• Transactions of the Korean hydrogen and new energy society
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• v.22 no.6
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• pp.905-912
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• 2011

In this study, the novel concept catalytic reactor was designed for water-gas shift reaction (WGS) under high pressure. The novel concept catalytic reactor was composed of an autoclave, the catalyst, and liquid water. Cu-ZnO/$Al_2O_3$ as the low temperature shift catalyst was used for WGS reaction. WGS in the novel concept catalytic reactor was carried out at the ranges of 150~$250^{\circ}C$ and 30~50 atm. The liquid water was filled at the bottom of the autoclave catalytic reactor and the catalyst of pellet type was located at the gas-liquid water interface. It was concluded that WGS reaction occurred over the surface of catalysts partially wetted with liquid water. The conversion of CO for WGS was also controlled with changing content of Cu and ZnO used as the catalytic active components. Meanwhile, the catalyst of honey comb type coated with Cu-ZnO/$Al_2O_3$ was used in order to increase the contact area between wet-surface of catalyst and the reactants of gas phase. It was confirmed from these experiments that $H_2$/CO ratio of the simulated coal gas increased from 0.5 to 0.8 by WGS at gas-liquid water interface over the wet surface of honey comb type catalyst at $250^{\circ}C$ and 50 atm.

• 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.

• Transactions of the Korean hydrogen and new energy society
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• v.32 no.6
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• pp.455-463
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• 2021

In this study, CeO₂ support is synthesized from cerium hydroxy carbonate prepared using precipitation/digestion method using KOH and K₂CO₃ as the precipitants. The Cu was impregnated to CeO₂ support with the different loading (Cu loading=10-40 wt. %). The prepared Cu/CeO₂ catalysts were applied to a single stage water gas shift (WGS) reaction. Among the prepared catalysts, the 20Cu/CeO₂ catalyst contained 20 wt.% of Cu showed the highest CO conversion (Xco=68% at 400℃). This result was mainly due to a large amount of active sites. In addition, the activity of the 20 Cu/CeO₂ catalyst was maintained without being deactivated for 100 hours because of the strong interaction between Cu and CeO₂. Therefore, it was confirmed that 20 Cu/CeO₂ is a suitable catalyst for a single WGS reaction.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.19 no.3
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• pp.112-118
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• 2018

In order to meet the strict emission regulations for internal combustion engines based on fossil fuel, the proportion of after-treatments for vehicles and vessels is gradually increasing. Diesel engines have high power, good fuel economy, and lower $CO_2$ emissions, and their market shares are increasing in commercial vehicles and passenger cars. However, NOx is generated in the localized high-temperature combustion regions, and particulate matter is formed in the zones of diffusion combustion. LNT and urea-SCR catalysts have been developed for after-treatment of the exhaust gas to reduce NOx in diesel vehicles. This study aims to improve the NOx reduction performance of Cu SCR catalyst, which is widely used in light, medium, and heavy-duty diesel engines. The de-NOx performance of $5Cu-2ZrO_2$/93Zeolyst(Si/Al=13.7) SCR catalyst was about 5-50% higher than that of $5Cu-2ZrO_2$/93Zeolite(Si/Al=2.9) at catalyst temperatures of $300^{\circ}C$ or higher. The zeolite had lower metal dispersion than zeolyst, and the reaction rate of the catalyst decreased as the average particle size increased. The $10Cu-2ZrO_2$/88Zeolyst catalyst loaded with 10wt% Cu had the highest NOx conversion rate of 40% at $200^{\circ}C$ and about 65% at $350^{\circ}C$. The ion exchange rate of Cu ions increased with that of Al, the crystalline compound of zeolite, and the de-NOx performance was improved by 20-40% compared to other catalysts.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.3
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• pp.511-521
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• 2000

Investigation was carried out lean burn de-NOx properties of Pt-$TiO_2$ bifunctional catalyst by propylene in order to get the high de-NOx activity and the wide temperature window under coexistence of $SO_2$ and $H_2O$. Only noncatalyst and carrier catalyst themselves had NOx conversion activity at high temperature over $400^{\circ}C$. NOx conversion activity of catalysts exchanged copper ion resulted in Cu-$TiO_2$>Cu-ZSM-5>Cu-$Al_2O_3$>CU-YZ>Cu-AZ. Catalysts impregnated with platinum based on titania gave the results of high NOx conversion activity at low temperature. $250^{\circ}C$. Bifunctional catalysts based on Pt-$TiO_2$ showed high NOx conversion activity both at a low zone of $300^{\circ}C$ and a high zone of $500^{\circ}C$. Pt-$TiO_2$/$Al_2O_3$ catalyst gave the highest NOx conversion activity at a low temperature zone. and Pt-$TiO_2$/$Mn_2O_3$(21) catalyst gave the highest NOx conversion activity at a high temperature zone. Under the coexistence of $SO_2$ and $H_2O$. NOx conversion activities of 0.55wt%Pt-$TiO_2$/5wt%Cu-ZSM-5 catalyst was high both at a low and high temperature zone, and increased depending on oxygen concentration. 0.55wt%Pt-$TiO_2$/5wt%Cu-ZSM-5 catalyst showed the best correlation between de-NOx activities and the propyl ere conversion rates to CO on the log function.

