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

• Korean Chemical Engineering Research
• /
• 제50권2호
• /
• pp.358-364
• /
• 2012

철 촉매를 이용한 Fischer-Tropsch 합성 반응과 수성 가스 전환 반응에 대한 반응 메커니즘과 반응 속도식을 5 채널 고정층 반응기를 이용하여 조사하였다. 실험 조건은, 반응물 합성가스 $H_2$/CO 비 0.5~2, 반응물 공급 유량 60~80 ml/min, 반응 온도 $255{\sim}275^{\circ}C$로서 반응 압력은 1.5 MPa을 유지하였다. F-T 합성 반응의 반응 속도식($r_{FT}$)은 반응 속도 결정 단계로서 분자로 흡착된 CO와 기상의 수소 분자와의 반응을 바탕으로 하는 Eley-Rideal 반응 메카니즘을 통해 계산되었고, WGS 반응의 반응 속도식($r_{WGS}$)은 formate 중간체 생성 반응을 반응 속도 결정 단계로 가정하여 결정되었다. 실험 결과, F-T 합성 반응의 반응 속도식과 WGS 반응의 반응 속도식은 각각 탄화수소 생성과 $CO_2$ 생성에 대한 반응 속도 실험값을 잘 모사하였고, 또한 power law에 근거한 CO 전환 반응에 대한 반응 속도식도 실험값과 잘 일치하였다. 이처럼, 각각의 반응 메카니즘을 바탕으로 도출된 반응 속도식($r_{FT}$, $r_{WGS}$, $-r_{CO}$)은 실험값과 여러 가지 기존 문헌에서 보고된 반응 속도식 모델과 잘 일치하였다.

• Korean Chemical Engineering Research
• /
• 제45권6호
• /
• pp.582-590
• /
• 2007

Water gas shift reaction(WGSR)이 일어나는 파이럿 규모 고온반응기에서의 거동 및 성능을 예측하기 위하여 수학적 모델을 수립하고 모사를 수행하였다. 반응기의 형상, 유체 및 열 이동에 대해 상세한 모델링이 가능한 전산유체역학 기법과 공정시스템 공학에서 사용되는 공정모사 기법을 함께 사용한 multiscale 모델링 및 모사를 수행하였으며, 그 결과를 일반 공정모사와 비교하였다. Multiscale 모사를 통해 CO의 전환율은 최고 0.85, 발열반응으로 인해 충전층의 온도는 약 720 K까지 오름을 알 수 있었다. 또한 동적모사를 통해 시간에 따른 반응기내에서의 온도분포, 전환율 분포 등의 주요한 변수 및 성능들의 시간에 따른 변화를 예측할 수 있었다. Multiscale 모사 기법은 파이럿 규모의 반응기뿐 아니라 상업규모의 공정에 대해 실제 상황을 상세히 반영하여 정확한 예측이 가능하므로, 상업공정 설계에 주요한 기술로 사용될 수 있다.

• 한국수소및신에너지학회논문집
• /
• 제24권6호
• /
• pp.543-549
• /
• 2013

In this study, $La_{0.9}Sr_{0.1}Cr_{0.7}M_{0.3}O_{3{\pm}{\delta}}$ (M=Mn, Ru, Fe, Ni) were prepared by sol-gel method and water gas shift reaction with simulated coal-derived syngas between $400{\sim}650^{\circ}C$ was conducted to evaluate the catalytic activity of prepared catalysts. Physico-chemical properties were characterized by XRD, BET, SEM-EDS and TPR. The formation of perovskite crystallite, $LaCrO_3$ was confirmed and the highest surface area was measured with $La_{0.9}Sr_{0.1}Cr_{0.7}Mn_{0.3}O_{3{\pm}{\delta}}$. Equilibrium conversion of CO above $550^{\circ}C$ was achieved except $La_{0.9}Sr_{0.1}Cr_{0.7}Fe_{0.3}O_{3{\pm}{\delta}}$. and methanation reaction was carried out as side reaction of water gas shift reaction with $La_{0.9}Sr_{0.1}Cr_{0.7}Ni_{0.3}O_{3{\pm}{\delta}}$ and $La_{0.9}Sr_{0.1}Cr_{0.7}Ru_{0.3}O_{3{\pm}{\delta}}$. Conclusively, $La_{0.9}Sr_{0.1}Cr_{0.7}M_n{0.3}O_{3{\pm}{\delta}}$ was the most suitable catalyst of water gas shift reaction above $500^{\circ}C$ for CO conversion and hydrogen production.

