• Bulletin of the Korean Chemical Society
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• v.13 no.1
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• pp.37-41
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• 1992

The reactions of nitrous acid with hydrogen peroxide in acidic aqueous solution in the presence of several added anions have been studied at $0^{\circ}C$ and pH 2-4 to investigate the nucleophilic catalysis of these anions. From the dependence of reaction rates on the anion concentrations, significant catalytic effects were found for $Cl^-,\;Br^-,\;SCN^-$, in order of effect $SCN^-\;{\approx}\;Br^->Cl^-$, while no observable effect was found for ${ClO_4}^-$ and ${NO_3}^-$. These results support O-nitrosation reaction is the rate-determining step and NOX formed in the presence of an anion ($X^-$) also acts as a nitrosating agent and accelerates the overall reaction rate. The order of reactivity was found to be NOCl>NOBr>NOSCN, which is consistent with the results of N-nitrosation and S-nitrosation reactions.

• Bulletin of the Korean Chemical Society
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• v.15 no.2
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• pp.126-132
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• 1994

RhCl [P($C_6H_5)_3]_3$ complexes have been incorporated in polysulfone (PS) as a dispersion medium using cosolvent (THF). The interactions between Rh(Ⅰ) complexes and polysulfone polymer molecules are examined by infrared spectroscopy and thermal analysis. The chemical reactivity of Rh in PS films has been investigated by reacting Rh sites with CO, $H_2,\;D_2,\;O_2\;NO,\;C_2H_2\;and\;C_2H_4$ in the temperature range $25-200^{\circ}C$. Various Rh-carbonyl, -hydride and -nitrosyl species formed in PS films are characterized by their infrared spectra. Rh complexes in PS film show interesting catalytic reactivities in the reactions such as hydrogenation of $C_2H_2\;and\;C_2H_4$, oxidation of CO, and reduction of NO by CO or $H_2$ gas under relatively mild conditions.

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.566-572
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• 2007

Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.

• Korean Chemical Engineering Research
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• v.43 no.4
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• pp.452-457
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• 2005

Foam-type MFI zeolite catalyst was prepared by dispersing fine ($-0.2{\mu}m$) particles of MFI zeolite on silicalite foam. Catalytic cracking of n-octane was investigated over the foam-type catalyst and Delplot method was employed to interpret product compositions for deducing reaction mechanism. The Si/Al molar ratio of dispersed MFI zeolite was estimated 25 and its dispersed amount of silicalite foam was 25 wt％. Since the apparent density of the foam type catalyst was very low $0.11g{\cdot}cm^{-3}$, the catalyst loading amount could be varied from 0.02 g to 0.5 g without concerning pressure drop, providing a wide variance in the residence time of the reactants and products. The conversion and olefin yield in the catalytic cracking of n-octane increased with the catalyst loading. The product composition was very simple and could be explained by applying the protolytic cracking mechanism when the catalyst loading was small. Higher loading of the catalyst brought about further reactions of cracked products, accumulating lower olefin and paraffin with low reactivity in product stream and resulting in complex product composition.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.8
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• pp.859-869
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• 2005

The commercial $V_2O_5-WO_3/TiO_2$ catalysts which had been exposed to the off gas from incinerator for a long time were regenerated by physical and chemical treatment. The catalytic properties and NOx conversion reactivity of those catalysts were examined by analysis equipment and NOx conversion experiment. The characterization of the catalysts were performed by XRD(x-ray diffractometer), BET, POROSIMETER, EDX(energy dispersive x-ray spectrometer), ICP(inductively coupled plasma), TGA(thermogravimetric analyzer) and SEM (scanning electron microscopy). NOx conversion experiment were performed with simulated off gas of the incinerator and $NH_3$ was used as a reductant of SCR reaction. Among the regeneration treatment methods which were applied to regenerate the aged catalysts in this study, it showed that the heat treatment method had excellent regeneration effect on the catalytic performance for NOx conversion. The catalytic performance of the regenerated catalysts with heat treatment method were recovered over than 95% of that of fresh catalyst. For the regenerated catalysts with the acid solution(pH 5) and the alkali solution(pH 12), the catalytic performance were recovered over than 90% of that of fresh catalyst. From the characterization results of the regenerated catalysts, the specific surface area was recovered in the range of $85{\sim}95%$ of that of fresh catalyst. S and Ca element, which are well known as the deactivation materials for the SCR catalysts, accumulated on the aged catalyst surface were removed up to maximum 99%. Among the P, Cr, Zn and Pb elements accumulated on the aged catalyst surface, P, Cr and Zn element were removed up to 95%. But the Pb element were removed in the range of $10{\sim}30%$ of that of fresh catalyst.

• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.1-8
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• 2005

In this study, $TiO_2$ powders were prepared by hydro-thermal synthesis with titanium tetra isopropoxide. The prepared $TiO_2$ and the commercial $TiO_2$(P-25, Degussa) were by impregnating $H_2PtCl_6$ solution or the leached solution from the waste catalytic converter of automobile. Modified photocatalysts were analyzed by ICP-AES, UV-DRS, XRD, SEM. And band-gap energy of modified photo-catalyst was found to decreased to 1.76eV and basic structure was changed upon modification by leached solution. Modified photocatalysts were coated on the wallpaper after using mixed solution with adhesive materials(PVC). And then to know the modified photo catalysts tested the reactivity and quantum efficiency in the mixed gas with NO as reactants in the photo catalytic reactor. In the gas phase, photo-catalytic activity of NO was the highest for modified P-25 catalysts(P-25(w)) that P-25(w) was impregnated by leached solution of wasted catalytic converter.

• Clean Technology
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• v.21 no.1
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• pp.53-61
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• 2015

In this study, we have investigated the kinetics on the char-CO₂ catalytic gasification reaction. Thermogravimetric analysis (TGA) experiments were carried out for char-CO₂ catalytic gasification of an Indonesian Kideco sub-bituminous. Na₂CO₃ and K₂CO₃ were selected as catalysts which were physically mixed with coal. The char-CO₂ catalytic gasification reaction showed a rapid increase of carbon conversion rate at 850 ℃, 60 vol% CO₂, and 7 wt% Na₂CO₃. At the isothermal conditions ranging from 750 ℃ to 900 ℃, the carbon conversion rates increased as the temperature increased. Four kinetic models for gas-solid reaction including the shrinking core model (SCM), random pore model (RPM), volumetric reaction model (VRM), and modified volumetric reaction model (MVRM) were applied to the experimental data against the measured kinetic data. The gasification kinetics were suitably described by the MVRM for the Kideco sub-bituminous. The activation energies for each char mixed with Na₂CO₃ and K₂CO₃ were found 55-71 kJ/mol and 69-87 kJ/mol.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1506-1510
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• 2014

A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. Dissection of $k_{obsd}$ into $k_{EtO}$- and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

• Applied Chemistry for Engineering
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• v.27 no.5
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• pp.490-494
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• 2016

This paper describes the very efficient and highly enantioselective ring opening of terminal epoxides with alkyl and arene sulfonic acid. The dinuclear chiral (salen) Co complexes bearing Lewis acids of Al, Ga and In catalyze the reaction enantioselectively in the presence of tetrabutylammonium chloride using tert-butyl methyl ether as a solvent. The variation of the anion of the tetra butyl ammonium salt has significant impact on the reactivity and selectivity of the asymmetric ring opening of phenyl glycidyl ether with p-toluenesulfonic acid. The order of reactivity and selectivity was found to be $Cl^-$ > $l^-$ > $Br^-$ > $OH^-$. Strong synergistic effects of the different Lewis acid centers of Co-Al, Co-Ga and Co-In complexes were observed in the catalytic process. The dinuclear chiral salen catalyst containing $AlCl_3$ was found to be most active and highly enantioselective (91% ee).

• Journal of Korean Society of Environmental Engineers
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• v.27 no.9
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• pp.970-977
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• 2005

The commercial $V_2O_5-WO_3/TiO_2$ catalysts which had been exposed to the off gas from incinerator for a long time were remanufactured by washing with distilled water and arid solution and reimpregnation with catalytic active components($V_2O_5-WO_3$). The catalytic properties and NOx conversion reactivity of those catalysts were examined by analysis equipment and NOx conversion experiment. Under the experimental condition used in this study, the remanufactured catalysts activated by distilled water ultra sonic cleaning, the catalytic activity was recovered in the range of $66{\sim}93%$ of that of the fresh and the maximum activity was showed when the ultra sonic cleaning time was more than 3 minutes. The remanufactured catalysts by acid solution ultra sonic cleaning, the catalytic activity was recovered in the range of $81{\sim}97%$ of that of the fresh catalyst and the maximum catalytic activity was shooed when the pH of the acid solution was 5. The remanufactured catalysts by reimpregnation with $V_2O_5$ and $WO_3$, the catalytic activity was recovered in the range of $87{\sim}100%$ of that of the fresh catalyst. Maximum catalytic activity was showed when the $V_2O_5$ was reimpregnated more than 1.0 wt %. In this case, the catalytic activity was recovered 97% of that of the fresh catalyst especially at the $150^{\circ}C$ of the experimental temperature.