• 한국신재생에너지학회:학술대회논문집
• /
• 2009.11a
• /
• pp.199-202
• /
• 2009

본 연구에서는 내부 개질반응에서 사용되는 고함량의 니켈촉매(Ni/Al2O3계열 촉매)제조를 위해, 요소(urea)를 이용한 균일용액 침전법을 이용하여 니켈이 고분산된 52wt% Ni/$Al_2O_3$ 촉매를 제조하였다. 제조 촉매는 BET 표면적, 니켈분산도, 니켈표면적 등 물리.화학적 물성 모두 우수하였으며, 환원 패턴은 상용촉매와 비슷하게 나타났다. 실제 반응온도인 $650^{\circ}C$에서 소성하여 화학흡착을 비교한 결과,상용촉매는 니켈분산도 및 니켈표면적이 감소한 반면 균일용액 침전법으로 제조한 촉매는 거의 변화가 없었다. 개질 성능 또한 상용촉매보다 우수하였는데, 이것은 균일용액 침전법으로 제조한 촉매는 활성점(니켈)이 지지체에 나노사이즈로 고르게 잘 분산되었기 때문이라고 판단하였다. 또한 합성온도 조절을 통해, $650^{\circ}C$ 소성 후에 물성변화를 살펴보았고 합성온도 $85^{\circ}C$에서 고분산 니켈 촉매 제조가 가능하였다.

• Clean Technology
• /
• v.19 no.1
• /
• pp.51-58
• /
• 2013

In this study, kinetics data was obtained for steam reforming reaction of ethane over the nickel catalyst. The variables of steam reforming reaction were reaction temperature, partial pressure of ethane, and mole ratio of steam and ethane. Parameters for the power rate law kinetic model and the Langmuir-Hinshelwood model were obtained from the kinetic data. Also, sizing of steam reforming reactor was performed by using PRO/II simulator. For the steam reforming reaction of ethane, Langmuir-Hinshelwood model determining the reaction rate by the surface reaction was better suited than a simple power rate law kinetic model. On water-gas-shift reaction, power rate law kinetic model was well fitted to the kinetic data. Reactor size can be calculated for production of hydrogen through PRO/II simulation.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.223.2-223.2
• /
• 2010

