• Korean Journal of Chemical Engineering
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• v.36 no.2
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• pp.191-196
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• 2019

The phase of Cu,Zn,Al precursors strongly affects the activity of their final catalysts. Herein, the Cu,Zn,Al precursor was prepared by precipitation of $Al^{3+}$ onto primitive, amorphous Cu,Zn precipitate. This precursor turned out to be a phase mixture of zincian malachite and hydrotalcite in which the latter phase was less abundant compared to the co-precipitated precursor. The final catalyst derived from this precursor exhibited a little higher copper surface area and methanol synthesis activity than the co-precipitated counterpart. Therefore, the two precursor phases need to be mixed in an adequate proportion for the preparation of active $Cu/ZnO/Al_2O_3$ catalyst.

• Journal of Hydrogen and New Energy
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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.

• Journal of Hydrogen and New Energy
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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.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1241-1246
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• 2010

Ternary Cu/ZnO/$Al_2O_3$ catalysts were prepared by a co-precipitation method. The precursor structures were monitored during the aging. The first precipitate structure was amorphous georgeite, which transformed into the unknown crystalline structure. The transition crystalline structure was assigned to the crystalline georgeite, which was suggested with elemental analysis, IR and XRD. The final structure of precursors was malachite. The Cu surface area of the resulting Cu/ZnO/$Al_2O_3$ was maximized to be 30.6 $m^2$/g at the aging time of 36 h. The further aging rapidly decreased Cu surface areas of Cu/ZnO/$Al_2O_3$. ZnO characteristic peaks in oxide samples almost disappeared after 24 h aging, indicating that ZnO was dispersed in around bulk CuO. TOF of the prepared catalysts of the Cu surface area ranges from 13.0 to 30.6 $m^2/g_{cat}$ was to be 2.67 ${\pm}$ 0.27 mmol/$m^2$.h in methanol synthesis at the condition of $250^{\circ}C$, 50 atm and 12,000 mL/$g_{cat}$. h irrespective of the XRD and TPR patterns of CuO and ZnO structure in CuO/ZnO/$Al_2O_3$. The pH of the precipitate solution during the aging time can be maintained at 7 by $CO_2$ bubbling into the precipitate solution. Then, the decrease of Cu surface area by a long aging time can be prevented and minimize the aging time to get the highest Cu surface area.

• Journal of Hydrogen and New Energy
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• v.7 no.2
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• pp.147-155
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• 1996

The aim of this study is the development of technologies of methanol production from carbon dioxide by catalytic hydrogenation. Experiments about carbon dioxide hydrogenation by catalyst mixed with CuO, ZnO, $Cr_2O_3$ and $Al_2O_3$ were conducted to find optimum catalyst and reaction condition. Reactions were carried out at atmospheric and high pressures between 200 to $350^{\circ}C$. High yield of methanol was obtained with $Cu/ZnO/Cr_2O/Cr_2O_3/Al_2O_3$ catalyst at $250^{\circ}C$ and above 30 atmospheric pressure. There was not any increament of hydrogenation reactivity for the catalysts which was made by the addition of Pd to $Cu/ZnO/Cr_2O/Cr_2O_3/Al_2O_3$.

• Clean Technology
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• v.23 no.4
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• pp.429-434
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• 2017

To investigate the effect of magnesium oxide addition, $Cu/ZnO/MgO/Al_2O_3$ (CZMA) catalysts were prepared using co-precipitation method with fixed molar ratio of Cu/Zn/Mg/Al as 45/45/5/5 mol% for low-temperature water gas shift reaction. Synthesized catalysts were characterized by using BET, $N_2O$ chemisorption, XRD, $H_2-TPR$ and $NH_3-TPD$ analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of $200{\sim}320^{\circ}C$. At the same condition, magnesium oxide added catalyst (CZMA 400) showed that the lowest reduction temperature and stable presence of $Cu^+$, that is active species and abundant weak acid site. Also magnesium oxide added catalysts (CZMA) showed higher catalytic activity at temperature range above $240^{\circ}C$ than the catalyst without magnesium oxide (CZA). Consequently, CZMA 400 catalyst is considered to be excellent catalyst showing CO conversion of 77.59% without deactivation for about 75 hours at $240^{\circ}C$, GHSV $28,000h^{-1}$.

