• 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.

• Journal of Electrochemical Science and Technology
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• v.11 no.4
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• pp.336-345
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• 2020

Nickel-doped lanthanum cobalt oxide (LaCo_1-xNi_xO_3-δ, LCN) was investigated as an alternative anode material for solid oxide fuel cells. To improve its catalytic activity for steam methane reforming (SMR) reaction, Ni²⁺ was substituted into Co³⁺ lattice in LaCoO₃. LCN anode, synthesized using the Pechini method, reacts with yttria-stabilized zirconia (YSZ) electrolyte at high temperatures to form an electrochemically inactive phase such as La₂Zr₂O₇. To minimize the interlayer by-products, the LCN was coated via a double-tape casting method on the Ni/YSZ anode as a catalytic functional layer. By increasing the Ni doping amount, oxygen vacancies in the LCN increased and the cell performance improved. CH₄ fuel decomposed to H₂ and CO via SMR reaction in the LCN functional layer. Hence, the LCN-coated Ni/YSZ anode exhibited better cell performance than the Ni/YSZ anode under H₂ and CH₄ fuels. LCN with 12 mol% of Ni (LCN12)-modified Ni/YSZ anode showed excellent long-term stability under H₂ and CH₄ conditions.

• Korean Chemical Engineering Research
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• v.56 no.2
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• pp.169-175
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• 2018

This study deals with a process for the recovery of hydrogen isotopes from methane ($CQ_4$) and water ($Q_2O$) containing tritium in the nuclear fusion exhaust gas (Q is Hydrogen, Deuterium, Tritium). Steam Methane Reforming and Water Gas Shift reactions are used to convert $CQ_4$ and $Q_2O$ to $Q_2$ and the produced $Q_2$ is recovered by the subsequent Pd membrane. In this study, one circulation loop consisting of catalytic reactor, Pd membrane, and circulation pump was applied to recover H components from $CH_4$ and $H_2O$, one of $CQ_4$ and $Q_2O$. The conversion of $CH_4$ and $H_2O$ was measured by varying the catalytic reaction temperature and the circulating flow rate. $CH_4$ conversion was 99% or more at the catalytic reaction temperature of $650^{\circ}C$ and the circulating flow rate of 2.0 L/min. $H_2O$ conversion was 96% or more at the catalytic reaction temperature of $375^{\circ}C$ and the circulating flow rate of 1.8 L/min. In addition, the amount of $CQ_4$ generated by Korean Demonstration Fusion Power Plant (K-DEMO) in the future was predicted. Then, the treatment process for the $CQ_4$ was proposed and HAZOP (hazard and operability) analysis was conducted to identify the risk factors and operation problems of the process.

• Journal of the Korean Applied Science and Technology
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• v.20 no.3
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• pp.230-236
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• 2003

Synthesis gas is commercially produced by a steam reforming process. However, the process is highly endothermic and energy-consuming. Thus, this study was conducted to produce synthesis gas by the partial oxidation of methane to decrease the energy cost. Supported Ni catalysts were prepared by the impregnation method. To examine the activity of the catalysts, a differential fixed bed reactor was used, and the reaction was carried out at $750{\sim}850^{\circ}C$ and 1 atm. The fresh and used catalysts were characterized by XRD, XPS, TGA and AAS. The highest catalytic activity was obtained with the 13wt% Ni/MgO catalyst, with which methane conversion was 81%, and $H_2$ and CO selectivities were 94% and 93%, respectively. 13wt% Ni/MgO catalyst showed the best $MgNiO_2$ solid solution state, which can explain the highest catalytic activity of the 13wt% Ni/MgO catalyst.

• Journal of the Korean Applied Science and Technology
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• v.21 no.3
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• pp.225-230
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• 2004

Synthesis gas is a high valued compound as a basic chemicals at various chemical processes. Synthesis gas is mainly produced commercially by a steam reforming process. However, the process is highly endothermic so that the process is very energy-consuming process. Thus, this study was carried out to produce synthesis gas by the partial oxidation of methane to decrease the energy cost. The effects of reaction temperature and flow rate of reactants on the methane conversion, product selectivity, product ratio, and carbon deposition were investigated with 13wt% Ni/MgO catalyst in a fluidized bed reactor. With the fluidized bed reactor, $CH_4$ conversion was 91%, and Hz and CO selectivities were both 98% at 850$^{\circ}C$ and total flow rate of 100 mL/min. These values were higher than those of fixed bed reactor. From this result, we found that with the use of the fluidized bed reactor it was possible to avoid the disadvantage of fixed bed reactor (explosion) and increase the productivity of synthesis gas.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.3
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• pp.293-300
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• 2006

KIER has been developing a Ru-based preferential oxidation catalysts and a novel fuel processing system to provide hydrogen rich gas to residential PEMFCs system. The catalytic activity of Ru-based catalysts was investigated at different Ru loading amount and different support structure. The obtained result indicated that 2 wt% loaded Ru-based catalyst supported on ${\alpha}-Al_2O_3$ showed high activity in low temperature range and suppressed the methanation reaction. The developed prototype fuel processor showed thermal efficiency of 78% as a HHV basis with methane conversion of 92%. CO concentration below 10 ppm in the produced gas is achieved with separate preferential oxidation unit under the condition of $[O_2]/[CO]=2.0$. The partial load operation have been carried out to test the performance of fuel processor from 40% to 80% load, showing stable methane conversion and CO concentration below 10 ppm. The durability test for the daily start-stop and 8 h operation procedure is under investigation and shows no deterioration of its performance after 50 start-stop cycles. In addition to the system design and development.

