• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.111.1-111.1
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• 2010

석탄가스화복합발전(IGCC: Integrated Gasification Combined Cycle)의 고온 고압 합성가스로부터 $CO_2$를 저비용으로 포집하기 위한 연소전 포집 기술 중 유동층 촉진수성가스전환(SEWGS) 공정이 제안되어 연구개발 중에 있다. 연소전 $CO_2$ 포집을 위한 SEWGS 공정은 동일한 2탑 순환 유동층 반응기에서 고온 고압의 합성가스($H_2$, CO)를 유동층 WGS 촉매를 사용하여 CO를 $CO_2$로 전환하는 동시에 전환반응으로 생성된 $CO_2$를 흡수제를 이용하여 포집하는 기술이다. 본 연구는 $CO_2$ 회수와 WGS 반응이 동시에 이루어지는 공정에 적용 가능한 건식 재생 흡수제 및 유동층 WGS 촉매 개발을 목표로 $CO_2$ 흡수제(P Series) 및 WGS 촉매(PC Series) 조성을 제안하고 분무건조기를 이용하여 6~8kg/batch로 성형 제조하였다. 제조된 $CO_2$ 흡수제 및 촉매의 특성 평가 결과 내마모도(Attrition resistance)를 포함한 물리적 특성이 유동층 공정의 요구조건을 만족하는 결과를 얻을 수 있었다. 또한, 모사 석탄 합성가스를 이용하여 20bar, $200^{\circ}C$ 흡수/$400^{\circ}C$ 재생 조건에서 열중량 분석기(TGA) 및 가압 유동층(Fluidized-bed) 반응기를 통한 흡수제의 $CO_2$ 흡수능 평가를 수행하였다. 그 결과 내마모도(AI) 3% 이하로 기계적 강도가 우수하며, $CO_2$ 흡수능 17.6 wt%(TGA) 및 11wt%(가압 유동층)를 나타냈다. 유동층 WGS 특성 평가 결과 내마모도가 7~35%로 우수하였고, CO 전환율은 $200^{\circ}C$에서 80% 이상으로, 유동층 SEWGS 공정에 적용 가능한 특성을 확인하였다.

• Transactions of the Korean hydrogen and new energy society
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• v.22 no.4
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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.

• Clean Technology
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• v.29 no.4
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• pp.321-326
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• 2023

Recently, there has been a growing interest in clean hydrogen energy that does not emit carbon dioxide during combustion due to the increasing focus on carbon neutral. Research related to hydrogen production continues, and in this study, we applied waste-derived synthesis gas to the water-gas shift reaction to simultaneously treat waste and produce high-purity hydrogen. To enhance catalytic activity in the high-temperature water-gas shift (HT-WGS) reaction, magnesium was used as a support material alongside cerium. Cu-CeO₂-MgO catalysts were synthesized, with copper acting as the active component for the HT-WGS reaction. A study on the catalytic activity based on the preparation method was conducted, and the Cu-CeO₂-MgO catalyst prepared by impregnation method exhibited the highest activity in the HT-WGS reaction. The observed superior performance of the Cu-CeO₂-MgO catalyst prepared through the impregnation method can be attributed to its significantly higher oxygen storage capacity and amount of active Cu species.

• Transactions of the Korean hydrogen and new energy society
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• v.25 no.4
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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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.230.1-230.1
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• 2010

조촉매(Promotor)인 Na은 수성가스전이(Water Gas Shift, WGS) 반응 시 생성된 포름산염의 C-H결합을 쉽게 분해하는 역할을 한다. 본 연구에서는 $Pt/CeO_2$ 촉매의 성능 향상을 위해 Na의 담지량을 변화시켜 촉매적 활성을 비교하여 보았다. 제조된 담체는 침전법(Precipitation)을 사용하여 제조하였으며 $500^{\circ}C$에서 6시간 소성하였다. Pt 담지량은 1wt%로 고정하였고 Na 담지량은 1 wt%~5 wt%로 변화를 주어 동시(공)-함침법(Co-incipient wetness method)으로 담지 시켰다. 반응 실험은 공간속도(Gas Hourly Space Velocity, GHSV) $45,385h^{-1}$에서 수행하였다. WGS 반응 결과 3 wt%의 Na이 담지된 $Pt/CeO_2$ 촉매의 경우를 제외하고 나머지 Na이 담지된 촉매들은 비교적 높은 CO의 전환율을 나타내었다. 특히 2 wt%의 Na이 담지된 $Pt/CeO_2$ 촉매는 가장 높은 CO의 전환율을 나타내었다. 따라서 Na 담지량의 변화가 포름산염의 C-H결합 분해에 영향을 미친다는 것을 알 수 있다.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2009.11a
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• pp.213-216
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• 2009

WGS(Water Gas Shift)반응은 일산화탄소(CO)를 이산화탄소($CO_2$)로 전환하는 반응으로 일체형 수소생산시스템의 실현을 위한 고순도 수소생산에 있어서 중요한 단계이다. WGS 반응은 열역학적 평형을 고려하여 고온전이반응(HTS: High Temperature Shift)과 저온전이반응(LTS: Low Temperature Shift) 두 단계 반응으로 진행된다. 두 단계 공정의 통합을 위해 낮은 온도에서 높은 활성을 갖는 WGS 반응용 촉매 개발이 필요하다. 최근 낮은 온도에서 높은 활성을 갖는 귀금속 촉매에 다양한 담체를 적용시킨 연구가 활발히 진행되고 있다. 선행 연구 결과, Ce-$ZrO_2$ 구조는 Ce/Zr 비에 따라 다양한 특성 변화를 관찰하였다. 따라서 낮은 온도에서 높은 활성을 갖는 WGS 반응용 촉매 제조를 위해 환원성 담체인 $CeZrO_2$에 Pt 을 담지시켜 성능을 평가하였다. 제조된 모든 담체는 공침법(Co-precipitation)으로 제조 하였으며 $500^{\circ}C$에서 6시간 소성하였다. 제조된 담체에 백금(Pt)을 함침법(Incipient Wetness Impregnate)으로 담지시켰다. 특성분석은 BET를 이용하여 표면적을 측정하였다. 촉매 반응 실험조건은 $200^{\circ}C{\sim}400^{\circ}C$ 온도범위에서 기체공간속도(GHSV: Gas Hourly Space Velocity) 45,000 ml/$h{\cdot}g-cat$ 으로 혼합가스($H_2$:60%, $N_2$:20%,$CH_4$:1%,CO:9%,$CO_2$:10%)를 흘려 반응 후 배출되는 가스를 Micro-Gas Chromatography 를 이용하여 측정하였다.

• Transactions of the Korean hydrogen and new energy society
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• v.25 no.2
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.26 no.2
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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.

• Transactions of the Korean hydrogen and new energy society
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• v.24 no.6
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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.