• Korean Chemical Engineering Research
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• v.56 no.6
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• pp.914-920
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• 2018

The intrinsic kinetic parameters of steam-methane reforming reactions over commercial nickel-based catalyst were determined. The reaction rate equations were derived from the reaction mechanism-based Langmuir-Hinshelwood chemisorption theory. As the experimental variables for the kinetic study, the reaction temperature ranged from 630 to $750^{\circ}C$ and the steam-to-carbon ratio also varied from 2.7 to 3.5. Based on the experimental data, the efficient optimization algorithm was used to determine the intrinsic kinetic parameters due to the high-dimensional objective function. It is confirmed that the parameter estimation results showed good agreement with the experimental values. Thus, this proposed mathematical reaction model can be used as the basic information to design a catalytic reactor and to optimize operating conditions.

• Journal of the Korean Institute of Gas
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• v.27 no.1
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• pp.78-85
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• 2023

Fixed-bed reactor Computational Fluid Dynamics (CFD) simulation of methanol steam reforming reaction was performed using the intrinsic kinetic data of the copper-impregnated hydrotalcite catalyst. The activation energy of the copper hydrotalcite catalyst obtained from the previous study results was 97.4 kJ/mol, and the pre-exponential was 5.904 × 10¹⁰. Process simulation was performed using the calculated values and showed a similar tendency to the experimental results. And the conversion rate according to the change of the reaction temperature (200 - 450 ℃) and the molar ratio of methanol and water was observed using the intrinsic kinetic data. In addition, mass and heat transfer phenomena analysis of a commercial reactor (I.D. 0.05 - 0.1m, Length 1m) was predicted through axial 2D Symmetry simulation using the power law model of the above kinetic constants.

• 한국신재생에너지학회:학술대회논문집
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• 2005.06a
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• pp.303-305
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• 2005

현재 인류가 직면하고 있는 에너지 및 환경 문제를 해결할 수 있는 최선의 대안으로서 수소 에너지 및 연료전지 기술에 대한 연구가 활발히 진행 중이다. 본 연구에서는 디메틸 에테르를 이용한 수소 생산 기술에 대한 연구를 수행하였다 디메틸 에테르(BATE)는 안정한 화합물로서 비 활성적이고 부식성이 없으며 발암성 및 마취성이 얼어 인체에 무해한 청청 연료로서 각광을 받고 있으며 특히 기존의 LPG 인프라를 그대로 사용할 수 있는 장점 등으로 수소 스테이션 및 소형 연료전지용 수소 발생기 등에의 적용을 위한 연구가 활발히 진행 중이다. 본 연구에서는 이러한 응용을 위한 수소 발생기용 DME 개질 반응기의 개발을 위하여 본 반응에 대한 촉매 종류의 영향, 공간속도의 최적화, 반응 메카니즘에 따른 촉매 선정, 반응온도 등의 다양한 반웅 조건에 대한 영향을 확인하고 실제 소형 연료전지를 위한 수소공급 장치로서 적용코자 마이크로채널 반응기에 적용하여 마이크로채널 DME 개질반응기의 컴팩트한 수소공급 장치로서의 적용 가능성을 평가하였다.

• Applied Chemistry for Engineering
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• v.9 no.7
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• pp.1070-1078
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• 1998

Thermodynamic analysis on carbon dioxide reforming of methane was performed using a computer program which can handle condensed species in the products, and the reforming experiments were conducted over $Al_2O_3$, $La_2O_3$, ZSM-5, MCM-41, KIT-1 supported nickel catalysts, and a commercial ICI 46-1. It was estabished that a system which consists of $CH_4$, $CO_2$, CO, $H_2$, $H_2O$, and C is appropriate for theoretical equilibrium calculations and addition of water vapor or oxygen was found to diminish the contribution of carbon dioxide in reforming. Silicate molecular sieve-supported catalysts such as Ni/ZSM-5, Ni/MCM-41, Ni/KIT-1 were effective for high $CH_4$ and $CO_2$ conversions as well as for high CO yield. Coke formation was suppressed when CaO was added as a promoter. Ni/Ca/KIT-1 which contains 10% Ni with 3% Ca showed conversion approaching equilibrium levels above $650^{\circ}C$ and maintained constant activity over 20 h. Despite increased space velocity, relatively high conversion and CO yield were observed.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.36 no.3
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• pp.343-350
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• 2012