• Clean Technology
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• v.28 no.1
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• pp.1-8
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• 2022

To confirm the applicability of the water gas shift reaction for the production of high purity hydrogen for petroleum cokes, an unutilized low grade resource, Cu/ZnO/MgO/Al₂O₃ (CZMA), catalyst was prepared using the co-precipitation method. The prepared catalyst was analyzed using BET and H₂-TPR. Catalyst reactivity tests were compared and analyzed in two cases: a single LTS reaction from syngas containing a high concentration of CO, and an LTS reaction immediately after the syngas passed through a HTS reaction without condensation of steam. Reaction characteristics in accordance with steam/CO ratio, flow rate, and temperature were confirmed under both conditions. When the converted low concentration of CO and steam were immediately injected into the LTS, the CO conversion was rather low in most conditions despite the presence of large amounts of steam. In addition, because the influence of the steam/CO ratio, temperature, and flow rate was significant, additional analysis was required to determine the optimal operating conditions. Meanwhile, carbon deposition or activity degradation of the catalyst did not appear under high CO concentration, and high CO conversion was exhibited in most cases. In conclusion, it was confirmed that when the Cu/ZnO/MgO/Al₂O₃ catalyst and the appropriate operating conditions were applied to the syngas composition containing a high concentration of CO, the high concentration of CO could be converted in sufficient amounts into CO₂ by applying a single LTS reaction.

• Clean Technology
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• v.27 no.1
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• pp.9-16
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• 2021

Since the active matrix organic light-emitting diode (AMOLED) encapsulation process is very vulnerable to moisture and oxygen, high-purity nitrogen with minimal moisture and oxygen must be used. In this study, a copper-based catalyst used to remove oxygen from nitrogen in the AMOLED encapsulation process was optimized. Two-component and three-component catalysts composed of CuO, Al2O3, or ZnO were prepared through a co-precipitation method. The prepared catalysts were characterized by using BET, XRD, TPR, and XRF analysis. In order to verify the oxygen removal performance of the catalyst, several catalytic reactions were conducted in a fixed bed reactor, and the corresponding oxygen contents were measured through an oxygen analyzer. In addition, reusability of the catalysts was proven through repetitive regeneration. The properties and oxygen removal capacity of the catalysts prepared with CuO and Al2O3 ratios of 6 : 4, 7 : 3, and 8 : 2 were compared. The number of active sites of the catalyst with a ratio of CuO and Al2O3 of 8 : 2 was the highest among the 2-component catalysts. Moreover, the reducibility of the catalyst with a ratio of CuO and Al2O3 of 8 : 2 was the best as it had the highest CuO dispersion. As a result, the oxygen removal ability of the catalyst with a ratio of CuO and Al2O3 of 8 : 2 was the best among the 2-component catalysts. The best oxygen removal capacity was obtained when 2wt% of ZnO was added to the sub-optimized catalyst (i.e., CuO : Al2O3 = 8 : 2) probably due to its outstanding reducibility. Furthermore, the optimized catalyst kept its performance during a couple of regeneration tests.

• Journal of Hydrogen and New Energy
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• v.26 no.5
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• pp.423-430
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• 2015

$Cu/ZnO/Al_2O_3$ catalysts for water gas shift (WGS) reaction were synthesized by co-precipitation method with the fixed molar ratio of Cu/Zn/Al precursors as 45/45/10. Copper and zinc precursor were added into sodium carbonate solution for precipitation and aged for 24h. During the aging period, aluminum precursor was added into the aging solution with different time gap from the precipitation starting point: 6h, 12h, and 18h. The resulting catalysts were characterized with SEM, XRD, BET surface measurement, $N_2O$ chemisorption, TPR, and $NH_3$-TPD analysis. The catalytic activity tests were carried out at a GHSV of $27,986h^{-1}$ and a temperature range of 200 to $400^{\circ}C$. The catalyst morphology and crystalline structures were not affected by aluminum precursor addition time. The Cu dispersion degree, surface area, and pore diameter depended on the aging time of Cu-Zn precipitate without the presence of $Al_2O_3$ precursor. Also, the interaction between the active substance and $Al_2O_3$ became more stronger as aging duration, with Al precursor presented in the solution, increased. Therefore, it was confirmed that aluminum precursor addition time affected the catalytic characteristics and their catalytic activities.

• 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.