용융탄산염 연료전지(MCFC)는 $650^{\circ}C$에서 작동하는 고온형 연료전지 시스템이다. 이 시스템은 천연가스 등을 개질하여 생산된 수소를 바로 전기로 생산할 수 있는 시스템으로 열효율이 높으며, 현재 대체 발전시스템으로 각광을 받고 있다. MCFC는 개질방식에 따라 내부개질 방식과 외부개질 방식이 있다. 내부개질 방식은 수소를 생산하는 개질기가 스택내부에 장착된 형식으로 천연가스를 스택내부에서 개질하여 바로 전기를 생산하는 방식이다. 이 내부개질반응에 사용되는 촉매로는 알루미나에 담지된 니켈(Ni) 계열촉매이 주로 쓰이고 있다. 또한 내부개질촉매의 형태는 작은 원주형의 촉매형태로 성형되어 사용된다. 이 성형된 촉매의 크기가 바로 내부개질 스택의 크기를 결정하는 중요한 요소이다. 그래서 촉매의 크기는 되도록이면 작게 성형하는 것이 중요하다. 그러나 촉매의 크기가 너무 작으면 촉매를 성형하는데 큰 어려움이 생기게 된다. 본 연구에서는 니켈 촉매를 공침법이 아닌 균일용액침전법을 이용하여 제조하였으며, 이 촉매를 이용하여 지름이 약 2 mm 이하로 촉매를 압출성형하는 방법을 연구하였다. 먼저 요소(urea)를 이용한 균일용액침전법으로 촉매를 제조하였다. 최적의 촉매 합성조건을 살펴보기 위해서, 반응 온도를 80, 85, 90, 95, $100^{\circ}C$로 변화 시키면서 제조된 촉매의 특성을 살펴보았다. 그리고 촉매의 적절한 니켈 양을 알아보기 위해서 니켈의 양을 30, 40, 50, 60, 70 wt%로 변화 시켰으며, 조촉매로 사용되는 MgO 양을 5, 10, 15, 20 wt%로 변화 시켜서 제조된 촉매의 특성을 살펴보았다. 물성을 비교하기 위해서, X-선 회절분석(XRD) 및 TPR, 물리화학흡착을 하였다. 그 결과 침전반응온도가 $80^{\circ}C$에서 촉매가 가장 좋은 물성을 보였으며, 우수한 개질성능을 보였다. 그리고 촉매 활성물질인 니켈의 함량은 50 wt% 정도가 가장 적절한 함량이었으며, MgO의 함량이 15 wt%일 때 가장 우수한 물성과 개질 성능을 보여주었다. 이 촉매들은 공침법으로 제조된 상용촉매와 비교하였을 때, 보다 우수한 물성과 개질성능 보였다. 그래서 이 촉매를 균일침전법을 이용하여 대량으로 제조한 다음 압출성형 방법을 이용하여 촉매를 원주형으로 제조하였다. 먼저 제조된 촉매는 별도의 분쇄작업(볼밀 혹은 제트밀)을 거치지 않아도 입자사이즈가 약 $4{\mu}m$ 수준이 나오도록 촉매 제조조건을 조절 하였다. 그리고 소량의 Methyl cellulose(MC) 바이더와 물만 사용하여 촉매를 혼합한 다음 스크류 압출기를 이용하여 촉매를 성형하였다. 이 촉매는 지름이 약 2 mm 이하로 제조할 수 있었으며, 기계적 강도는 타정기로 성형한 상용촉매보다 우수하였다. 그리고 촉매 성능 또한 상용촉매와 비교하였을 때, 우수한 성능 보였다. MCFC용 내부개질 촉매로 균일용액침전법을 사용한 촉매가 적합하다고 판단되며, 압출성형에도 적합하다고 판단되었다.

• 한국신재생에너지학회:학술대회논문집
• /
• 2007.11a
• /
• pp.63-66
• /
• 2007

Reformers which produce hydrogen from natural gas are essential for the operation of residential PEM fuel cells. For this purpose, steam-methane reforming reactions with Ni catalysts is primarily utilized. Commercial Ni catalysts are generally made to have porous pellet shapes in which Ni catalyst particles are uniformly dispersed over Alumina support structures. This study numerically investigates the reduction of catalyst effectiveness due to the mass transport resistances posed by porous structures of spherical catalyst pellets. The multi-component diffusion through porous media and the accurate kinetics of reforming reaction is fully considered in the numerical model. The preliminary results on the variation of the effectiveness factor according to different operation conditions are presented, which is planned to be used to develop correlations in future studies.

• Korean Chemical Engineering Research
• /
• v.50 no.5
• /
• pp.908-912
• /
• 2012

Lauan sawdust was gasified by steam reforming for hydrogen production from biomass waste. The fixed bed gasification reactor with 1m height and 10.2 cm diameter was utilized for the analysis of temperature and catalysts effect. Steam was injected to the gasification reactor for the steam reforming effect. Lauan sawdust was mixed with potassium carbonate, sodium carbonate, calcium carbonate, sodium carbonate + potassium carbonate and magnesium carbonate + calcium carbonate catalysts of constant mass fraction of 8:2 which was injected to the fixed gasification equipment. The compositions of production gas of gasification reaction were analyzed at the temperature range from $400^{\circ}C$ to $700^{\circ}C$. Fractions of hydrogen, methane and carbon monoxide gas in the production gas increased when catalysts were used. Fractions of hydrogen, methane and carbon monoxide gas were increased with increasing temperature. The highest hydrogen yield was obtained with sodium carbonate catalyst.