A planar solid oxide fuel cell (PSOFC) is studied in its application in a high-temperature stationary power plant. Even though PSOFCs with external reformers are designed for application from the distributed power source to the central power plant, such PSOFCs may sacrifice more system efficiency than internally reformed SOFCs. In this study, modeling of the PSOFC with an external reformer was developed to analyze the feasibility of thermal energy utilization for the external reformer. The PSOFC system model includes the stack, reformer, burner, heat exchanger, blower, pump, PID controller, 3-way valve, reactor, mixer, and steam separator. The model was developed under the Matlab/Simulink environment with Thermolib$^{(R)}$ modules. The model was used to study the system performance according to its configuration. Three configurations of the SOFC system were selected for the comparison of the system performance. The system configuration considered the cathode recirculation, thermal sources for the external reformer, heat-up of operating gases, and condensate anode off-gas for the enhancement of the fuel concentration. The simulation results show that the magnitude of the electric efficiency of the PSOFC system for Case 2 is 12.13% higher than that for Case 1 (reference case), and the thermal efficiency of the PSOFC system for Case 3 is 76.12%, which is the highest of all the cases investigated.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.231-231
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• 2010

아직까지 국내에서 사용하는 대부분의 에너지는 화석연료에 의존하고 있다. 지하자원에서 나오는 석탄, 석유와 같은 화석연료는 다른 에너지원에 비해 운송이 간편하고 쉽게 이용할 수 있는 장점이 있지만, 환경오염의 문제성과 오일가상승, 자원의양 및 저장장소가 한정되어 있다는 단점을 가지고 있다. 이에 따라 수소와 같은 대체에너지를 이용하여 환경오염을 예방하고 무한히 사용할 수 있는 에너지원을 개발하기 위한 대체 방안들이 연구되고 있다. 폐기물 가스화시 발생되는 합성가스(CO, $CO_2$, $CH_4$, $H_2$) 내 일차로 생성된 일산화탄소는 수증기와 반응함으로써 이산화탄소로 전환이 가능하다. 잔류 메탄은 이산화탄소를 이용하여 개질함으로써 합성가스내 수소농도를 높일 수 있다. 전환된 잔류가스(CO, $CO_2$, $H_2$)내 일산화탄소는 산소를 이용하여 이산화탄소로 산화시킬 수 있으며, 산화된 이산화탄소는 흡착제를 이용하여 제거가 가능하다. 본 연구에서는 실제 가스화시 발생되는 합성가스를 이용하기 위하여, RPF가스화시 발생되는 합성가스를 직접 포집하여 실험을 진행하였다. 합성가스내 소량의 메탄은 니켈촉매를 이용하여 수소로 전화시켰으며, 잔류하는 일산화탄소는 백금촉매, 이산화탄소는 탄산나트륨 흡착제를 이용하여 연속적으로 제거함으로써 순수한 수소를 제공하였다.

