• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.229.2-229.2
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• 2010

한 단계 수성가스전이반응(Single stage water gas shift reaction)을 위해 높은 산소저장능(OSC: Oxygen Storage Capacity)을 가진 $CeO_2$를 담체로 사용하여 $Pt/CeO_2$ 촉매를 설계하였다. 촉매의 제조 조건은 촉매 활성과 매우 밀접한 관계가 있다. 따라서 $Pt/CeO_2$ 촉매에 제조변수를 다양하게 변화하여 성능을 평가하였다. 촉매 반응 실험은 공간속도(GHSV: Gas Hourly Space Velocity) $45,515h^{-1}$에서 수행하였다. 본 연구에서는 $Pt/CeO_2$ 촉매를 최적화하기 위해 촉매 제조 조건 중 소성온도, 배치 당 제조질량, 전구체 그리고 pH 와 같은 다양한 제조 조건으로 촉매의 성능을 평가하였다.

• 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.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.840-843
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• 2009

폐자동차의 최종처분 과정에서 발생하는 자동차 파쇄 폐기물(Automobile Shredder Dust)은 대부분이 고분자 화합물로 높은 발열량을 가지고 있다. 또한 할로겐족 원소가 포함된 난연성 고분자류가 많아 다이옥신의 생성 우려가 높은 고분자류와 다이옥신 생성의 촉매 역할을 할 수 있는 금속성분이 많이 함유되어 있어 가스화용융시스템에 적용하여 처리하기에 매우 적합한 폐기물이다. 본 연구에서는 ASR의 가스화 용융 시설에서 고농도 CO를 함유한 합성가스를 수성가스전환반응(Water Gas Shift reaction, WGS)을 이용하여 수소의 수율을 높이는 기술을 제시하였다. 가스화 용융 설비에서 배출되는 합성가스 조성을 기준으로 적합한 고정층 WGS 반응기를 설계하고, 고온 촉매(KATALCO 71-5M)와 저온 촉매(KATALCO 83-3X)를 사용하여 실험하였다. 수성가스 반응 후의 가스 조성은 온도가 상승할수록 일산화탄소가 줄어들고 이에 따라 수소와 이산화탄소 발생량이 증가 되어 고온 촉매를 사용했을 경우 일산화탄소 전환율 ($1-CO_{out}/CO_{in}$)은 55.6에서 95.8%까지 상승하였다. 동일한 온도조건에서는 촉매에 관계없이 $CO/H_2$가 감소할수록 전환율도 감소하는 경향을 보였지만 동일한 합성가스 조성에서 일산화탄소 전환율을 비교하면 저온 촉매가 고온 촉매보다 매우 우수함을 알 수 있었다.

• 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.

• Journal of Hydrogen and New Energy
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• v.23 no.2
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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.

• Journal of Hydrogen and New Energy
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• v.24 no.1
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• pp.12-19
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• 2013

A gasification process with pre-combustion $CO_2$ capture process, which converts coal into environment-friendly synthetic gas, might be promising option for sustainable energy conversion. In the coal gasification for power generation, coal is converted into $H_2$, CO and $CO_2$. To reduce the cost of $CO_2$ capture and to maximize hydrogen production, the removal of CO and the additional production of hydrogen might be needed. In this study, a 2l/min water gas shift system for a coal gasifier has been studied. To control the concentration of major components such as $H_2$, CO, and $CO_2$, MFCs were used in experimental apparatus. The gas concentration in these experiments was equal with syngas concentration from dry coal gasifiers ($H_2$: 25-35, CO: 60-65, $CO_2$: 5-15 vol%). The operation conditions of the WGS system were $200-400^{\circ}C$, 1-10bar. Steam/Carbon ratios were between 2.0 and 5.0. The commercial catalysts were used in the high temperature shift reactor and the low temperature shift reactor. As steam/carbon ratio increased, the conversion (1-$CO_{out}/CO_{in}$) increased from 93% to 97% at the condition of CO: 65, $H_2$: 30, $CO_2$: 5%. However the conversion decreased with increasing of gas flow and temperature. The gas concentration from LTS was $H_2$: 54.7-60.0, $CO_2$: 38.8-44.9, CO: 0.3-1%.