• Clean Technology
• /
• v.15 no.2
• /
• pp.130-136
• /
• 2009

Commercial catalyst (Cu-Zn/$Al_2O_3$, Johnson Matthey Co., 83-3 Catalyst) was applied to the hydrogen production by steam reforming of methanol in the micro-channel reactor (MCR). The steam reforming of methanol was tested over Cu-Zn catalyst at temperatures in the range of 200 and 300$^{\circ}C$, the catalyst size of 0.05${\sim}$2.2 mm, the space velocity of 3,000${\sim}$10,000 $hr^{-1}$ in a fixed bed continuous flow reactor. The conversion of methanol and the yield $H_2$ preferred high temperatures and low space velocities, and had optimal results with the particle size of 0.35 mm. Based on the results from experiments with fixed bed reactor, two types of MCR, boat bed and stacked bed MCRs, were studied. The stacked bed type MCR showed better methanol conversion compared with the boat type one.

• 한국전기화학회:학술대회논문집
• /
• 2001.06a
• /
• pp.161-166
• /
• 2001

• Applied Chemistry for Engineering
• /
• v.10 no.5
• /
• pp.652-659
• /
• 1999

The trend of poisoning of reforming catalyst along with the position of anodic catalyst bed was studied. Keeping the conditions that steam to carbon ratio was 2.5, operating voltage was 0.75 V, current density was $140mA/cm^2$, the unit cell was operated during 24 hrs at a steady state. And then the cell was stopped, the catalysts packed in the position of inlet, middle and outlet were sampled individually and then the amount of carbon, Li and K poisoned were analysed. After 100 hrs operated, the catalysts at the same positions were analysed at the same manner. The result of this experiment was as followings. After 24 hrs operated, the poisoning amounts of Li and K in the catalyst were 0.27 wt% at inlet, 0.23 wt% at middle and the highest value 1.59 wt% at outlet. After 100 hrs, the amount of poisoning is the highest in the catalyst packed at the inlet of unit cell. The performance simulation of unit cell explained these trends of poisoning catalysts. The simulation told that the catalyst in the region of the inlet of unit cell treated the 90% of initial methane flow rate and the highest electrochemical reaction happened in this region. So the catalysts of this region were the most poisoned with carbon, Li and K and also the rate of poisoning is faster than that of the catalyst at other regions. The temperature at the region of outlet of unit cell was $30^{\circ}C$ higher than that of other regions, so more Li, and K vaporized than at other regions and little reforming reaction at this region made the catalysts poisoning rate low.

• Korean Chemical Engineering Research
• /
• v.62 no.1
• /
• pp.125-131
• /
• 2024

In this study, synthesized Ni/Ce_xZr_1-xO₂ catalysts were coated on the surface of honeycomb metalic monoliths to investigate catalytic activity in steam reforming of methane reactions. Supports with varying Ce/Zr ratios were synthesized to observe their behavior in the reforming reaction, and catalysts with Ni contents ranging from 5 wt% to 20 wt% were prepared to analyze the effect of Ni loading contents on catalytic activity. The catalysts were characterized by XRD, BET, TPR, and SEM. The TPR analysis indicated the formation of Ni-Ce-Zr oxide with a strong interaction between the active metal Ni and CeO₂-ZrO₂ support. The 15 wt% Ni/Ce_0.80Zr_0.20O₂ catalyst exhibited the highest activity and stability in the steam reforming of methane reaction. Catalysts with enhanced activity and stability were synthesized by manufacturing composite materials using excellent oxygen storage and donor properties of CeO₂ and the thermal properties of ZrO₂.

• 한국전산유체공학회:학술대회논문집
• /
• 2010.05a
• /
• pp.228-232
• /
• 2010

In this paper, various operating parameters of stream reforming process from methane in preconverter for MCFC is studied by numerical method. Commercial code is used to simulated the porous catalyst with user subroutine to model three dominant chemical reactions which are Stream Reforming(SR), Water-Gas Shift(WGS), and Direct Stram Reforming(DSR). The hydrogen production is tested with different wall temperature, Gas Hourly Space Velocity(GHSV), and different reactor shapes.