• 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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• 제27권6호
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• pp.621-627
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• 2016

Low-priced hydrogen is required in petrochemical industry for producing low-sulfur oil, and upgrading low-grade crude oil since environmental regulations have been reinforced. Steel industry can produce hydrogen from by-product gases such as Blast Furnace Gas (BFG), Coke Oven Gas (COG), and Linze Donawitz Gas (LDG) with water gas shift (WGS) reaction by catalysis. In this study, we optimized conditions for WGS reaction with commercial catalysts by BFG and LDG. In particular, the influence on activity of gas-hourly-space-velocity, and $H_2O/CO$ ratios at different temperatures were investigated. As a result, 99.9%, and 97% CO conversion were showed with BFG, and LDG respectively under $350^{\circ}C$ High Temperature Shift (HTS), $200^{\circ}C$ Low Temperature Shift (LTS), 3.0 of $H_2O/CO$, and $1500h^{-1}$ of GHSV. Furthermore, 99.9% CO conversion lasted for 250 hours with BFG as feed gas.

• Bulletin of the Korean Chemical Society
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• 제21권12호
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• pp.1233-1238
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• 2000

$Mo/{\gamma}-Al_2O_3catalysts$ modified with Fe, Co, and Ni were prepared by impregnation method and catalytic activity for water gas shift reaction was examined. The optimum amount of Mo loaded for the reaction was 10 wt% $MoO_3$ to ${\gamma}-Al_2O_3.$ The catalytic activity of $MoO_3/{\gamma}-Al_2O_3was$ increased by modifying with Fe, Co, and Ni in the order of Co${\thickapprox}$ Ni > Fe. The optimum amounts of Co and Ni added were 3 wt% based on CoO and NiO to 10 wt% $MoO_3/{\gamma}-Al_2O_3$, restectively. The TPR (temperature-programmed reduction) analysis revealed that the addition of Co and Ni enganced the reducibility of the catalysts. The results of both catalytic activity and TPR experiments strongly suggest that the redox property of the catalyst is an important factor in water gas shift reaction on the sulfided Mo catalysts, which could be an evidence of oxy-sulfide redox mechanism.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 추계학술대회 논문집
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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.

• 한국산학기술학회논문지
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• 제17권1호
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• pp.21-27
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• 2016

온실가스로 인한 지구 온난화는 전 세계적인 주요 문제로 인식되고 있으며, 많은 나라들은 $CO_2$ 배출 감축을 위한 많은 노력을 하고 있다. 연소 후, 연소 전, 순산소 연소의 다양한 $CO_2$ 포집 기술들이 개발되고 있으며, 그 중 본 연구에서는 연소 전 $CO_2$ 포집 기술로서 수성가스전환반응기와 기체분리막의 융합 시스템을 고찰하였다. CO 전환율을 높이기 위해 고온 수성가스반응과 저온 수성가스반응이 결합된 2단 WGS 반응기를 사용하였고, 비다공성 Pd/Cu 분리막을 이용하여 수소를 선택적으로 분리하여 $CO_2$를 농축하였다. 연소 전 $CO_2$ 포집에서의 활용을 고려하여 65% CO, 30 % $H_2$, 5% $CO_2$의 기체 혼합물에 대한 하이브리드 시스템의 성능을 CO 전환율과 수소 분리의 측면에서 평가하였다. 공급기체유량 1000ml/min에서 수성가스 전환반응의 운전조건으로 온도는 $200-400^{\circ}C$, 압력은 0-20bar, S/C 비는 2.5-5의 영역에서 성능을 평가하였다. 2단 수성가스전환반응기에서 CO의 전환율은 최고 99.5%이었으며, Pd/Cu 분리막을 통하여 $CO_2$를 83%로 농축시켰다.

• 한국수소및신에너지학회논문집
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• 제28권4호
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• pp.345-351
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• 2017

Single stage water-gas shift reaction has been carried out at a gas hourly space velocity of $150,494h^{-1}$ over $Cu-Ce_{0.8}Zr_{0.2}O_2$ catalysts prepared by a co-precipitation method. Cu loading was optimized to obtain highly active co-precipitated $Cu-Ce_{0.8}Zr_{0.2}O_2$ catalysts for single stage water-gas shift reaction. 80 wt.% $Cu-Ce_{0.8}Zr_{0.2}O_2$ exhibited the excellent catalytic performance as well as 100% $CO_2$ selectivity (CO conversion = 27% at $240^{\circ}C$ for 50 h). The high activity and stability of 80 wt.% $Cu-Ce_{0.8}Zr_{0.2}O_2$ are correlated to low activation energy and large amount of surface Cu atoms.

• 청정기술
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• 제29권4호
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• pp.321-326
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• 2023

최근 탄소중립과 관련하여 연소 시 이산화탄소 배출이 없어 청정한 수소에너지에 대한 관심이 증가하고 있다. 이에 따라 수소 생산에 관련된 연구가 계속되고 있으며 본 연구에서는 폐기물을 처리함과 동시에 고순도 수소를 생산하기 위해 폐기물 유래 합성가스를 수성가스전이반응에 적용하였다. 마그네슘을 세륨과 함께 지지체로 사용하여 고온수성가스전이(HT-WGS)반응에서 촉매의 활성을 향상시키고자 하였다. HT-WGS 반응의 활성물질로 구리를 사용해 Cu-CeO₂-MgO 촉매를 제조하였으며, 제조방법에 따른 촉매활성 연구를 진행하였다. HT-WGS 반응 결과 함침법으로 제조된 Cu-CeO₂-MgO 촉매가 가장 높은 활성을 보였으며, 이는 가장 높은 산소 저장능과 많은 활성 Cu 종을 가지는 특성에 기인한 결과이다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 추계학술대회 논문집
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• pp.84-84
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• 2007

• Bulletin of the Korean Chemical Society
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• 제32권10호
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• pp.3557-3558
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• 2011