• Clean Technology
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• v.21 no.3
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• pp.200-206
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• 2015

In order to investigate the effect of cerium oxide addition, Cu-ZnO-CeO₂ catalysts were prepared using co-precipitation method for water gas shift (WGS) reaction. A series of Cu-ZnO-CeO₂ catalyst with fixed Cu Content (50 wt%, calculated as CuO) and a given ceria content (e.g., 0, 5, 10, 20, 30, 40 wt%, calculated as CeO₂) were tested for catalytic activity at a GHSV of 95,541 h^-1, and a temperature range of 200 to 400 ℃. Cu-ZnO-CeO₂ catalysts were characterized by using BET, SEM, XRD, H₂-TPR, and XPS analysis. Varying composition of Cu-ZnO-CeO₂ catlysts led the difference characteristics such as Cu dispersion, and binding energy. The optimum 10 wt% doping of cerium facilitated catalyst reduction at lower temperature and improved the catalyst performance greatly in terms of CO conversion. Cerium oxide added catalyst showed enhanced activities at higher temperature when it compared with the catalyst without cerium oxide. Consequently, ceria addition of optimal composition leads to enhanced catalytic activity which is attributed to enhanced Cu dispersion, lower binding energy, and hindered Cu metal agglomeration.

• Transactions of the Korean hydrogen and new energy society
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• v.30 no.2
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• pp.95-102
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• 2019

In order to investigate the effect of water treatment on activity of WGS catalyst, $Cu/ZnO/MgO/Al_2O_3$ (CZMA) catalysts were synthesized by co-precipitation method. The prepared catalysts were water-treated at two different temperature (250, $350^{\circ}C$). Synthesized catalysts were characterized by using BET, SEM, $N_2O$ chemisorption, XRD, $H_2-TPR$ and XPS analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of $180-320^{\circ}C$. The reduction temperature decreased with water treatment and CZMA_250 catalyst showed the lowest reduction temperature and retained a large amount of $Cu^+$. Water-treated catalysts showed increased reactivity compared to untreated catalyst and the CZMA_250 catalyst showed higher catalytic activity on WGS reaction.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.19 no.9
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• pp.474-481
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• 2018

The policy-making and technological development of eco-friendly automobiles designed to increase their supply is ongoing, but the internal combustion engine still accounts for approximately 95% of automobiles in use. To meet the stricter emission regulations of internal combustion engines based on fossil fuels, the proportion of after-treatments for vehicles and (ocean going) vessels is increasing continuously. As diesel engines have high power and good fuel economy in addition to less CO2 emissions, their market share is increasing not only in commercial vehicles, but also in passenger cars. Because of the characteristics of the diesel combustion, however, NOx is generated in localized high-temperature combustion regions, and particulates are formed in the zones of diffusion combustion. LNT and urea-SCR catalysts have been developed for the after-treatment of exhaust gas to reduce NOx in diesel vehicles. This study examined the effect of a containing promoter on SCR catalysts to cope with the severe exhaust gas regulation. The de-NOx performance of the Mn-SCR catalyst was the best, and the de-NOx performance was improved as the ion exchange rate between Mn ion and Zeolyst was good and the activation energy was low. The de-NOx performance of the 7Cu-15Ba/78Zeoyst catalyst was 32% at $200^{\circ}C$ and 30% at $500^{\circ}C$, and showed the highest performance. The NOx storage material of BaO loaded as a promoter was well dispersed in the Cu-SCR catalyst and the additional de-NOx performance of BaO was affected by the reduction reaction of the Cu-SCR catalyst. Among the three catalysts, the 7Cu-15Ba/Zeolyst SCR catalyst was resistant to thermal degradation. The same type of CuO due to thermal degradation migrates and agglomerates because BaO reduces the agglomeration of the main catalyst CuO particles.

• Clean Technology
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• v.26 no.4
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• pp.286-292
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• 2020

This study confirmed the effect of the Cu/CeO2-X catalyst on the CO oxidation activity at low temperature through the catalyst's structure and reaction characteristics. The catalyst was prepared by the wet impregnation method. Cu/CeO2_X catalysts were manufactured by loading Cu (active metal) using CeO2 (support) formed at different calcination temperatures (300-600 ℃). Manufactured Cu/CeO2_X catalysts were evaluated for the low-temperature activity of carbon monoxide. The Cu/CeO2_300 catalyst showed an activity of 90% at 125 ℃, but the activity gradually decreased as the calcination temperature of the CeO2-X and Cu/CeO2_600 catalysts showed an activity of 65% at 125 ℃. Raman, XRD, H2-TPR, and XPS analysis confirmed the physicochemical properties of the catalysts. Based on the XPS analysis, the lower the calcination temperature of the CeO2 was, the higher the unstable Ce3+ species (non-stoichiometric species) ratio became. The increased Ce3+ species formed a solid solution bond between Cu and CeO2-X, and it was confirmed by the change of the CeO2 peak in Raman analysis and the reduction peak of the solid solution structure in H2-TPR analysis. According to the result, the formation of the solid solution bond between Cu and Ce has been enhanced by the redox properties of the catalysts and by CO oxidation activity at low temperatures.

• Applied Chemistry for Engineering
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• v.23 no.3
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• pp.348-351
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• 2012

The effect of the addition of Cu on the catalytic activity of the $Mn/CeO_2-ZrO_2$ catalyst for the low-temperature SCR reaction of NO was investigated. Three different amounts of Cu, 5, 10, and 15 wt%, were impregnated on the $Mn/CeO_2-ZrO_2$ catalyst. The characteristics of the synthesized catalysts were examined by BET, XRD, XPS, and $H_2-TPR$ analyses. The de-NOx efficiency of the Cu-added catalysts increased with the amount of Cu. When 15 wt% Cu was impregnated, the deNOx efficiency was the highest, reaching as high as 99%. The increased deNOx efficiency is attributed to the enhanced reducing power stemming from the interaction between Mn and Cu on the catalyst surface.