• 청정기술
• /
• 제28권1호
• /
• pp.1-8
• /
• 2022

미활용 저급자원인 석유코크스를 대상으로 고순도의 수소 생산을 위한 수성가스전이반응에 적용가능성을 확인하기 위하여 Cu/ZnO/MgO/Al₂O₃ (CZMA) 촉매를 공침법을 사용하여 제조하였다. 제조된 촉매는 BET, H₂-TPR을 사용하여 분석되었다. 촉매의 반응성 테스트는 고농도의 CO를 포함하는 합성가스로부터 단일 Low Temperature Shift 반응을 거치는 경우와 High Temperature Shift 반응을 거친 후 스팀의 응축 없이 즉시 LTS 반응을 거치는 두 가지의 경우를 비교 및 분석하였다. 두 조건에서 steam/CO 비, 유량 및 유속, 온도에 따른 반응특성을 확인하였다. 전환된 저농도의 CO와 스팀이 응축 없이 LTS로 즉시 주입되는 경우 많은 양의 스팀이 존재함에도 불구하고 대부분의 조건에서 다소 낮은 CO 전환율을 나타냈다. 또한 steam/CO비, 온도 및 유속에 대한 영향이 크게 나타나 최적의 조업조건을 결정하기에 추가적인 분석이 요구되었다. 반면, 고농도의 CO 기체를 포함하는 조건에서는 탄소침적 또는 촉매의 활성 저하가 나타나지 않았으며 대부분의 조건에서 높은 CO 전환율을 나타내었다. 결론적으로 Cu/ZnO/MgO/Al₂O₃ 촉매를 적용하여 고농도의 CO를 포함하는 합성가스 조성에서 적절한 조업조건을 적용시키면 단일 LTS 반응을 적용해도 고농도의 CO를 CO₂로 충분히 전환 가능함을 확인하였다.

• 한국가스학회:학술대회논문집
• /
• 한국가스학회 2005년도 추계학술발표회 논문집
• /
• pp.83-87
• /
• 2005

The kinetics of the direct synthesis of DME was studied under different conditions over a temperature range of $220\~280^{\circ}C$, syngas ratio $1.2\~ 3.0$ All experiment were carried out over hybrid catalyst, composed to a methanol synthesis catalyst (Cu/ZnO/$Al_2O_3$) and a dehydration Catalyst ($\gamma$-Al_2O_3$) The observed reaction rate qualitatively follows a Langmiur-Hinshellwood type of reaction mechanism. Such a mechanism is considered with three reaction, methanol synthesis, methanol dehydration and water gas shift reaction. From a surface reaction with dissociative adsorption of hydrogen, methanol and water, individual reaction rate was determined

• Environmental Engineering Research
• /
• 제23권3호
• /
• pp.339-344
• /
• 2018

The Cu loading of a cubic $Ce_{0.8}Zr_{0.2}O_2$-supported Cu catalyst was optimized for a single-stage water gas shift (WGS) reaction. The catalyst was prepared by a co-precipitation method, and the WGS reaction was performed at a gas hourly space velocity of $150,494h^{-1}$. The results revealed that an 80 wt% $Cu-Ce_{0.8}Zr_{0.2}O_2$ catalyst exhibits excellent catalytic performance and 100% $CO_2$ selectivity ($X_{CO}=27%$ at $240^{\circ}C$ for 100 h). The high activity of 80 wt% $Cu-Ce_{0.8}Zr_{0.2}O_2$ catalyst is attributed to the presence of abundant surface Cu atoms and the low activation energy of the resultant process.

• Biotechnology and Bioprocess Engineering:BBE
• /
• 제10권3호
• /
• pp.270-274
• /
• 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.

• 한국수소및신에너지학회논문집
• /
• 제28권1호
• /
• pp.1-8
• /
• 2017

Cu/Mn/Ce catalysts for water gas shift (WGS) reaction were synthesized by urea-nitrate combustion method with the fixed molar ratio of Cu/Mn as 1:4 and 1:1 with the doping concentration of Ce from 0.3 to 0.8 mol%. The prepared catalysts were characterized with SEM, BET, XRD, XPS, $H_2$-TPR, $CO_2$ TPD, $N_2O$ chemisorption analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of 200 to $400^{\circ}C$. The Cu/Mn(CM) catalysts formed Cu-Mn mixed oxide of spinel structure ($Cu_{1.5}Mn_{1.5}O_4$) and manganese oxides ($MnO_x$). However, when a small amount of Ce was doped, the growth of $Cu_{1.5}Mn_{1.5}O_4$ was inhibited and the degree of Cu dispersion were increased. Also, the doping of Ce on the CM catalyst reduced the reduction temperature and the base site to induce the active site of the catalyst to be exposed on the catalyst surface. From the XPS analysis, it was confirmed that maintaining the oxidation state of Cu appropriately was a main factor in the WGS reaction. Consequently, Ce as support and dopant in the water gas shift reaction catalysts exhibited the enhanced catalytic activities on CM catalysts. We found that proper amount of Ce by preparing catalysts with different Cu/Mn ratios.

• 한국가스학회:학술대회논문집
• /
• 한국가스학회 2006년도 추계학술발표회 논문집
• /
• pp.153-156
• /
• 2006