• 한국수소및신에너지학회논문집
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• 제25권4호
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• pp.355-363
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• 2014

Thermal shock or overheating of WGS catalyst for SEWGS system during hydrogen pre-treatment can cause reactivity decay of the catalyst. To select appropriate pre-treatment condition, temperature profiles of catalyst bed (or outside fluidized particle bed of bed insert) during pre-treatment were measured and then CO conversions of those catalysts during WGS reaction were also measured and compared. Drastic overheating of catalyst took place when we reduce catalyst at fixed bed condition and these catalysts showed low CO conversion during WGS reaction. On the contrary, there was no overheating of catalyst at fluidized bed condition not only physical mixing case but also bed insert case. Spring type bed insert showed acceptable CO conversion even at low WGS content. Consequently, feasibility of high CO conversion without decay of reactivity of catalyst and holding the WGS catalyst inside the SEWGS reactor as tablet shape were confirmed using spring type bed insert.

• 한국수소및신에너지학회논문집
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• 제22권4호
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• pp.465-473
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• 2011

To find the optimum mixing ratio of WGS catalyst with $CO_2$ absorbent for SEWGS process, water gas shift reaction tests were carried out in a fluidized bed reactor using commercial WGS catalyst and sand (as a substitute for $CO_2$ absorbent). WGS catalyst content, gas velocity, and steam/CO ratio were considered as experimental variables. CO conversion increased as the catalyst content increased during water gas shift reaction. Variations of the CO conversion with the catalyst content were small at low gas velocity. However, those variations increased at higher gas velocity. Within experimental range of this study, the optimum operating condition(steam/CO ratio=3, gas velocity = 0.03 m/s, catalyst content=10 wt.%) to get high CO conversion and $CO_2$ capture efficiency was confirmed. Moreover, long time water gas shift reaction tests up to 20 hours were carried out for two cases (catalyst content = 10 and 20 wt.%) and we could conclude that the WGS reactivity at those conditions was maintained up to 20 hours.

• 한국수소및신에너지학회논문집
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• 제24권6호
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• pp.535-542
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• 2013

To enhance the performance of SEWGS system by holding the WGS catalyst in a SEWGS reactor using bed inserts, effect of bed insert geometry on CO conversion of WGS catalyst was measured and investigated. Small scale fluidized bed reactor was used as experimental apparatus and tablet shaped WGS catalyst and sand particle were used as bed materials. The cylinder type and the spring type bed inserts were used to hold the WGS catalysts. The CO conversion of WGS catalyst with the change of steam/CO ratio was determined based on the exit gas analysis. Moreover, gas flow direction was confirmed by bed pressure drop measurement for each case. The measured CO conversion using the bed inserts showed high value comparable to previous results even though at low catalyst content. Most of input gas flowed through the bed center side when we charged tablet type catalyst into the cylinder type bed insert and this can cause low $CO_2$ capture efficiency because the possibility of contact between input gas and $CO_2$ absorbent is low in this case. However, the spring type bed insert showed good reactivity and good distribution of gas, and therefore, the spring type bed insert was selected as the best bed insert for SEWGS process.

• 한국수소및신에너지학회논문집
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• 제22권6호
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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.

• 한국수소및신에너지학회논문집
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• 제26권2호
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• pp.96-104
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• 2015

Reactivity of commercial WGS catalyst and four new catalysts(RMC-3, PC-73, PC-67SU, PC-59) manufactured with various compositions by Korea Electric Power Research Institute(KEPCO RI) were compared to select suitable WGS catalyst for SEWGS system. Steam/CO ratio, gas velocity, flow rates of syngas, and temperature were considered as operating variables. As a result, commercial catalyst showed the highest CO conversion and RMC-3 catalyst showed also high CO conversion. Therefore, commercial and RMC-3 catalysts were selected as applicable catalysts. However, PC-73 catalyst showed low CO conversion at low temperature($200^{\circ}C$) but showed good reactivity at high temperature($225{\sim}250^{\circ}C$), and therefore, PC-73 catalyst was selected as applicable catalyst for high temperature operation. Continuous operations up to 24 hours for those three catalysts(commercial, RMC-3, PC-73) were conducted to check reactivity decay of catalysts. All three catalysts maintained their original reactivity.