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.111-114
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• 2010

In the attrition reactor for the American Society for Testing and Materials (ASTM) D5757-95, the attrition characteristics of catalysts for water gas shift reaction were investigated. The effects of attrition characteristics of low temperature shift catalysts (LTS) and high temperature shift catalysts (HTS) on fluidization phenomena and average particle size were investigated and compared with the attrition characteristics of sand particles. The particle size of catalysts was decreased and particle size distribution in attrition tube was changed due to the effect of gas injection. About 40~50 wt% samples of original catalyst particles were entrained and lost. The amount of fly ash of LTS catalyst was less than that of HTS. Also, the weight of entrained particles which had original particle size of $212{\sim}300{\mu}m$ was lower than any other cases.

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.582-590
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• 2007

In view of the analysis of the phenomena and the prediction of the performance, mathematical modelling and simulation of a high temperature pilot reactor for water gas shift reaction (WGSR) has been carried out. Multiscale simulation incorporated computational fluid dynamics (CFD) technique, which has the capability to deal with the reactor shape, fluid and energy transport with extensive degree of accuracy, and process modeling technique, which, in turn is responsible for reaction kinetics and mass transport. This research employed multiscale simulation and the results were compared with those from process simulation. From multiscale simulation, the maximum conversion of was predicted approximately 0.85 and the maximum temperature at the reactor was calculated 720 K, resulting from the heat of reaction. Dynamic simulation was also performed for the time transient profile of temperature, conversion, etc. Considering the results, it is concluded that multiscale simulation is a safe and accurate technique to predict reactor behaviors, and consequently will be available for the design of commercial size chemical reactors as well as other commercial unit operations.

• Biotechnology and Bioprocess Engineering:BBE
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• v.10 no.3
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• pp.270-274
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• 2005

A reactor-scale hydrogen (H2) production via the water-gas shift reaction of carbon monoxide (CO) and water was studied using the purple nonsulfur bacterium, Rhodopseudomonas palustris P4. The experiment was conducted in a two-step process: an aerobic/chemoheterotrophic cell growth step and a subsequent anaerobic $H_2$ production step. Important parameters investigated included the agitation speed. inlet CO concentration and gas retention time. P4 showed a stable $H_2$ production capability with a maximum activity of 41 mmol $H_2$ g $cell^{-1}h^{-1}$ during the continuous reactor operation of 400 h. The maximal volumetric H2 production rate was estimated to be 41 mmol $H_2 L^{-1}h^{-1}$, which was about nine-fold and fifteen-fold higher than the rates reported for the photosynthetic bacteria Rhodospirillum rubrum and Rubrivivax gelatinosus, respectively. This is mainly attributed to the ability of P4 to grow to a high cell density with a high specific $H_2$ production activity. This study indicates that P4 has an outstanding potential for a continuous H2 production via the water-gas shift reaction once a proper bioreactor system that provides a high rate of gas-liquid mass transfer is developed.

• Korean Chemical Engineering Research
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• v.50 no.2
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• pp.358-364
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• 2012

The kinetics of the Fischer-Tropsch synthesis and water gas shift reactions over a precipitated iron catalyst were studied in a 5 channel fixed-bed reactor. Experimental conditions were changed as follows: synthesis gas $H_2$/CO feed ratios of 0.5~2, reactants flow rate of 60~80 ml/min, and reaction temperature of $255{\sim}275^{\circ}C$ at a constant pressure of 1.5 MPa. The reaction rate of Fischer-Tropsch synthesis was calculated from Eley-Rideal mechanism in which the rate-determining step was the formation of the monomer species (methylene) by hydrogenation of associatively adsorbed CO. Whereas water gas shift reaction rate was determined by the formation of a formate intermediate species as the rate-determining step. As a result, the reaction rates of Fischer-Tropsch synthesis for the hydrocarbon formation and water gas shift for the $CO_2$ production were in good agreement with the experimental values, respectively. Therefore, the reaction rates ($r_{FT}$, $r_{WGS}$, $-r_{CO}$) derived from the reaction mechanisms showed good agreement both with experimental values and with some kinetic models from literature.