• Applied Chemistry for Engineering
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• v.17 no.1
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• pp.87-92
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• 2006

The steam reforming of methane over Ru-promoted $Ni/Al_2O_3$ was carried out. Compared with $Ni/Al_2O_3$, which needs pre-reduction by $H_2$, $Ru/Ni/Al_2O_3$ catalysts exhibited relatively higher activity than conventional $Ni/Al_2O_3$. According to $H_2-TPR$ of reduced or used catalysts and $CH_4-TPR$, it was revealed that the reduction of $RuO_x$ by $CH_4$ decomposition begins at a lower temperature ($220^{\circ}C$) and the reduced Ru facilitates the reduction of NiO, and leads to self-activation. To improve metal dispersion, the catalyst was soaked in 7 M aqueous $NH_4OH$ for 2 h at $45^{\circ}C$ while stirring. As a result, $Ru/Ni/Al_2O_3$ catalysts with aqueous $NH_4OH$ treatment have higher activity, larger metal surface area (by $H_2$-chemisorption), and small particle size (by XRD and XPS). It is noted that the amount of noble metal could be reduced by aqueous $NH_4OH$ treatment.

• Clean Technology
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• v.21 no.1
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• pp.68-75
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• 2015

In this study, we investigated the structure and properties of a highly heat conductive metal-ceramic core-shell CoAl₂O₄@Al micro-composite for heterogeneous catalysts support. The CoAl₂O₄@Al was prepared by hydrothermal surface oxidation of Al metal powder, which resulted in the structure with a high heat conductive Al metal core encapsulated by a high surface area CoAl₂O₄ shell. For comparison, CoAl₂O₄ was also prepared by co-precipitation method and also utilized for a catalyst support. Rh catalysts supported on CoAl₂O₄@Al and CoAl₂O₄ were prepared by incipient wetness impregnation and characterized by N₂ adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), CO chemisorption, and temperature-programmed reduction (TPR). The properties of catalysts were investigated for glycerol steam reforming reaction for hydrogen production at 550 ℃. Rh/CoAl₂O₄@Al exhibited about 2.8 times higher glycerol conversion turnover frequency (TOF) than Rh/CoAl₂O₄ due to facilitated heat transport through the core-shell structure. The CoAl₂O₄@Al and CoAl₂O₄ also showed some catalytic activities due to a partial reduction of Co on the support, and a higher catalytic activity was also found on the CoAl₂O₄@Al core-shell than CoAl₂O₄. These catalysts, however, displayed deactivation on the reaction stream due to carbon deposition on the catalysts surface.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.33 no.1
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• pp.60-68
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• 2009

The steam reformer for hydrogen production from methane is studied by a numerical method. Langmuir- Hinshelwood model is incorporated for catalytic surface reactions, and the pseudo-homogeneous model is used to take into account local equilibrium phenomena between a catalyst and bulk gas. Dominant chemical reactions are Steam Reforming (SR) reaction, Water-Gas Shift (WGS) reaction, and Direct Steam Reforming (DSR) reaction. The numerical results are validated with experimental results at the same operating conditions. Using the validated code, parametric study has been numerically performed in view of the steam reformer performance. As increasing a wall temperature, the fuel conversion increases due to the high heat transfer rate. When Steam to Carbon Ratio (SCR) increases, the concentration of carbon monoxide decreases since WGS reaction becomes more active. When increasing Gas Hourly Space Velocity (GHSV), the fuel conversion decreases due to the heat transfer limitation and the low residence time. The reactor shape effects are also investigated. The length and radius of cylindrical reactors are changed at the same catalyst volume. The longer steam reformer is, the better steam reformer performs. However, system energy efficiency decreases due to the large pressure drop.

• Journal of the Korean Solar Energy Society
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• v.27 no.1
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• pp.75-81
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• 2007

Steam reforming of methane using Xe-arc solar simulator was studied for the application of concentrated solar energy into chemical reaction. The reactor, a volumetric absorber, consisted of a porous ceramic foam disk coated with commercial reforming catalyst. Operating temperature was in the range of $450\;-\;550^{\circ}C$ and the excess steam ratio to methane was from 3.0 to 5.0. At the steady-state condition, the conversion of methane Increased with temperature in the range of 15 % - 30 % and the experimentally determined conversion was found to be close to theoretical equilibrium conversion. It was also found that the CO selectivity slightly decreased with excess steam ratio. Finally, the conversion of methane decreased significantly with space velocity of reactants.