• Journal of the Korean Chemical Society
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• 제38권9호
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• pp.695-700
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• 1994

Hydrogenolysis reactions of CFC-113a catalyzed by various heterogeneous catalysts $(Rh/Al_2O_3,\;Pd/C,\;Ni,\;Al_2O_3,\;Active\;carbon)$ were investigated in the liquid and gas phases. In the liquid phase reaction, different catalysts showed different activities, but all catalysts used gave high selectivities toward HCFC-123 over 95%. It was noticeable that the neutral $Al_2O_3$ showed both a high activity and a selectivity in the liquid phase reaction. In the gas phase reaction, transition metals on carbon(Pd/C, Pt/C) were so active for hydrogenolysis of CFC-113a that they even catalyzed the production reaction of overhydrogenated compounds such as $HCFC-133a(CF_3CH_2Cl)\;and\;HFC-143a(CF_3CH_3)$. $Al_2O_3$, which showed the high activity in the liquid phase reaction, did not show a remarkable activity. When $Al_2O_3$ was used in the liquid phase reaction, the hydrogenolysis of CFC-113a proceeded without any side products in THF. However, the same reaction in MeOH produced side products, such as $CH_3OCH_3\;and\;CH_3CH_2OCH_3$ from solvent. Based on this result, including heterogeneous catalysts, it was concluded that the solvent played an important role in the liquid phase reaction.

• Clean Technology
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• 제29권2호
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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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2008년도 춘계학술대회 논문집
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• pp.260-262
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• 2008

최근 고유가의 지속과 국제적인 환경 규제에 대응하기 위하여 환경친화적인 대체연료의 개발이 시급한 가운데 재생가능한 동식물성 유지로부터 생산되는 바이오 디젤에 대한 연구가 활발히 진행되고 있다. 특히 자원 재활용 및 에너지 생산관점에서 폐유지로부터 바이오디젤 원료로 사용하는 연구가 활발히 진행되어 왔다. 이러한 폐유지로부터 바이오디젤을 효율적으로 생산하기 위해서는 폐유지내 함유되어 있는 유리지방산을 전처리공정에서 산촉매에 의한 에스테르화 반응에 의해 전환제거하고자 한다. 본 연구에서는 폐유지내 함유된 유리지방산 전환제거에 효과적인 불균일계 이온교환수지 촉매를 이용하여 공정변수 즉 사용된 촉매의 양, 반응온도, 유리지방산 농도에 따른 유리지방산 전환제거특성을 조사해 보았다. 또한 각각의 반응조건에서 속도상수를 계산하여 이온교환수지 촉매를 사용한 유리지방산 전환 제거에 필요한 활성화 에너지 값을 구하였다.

• Applied Chemistry for Engineering
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• 제5권2호
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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.

• Applied Chemistry for Engineering
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• 제17권6호
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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.

• Journal of Korean Society of Environmental Engineers
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• 제27권3호
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• pp.253-261
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• 2005

Catalytic wet oxidation of ppm levels of trichloroethylene (TCE) in water has been conducted using $TiO_2$-supported cobalt oxides at a given temperature and weight hourly space velocity. 5% $CoO_x/TiO_2$ might be the most promising catalyst for the wet oxidation at $36^{\circ}C$ although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Characterization of the $CoO_x$ catalyst by acquiring XPS spectra of both fresh and used Co surfaces gave different surface spectral features of each $CoO_x$. Co $2p_{3/2}$ binding energy of Co species exposed predominantly onto the outermost surface of the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $Co_2TiO_4$ and $CoTiO_3$. The spent catalyst possessed a 780.3 eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD measurements indicated that the phase structure of Co species in 5% $CoO_x/TiO_2$ catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

• Clean Technology
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• 제24권4호
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• pp.293-300
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• 2018

Sulfamethoxazole (SMX) is sulfaamide-based synthetic antibiotics, which are widely prescribed pharmaceutical compound to treat bacterial infections in both human and animals. Most of them are not completely decomposed as refractory substances. The environmental impact of pharmaceuticals as emerging contaminants has generated severe concerns. In this study, catalytic wet peroxide oxidation (CWPO) of SMX was carried out with $Cu/Al_2O_3$ catalyst and investigated the optimum reaction conditions of temperature, dosage of catalyst and concentration of $H_2O_2$ to completely decompose the SMX. It was observed that SMX was completely decomposed within 20 min using 0.79 mM $H_2O_2$ and 6 g $Cu/Al_2O_3$ catalyst at 1 atm and $40^{\circ}C$, but SMX was not fully mineralized and converted to intermediates as hydroylated-SMX, sulfanilic acid, 4-aminobenzenesulfinic acid and nitrobenzene. After that these are completely mineralized through organic acid. We proposed the decomposition reaction path ways of SMX by analyzing the behavior of these intermediates. To investigate the durability of heterogeneous catalyst, decomposition of SMX was observed by continuously recycling catalysts. When the heterogeneous catalyst of 10 wt% $Cu/Al_2O_3$ was continuously reused 5 times, decomposition of SMX was a little lowered, but the activity of catalyst was overall very stable.

• Korean Chemical Engineering Research
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• 제46권1호
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• pp.137-141
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• 2008

Copolymerization of ethylene and ${\alpha}$-olefin using $rac-Et[Ind]_2ZrCl_2/MAO$ catalyst embedded onto polysty-rene was examined. The embedded catalyst was prepared by polymerizing a small amount of styrene with $rac-Et[Ind]_2ZrCl_2$. The catalytic activities of the embedded catalyst were higher than those of the homogeneous catalystregardless of comonomer type and the characteristic of the active sites of the embedded catalyst was not affected duringthe embedding process. Based on the DSC and NMR analyses of the produced copolymers, it was thought that theembedded catalyst had similar or slightly better comonomer incorporation ability. Furthermore, the copolymers produced by the embedded catalyst had higher bulk densities and better particle morphology than those by the homogeneous catalyst.

• Journal of the Korean Ceramic Society
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• 제33권7호
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• pp.793-801
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• 1996

The effect of catalysts which was catalyzed by acid($HNO_3$) and base ($NH_4OH$) or not on the surface microst-ructures and consequent dielectric characteristics of the $PbTiO_3$ thin films prepared by sol-gel method were investigated. The result indicated that bse catalyst promoted the phase transformation of perovskite phase while acid catalyst was found to produce most uniform surface microstructure and improved dielectric properties However degradation of properties due to secondary phase formation and non-uniform microstructure at high annealing temperature (>75$0^{\circ}C$) by rapid diffusion of lead was unavoidable in any case as long as $Si_{(100)}$ \ $SiO_2$ \Pt substrate used.

• Applied Chemistry for Engineering
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• 제29권1호
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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.