• Journal of the Korean Applied Science and Technology
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• v.20 no.4
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• pp.289-295
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• 2003

Synthesis gas is produced commercially by a steam reforming process. However, the process is highly endothermic and energy intensive. Thus, this study was conducted to produce synthesis gas by the partial oxidation of methane to cut down the energy cost. Supported Ni catalysts were prepared by the impregnation method. To examine the activity of the catalysts, a differential fixed bed reactor was used, and the reaction was carried out at $750{\sim}850^{\circ}C$ and 1 atm. The fresh and used catalysts were characterized by XRD, XPS, TGA and AAS. The highest catalytic activity was obtained with the 13wt% Ni/MgO catalyst, with which methane conversion was 81%, and $H_2$ and CO selectivities were 94% and 93%, respectively. 13wt% Ni/MgO catalyst showed the best $MgNiO_2$ solid solution state, which can explain the highest catalytic activity of the 13wt% Ni/MgO catalyst.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.5
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• pp.528-532
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• 2007

The generation of high-purity hydrogen from hydrocarbon fuels is essential for efficient operation of fuel cell. In general, most feasible strategies to generate hydrogen from hydrocarbon fuels consist of a reforming step to generate a mixture of $H_2$, CO, $CO_2$ and $H_2O$(steam) followed by water gas shift(WGS) and CO clean-up steps. The WGS reaction that shifts CO to $CO_2$ and simultaneously produces another mole of $H_2$ was carried out in a two-stage catalytic conversion process involving a high temperature shift(HTS) and a low temperature shift(LTS). In the WGS operation, gas emerges from the reformer is taken through a high temperature shift catalyst to reduce the CO concentration to about $3\sim4%$ followed to about 0.5% via a low temperature shift catalyst. The WGS reactor was designed and tested in this study to produce hydrogen-rich gas with CO to less than 0.5%.

• Applied Chemistry for Engineering
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• v.8 no.3
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• pp.543-549
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• 1997

The direct reaction of carbon dioxide($CO_2$) with butane($C_4H_{10}$) to obtain synthesis gas and hydrocarbon compounds have been studied on nickel loaded catalysts. In the reaction of $CO_2$ with $C_4H_{10}$, Ni loaded catalysts showed similar activity with Pt catalyst and Coke deposition on the catalyst was severe by dehydrogenation of butane. The main products were carbon monoxide and hydrogen, when alumina and Y type zeolite were used as a support. Instead, a great deal of aromatic hydrocarbons were obtained on the Ni loaded ZSM-5 catalyst. The conversion of $CO_2$ increased with the increasing molar ratio of $CO_2$/$C_4H_{10}$ on Ni/ZSM-5, Ni/NaY and Ni/alumina catalyst, but the conversion decreased again from the ratio of 2. The value of $CO_2$ conversion was the highest at the 5wt% of Ni loading on ZSM-5 catalyst. A part of cokes deposited on the catalysts diminished when only $CO_2$ gas or water steam flowed into the reactor. The coke deposited on the catalysts was very reactive and it may be an important intermediate for the carbon dioxide reforming reaction.

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.656-662
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• 2007

Fuel reformer using plasma and shift reactor for CO oxidation were designed and manufactured as $H_2$ supply device to operate a polymer electrolyte membrane fuel cell (PEMFC). $H_2$ selectivity was increased by non-thermal plasma reformer using GlidArc discharge with Ni catalyst simultaneously. Shift reactor was consisted of steam generator, low temperature shifter, high temperature shifter and preferential oxidation reactor. Parametric screening studies of fuel reformer were conducted, in which there were the variations of the catalyst temperature, gas component ratio, total gas ratio and input power. and parametric screening studies of shift reactor were conducted, in which there were the variations of the air flow rate, stema flow rate and temperature. When the $O_2/C$ ratio was 0.64, total gas flow rate was 14.2 l/min, catalytic reactor temperature was $672^{\circ}C$ and input power 1.1 kJ/L, the production of $H_2$ was maximized 41.1%. And $CH_4$ conversion rate, $H_2$ yield and reformer energy density were 88.7%, 54% and 35.2% respectively. When the $O_2/C$ ratio was 0.3 in the PrOx reactor, steam flow ratio was 2.8 in the HTS, and temperature were 475, 314, 260, $235^{\circ}C$ in the HTS, LTS, PrOx, the conversion of CO was optimized conditions of shift reactor using simulated reformate gas. Preheat time of the reactor using plasma was 30 min, component of reformed gas from shift reactor were $H_2$ 38%, CO<10 ppm, $N_2$ 36%, $CO_2$ 21% and $CH_4$ 4%.