-Soo Lee
    • Clean Technology
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    • v.29 no.2
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    • pp.79-86
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    • 2023
  • The homogeneous catalyst, Ru-MACHO-BH, selectively performs hydrogenation reactions only on the carbonyl group of α, β-unsaturated aldehyde compounds with extremely high reactivity and selectivity. However, the hydrogenation of α, β-unsaturated aldehydes involves a heterogeneous Diels-Alder reaction, resulting in the formation of significant amounts of byproducts, such as dimers. In this study, we used the Ru-MACHO-BH catalyst (Carbonyl hydrido (tetrahydroborato) [bis (2-diphenyl phosphino ethyl) amino] ruthenium(II)) to selectively hydrogenate the carbonyl group of a specific type of α, β-unsaturated aldehyde called methacryl aldehyde, leading to the synthesis of methallyl alcohol. Simultaneously, we applied diols to inhibit the formation of byproducts. The results demonstrate that monoethylene glycol can significantly reduce the formation of diols. Based on these results, we effectively suppressed the formation of dimers containing vinyl groups in methacryl aldehyde by using hydroquinone, which can efficiently inhibit the chemical interaction of vinyl groups. Consequently, the conversion rate of methacryl aldehyde was increased. Ultimately, by reducing the amount of the expensive homogeneous catalyst Ru-MACHO-BH to 1/10, we achieved a selectivity of over 90% and a yield of over 80% for the desired product, methallyl alcohol. These results provide a method to minimize yield reduction while reducing the usage of expensive catalysts, thereby improving cost-effectiveness. We expect that the reaction could be applied to various kinds of selective hydrogenation and has been successfully run on an industrial scale.

Kinetics in Phase Transfer Catalysis with Heterogeneous Liquid-Liquid System (액-액 불균일계에서 상이동촉매의 반응속도론 해석)

  • Park, Sang-Wook;Moon, Jin-Bok;Hwang, Kyong-Son
    • Applied Chemistry for Engineering
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    • v.5 no.2
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    • pp.230-237
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    • 1994
  • The reaction conversions of n-butyl acetate in the alkaline hydrolysis of n-butyl acetate by Aliquat 336 were measured in a flat agitator and a dispersion agitator. These measured data was used to analyze the complicated reaction mechanism of the liquid-liquid heterogeneous reaction by a phase transfer catalyst with a pseudo-first order reaction model, a interfacial reaction model and a bulk-body reaction model. The pseudo-firsts order reaction model and the interfacial reaction model could be explained by the experimental data from the dispersion agitator and the bulk-boby reaction model could be explained by those from the flat agitator and the reaction rate constants were $3.1{\times}10^{-4}$, $7.3{\times}10^{-4}$, $6.6m^3/kmol.s$ from these models at $25^{\circ}C$, respectively.

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Scale-up Study of Heterogeneous Catalysts for Biodiesel Production from Nepalese Jatropha Oil (네팔산 자트로파 오일로부터 바이오디젤 제조를 위한 불균일계 촉매 Scale-up 연구)

  • Sim, Minseok;Lee, Seunghee;Kim, Youngbin;Ku, Huiji;Woo, Jaegyu;Joshi, Rajendra;Jeon, Jong-Ki
    • Clean Technology
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    • v.27 no.2
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    • pp.198-204
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    • 2021
  • This study focused on a two-step process using heterogeneous catalysts to produce biodiesel using Nepalese jatropha oil as a raw material. As a first step, the effect of the repetitive regeneration number of Amberlyst-15 on the esterification reaction of FFA in jatropha oil was investigated. Second, the possibility of a transesterification reaction scale-up using a dolomite bead catalyst was tested. Using 120 kg of jatropha seeds from Nepal, 30 L (27 kg) of jatropha oil was obtained, and the jatropha oil yield from the seeds was about 25.0 wt%. The acid value and FFA content of jatropha oil were measured to be 11.3 mgKOH g-1 and 5.65%, respectively. As a result of the esterification reaction of jatropha oil using the Amberlyst-15 catalyst in the form of beads, the acid value of the reaction product could be lowered to 0.26 mgKOH g-1 when the fresh Amberlyst-15 catalyst was used. As the regeneration of the Amberlyst-15 catalyst is repeated, the catalyst has been deactivated, and the esterification reaction performance has deteriorated. The cause of the deactivation seems to be due to the catalyst being broken and impurities being deposited. It was confirmed that the Amberlyst-15 catalyst could be reused up to 5 times for the esterification reaction of jatropha oil. In the second step, the transesterification reaction, a dolomite catalyst, was mass-produced and used in the form of beads. By transesterifying the pretreated jatropha oil in a spinning catalyst basket reactor equipped with 90 g of dolomite bead catalyst, 89.1 wt% of biodiesel yield was obtained in 2 hours after the start of the reaction, which was similar to the transesterification of soybean oil under the same conditions.

Synthesis of Styrenated Phenol Alkoxylate from Styrenated Phenol with Ethylene Carbonate over KOH/La2O3 Catalyst (KOH/La2O3 촉매상에서 Styrenated Phenol과 Ethylene Carbonate의 반응으로부터 Styrenated Phenol Alkoxylate의 합성)

  • Lee, Seungmin;Son, Seokhwan;Jung, Sunghun;Kwak, Wonbong;Shin, Eun Ju;Ahn, Hogeun;Chung, Minchul
    • Applied Chemistry for Engineering
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    • v.29 no.1
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    • pp.62-66
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    • 2018
  • Styrenated phenol alkoxylates (SP-A) were prepared from styrenated phenol (SP) and ethylene oxide (EO) under a homogeneous base catalyst. However, to use EO that is difficult to handle, a high-pressure reaction device capable of controlling the reaction process should be used. Additionally, when a homogeneous base catalyst is used, a neutralization process is required to remove residual bases after the reaction, and it is also difficult to separate the catalyst and the product. Therefore, in this study, we report the results of SP-A prepared from the reaction of SP and EC using only heterogeneous base catalysts. The heterogeneous base catalyst was obtained by supporting KOH on $La_2O_3$ and calcintion. Using EC instead of EO, it was possible to produce SP-A under the atmospheric rather than high-pressure reaction condition. Average molecular weights of synthesized SP-A varied greatly depending on reaction conditions. The average molecular weight of SP-A prepared using the $KOH/La_2O_3$ catalyst could be controlled arbitrarily by controlling the reaction temperature and added catalyst and EC amounts.