• 한국수소및신에너지학회논문집
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• 제24권2호
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• pp.150-159
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• 2013

To enhance the performance of SEWGS system by holding the WGS catalyst in a SEWGS reactor using bed inserts, effects of insert geometry and shape of WGS catalysts on CO conversion were measured and investigated. Small scale fluidized bed reactor was used as experimental apparatus and WGS catalyst (particle and tablet) and sand were used as bed materials. The parallel wall type and cross type bed inserts were used to hold the WGS catalysts. The CO conversion with steam/CO ratio was determined based on the exit gas analysis. The measured CO conversion using the bed inserts showed high value comparable to physical mixing cases. Moreover, gas flow direction was confirmed by bed pressure drop measurement for each case. Most of input gas flowed through the catalyst side when we charged tablet type catalyst into the bed insert and this can cause low $CO_2$ capture efficiency because the possibility of contact between input gas and $CO_2$ absorbent is low in this case. New bed insert geometry was proposed based on the results from this study to enhance contact between input gas and WGS catalyst and $CO_2$ absorbent.

• 한국수소및신에너지학회논문집
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• 제25권2호
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• pp.122-130
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• 2014

Attrition characteristics of WGS catalysts for pre-combustion $ CO_2$ capture were investigated to check attrition loss of those catalysts, to check change of particle size distribution during attrition tests, and to determine solid circulation direction of WGS catalysts in a SEWGS system. The cumulative attrition losses of two catalysts increased with increasing time. However, attrition loss under humidified condition was lower than that under non-humidified condition case for long-term attrition tests. Between two catalysts, attrition loss of PC-29 catalyst was higher than that of commercial catalyst for long-term attrition tests. However, the commercial catalyst generated much more fines than PC-29 catalyst during attrition. Therefore, we conclude that the PC-29 catalyst is more suitable for fluidized bed operation if we take into account the separation efficiency of cyclone. Based on the results from the tests for the effect of humidity on the attrition loss, we selected solid circulation direction from SEWGS reactor to regeneration reactor because the SEWGS reactor contains more water vapor than regeneration reactor.

• 한국수소및신에너지학회논문집
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• 제25권2호
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• pp.209-217
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• 2014

To enhance the performance of SEWGS system by holding the WGS catalyst in a SEWGS reactor, a spring type bed insert was developed. In this study, effects of operating variables such as steam/CO ratio, gas velocity, syngas concentration on CO conversion were investigated in a fluidized bed reactor using the spring type bed insert to hold the WGS catalyst as tablet shape. CO conversion increased initially as the steam/CO ratio increased. But further increment of the steam/CO ratio caused decreasing of CO conversion because of increment of gas velocity and decrement of syngas concentration. Moreover, CO conversion decreased as the gas velocity increased and the syngas concentration decreased at the same steam/CO ratio. Continuous operation up to 48 hours (2 days) was carried out to check reactivity decay of WGS catalyst supported by spring type bed insert. The average CO conversion was 99.04% and we could conclude that the WGS reactivity at those conditions was maintained up to 48 hours.

• 한국수소및신에너지학회논문집
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• 제23권4호
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• pp.337-345
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• 2012

To check effects of operating variables on reaction characteristics of WGS catalyst for SEWGS process, water gas shift reaction tests were carried out in a pressurized fluidized bed reactor using commercial WGS catalyst and sand(as a substitute for $CO_2$ absorbent) as bed materials. Simulated syngas(mixed with $N_2$) was used as a reactant gas. Operating temperature was $210^{\circ}C$ and operating pressure was 20 bar. WGS catalyst content, steam/CO ratio, gas velocity, and syngas concentration were considered as experimental variables. CO conversion increased as the catalyst content and steam/CO ratio increased. CO conversion at fluidized bed condition was higher than that of fixed bed condition. However, CO conversion were maintained almost same value within the fluidized bed condition. CO conversion decreased as the syngas concentration increased. The optimum operation condition was confirmed and long time water gas shift reaction test up to 24 hours at the optimum operating conditions was carried out.

• 한국수소및신에너지학회논문집
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• 제23권2호
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• pp.111-116
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• 2012

Na promoted Pt/$CeO_2$ catalysts with various Na amounts (1, 2, and 3wt%) have been applied to water gas shift reaction (WGS) at a gas hourly space velocity (GHSV) of 45515 $h^{-1}$. 1wt%Pt-2wt%Na/$CeO_2$ catalyst exhibited the highest WGS activity at $240^{\circ}C$ among the catalysts prepared in this study. In addition, 1wt%Pt-2wt%Na/$CeO_2$ catalyst showed relatively stable activity with time on stream. The high activity/stability of 1wt%Pt-2wt%Na/$CeO_2$ catalyst was correlated to its easier reducibility and higher oxygen storage capacity (OSC). As a result, 2wt% Na promoted Pt/$CeO_2$ can be a promising candidate catalyst for the single stage WGS, which requires high intrinsic activity at very high GHSV.