• Bulletin of the Korean Chemical Society
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• v.23 no.11
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• pp.1513-1518
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• 2002

Kinetic studies on the water-gas shift reaction catalyzed by magnetite/chromium oxide and copper/zinc oxide were carried out by using an in situ photoacoustic spectroscopic technique. The reactions were performed in a closed-circulation reactor system using a differential photoacoustic cell at total pressure of 40 Torr in the temperature range of 100 to $350^{\circ}C.$ The CO2 photoacoustic signal varying with the concentration of CO2 during the catalytic reaction was recorded as a function of time. The time-resolved photoacoustic spectra obtained for the initial reaction stage provided precise data of CO2 formation rate. The apparent activation energies determined from the initial rates were 74.7 kJ/mol for the magnetite/chromium oxide catalyst and 50.9 kJ/mol for the copper/zinc oxide catalyst. To determine the reaction orders, partial pressures of CO(g) and H2O(g) in the reaction mixture were varied at a constant total pressure of 40 Torr with N2 buffer gas. For the magnetite/chromium oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.93 and 0.18, respectively. For the copper/zinc oxide catalyst, the reaction orders with respect to CO and H2O were determined to be 0.79 and 0, respectively.

• Korean Chemical Engineering Research
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• v.45 no.1
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• pp.12-16
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• 2007

Temperature control of an autothermal methanol reforming reactor which uses the copper-zinc oxide catalyst was studied. Temperature at 1cm below the hot-spot point in the reactor was used for the controlled variable, and the air flow rate was used for the manipulated variable. A first order plus time delay model was identified and controller parameters were obtained by applying the IMC-PI tuning rule to the identified model. With this controller, we could control the reforming reactor temperature within ${\pm}5^{\circ}C$ over 100 hours. Change of the hot-spot point due to the catalyst degradation was investigated and it could be used to design an adaptive controller.

• 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.

• Journal of the Korean Chemical Society
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• v.32 no.1
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• pp.22-29
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• 1988

The reaction of methanol-water mixture to $CO_2$ and $H_2$ on alkaline earth metal-copper-zinc oxide has been studied in the temperature range of 150 ${\sim}\;300^{\circ}C$. Generally the addition of the alkaline earth metal to Cu/ZnO resulted in an enhancement of selectivity for $CO_2$ formation and a reduction of catalytic activity. Measurable activities were found from 150$^{\circ}C$, 200$^{\circ}C$, and 250$^{\circ}C$ on Mg/Cu/ZnO, Ca/Cu/ZnO, and Ba/Cu/ZnO respectively. However, the highest selectivity for $CO_2$ formation was observed in Ba/Cu/ZnO catalyst at 250$^{\circ}C$. The effect of alkaline earth metal or ZnO on the reactivity was investigated using temperature programmed desorption of $CO_2$ or temperature programmed reduction with $H_2$ over catalysts respectively. It was found that $CO_2$ interacts more strongly in the sequence of MgO < CaO < BaO and ZnO decereases the reduction temperature of CuO. From the results, it was suggested that ZnO activates $H_2$ in the redox process of Cu component and alkaline earth metals adsorbs $CO_2$ in the catalytic process.