• Korean Chemical Engineering Research
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• v.52 no.5
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• pp.678-687
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• 2014

The catalytic performance of silicon carbide supported nickel catalysts modified with or without second metal (Co, Cu and Zn) for the methanation of CO has been investigated in a fixed-bed reactor using a feed consisting of 25% CO and 75% $H_2$ without any diluent gas. It has been found that the introduction of Co species can clearly improve the catalytic activity of Ni/SiC catalyst, whereas the addition of Cu or Zn can result in a significant decrease in the catalytic activity. The characterizations by means of XRD, TEM, XPS, CO-TPD and $H_2$-TPR indicate that the addition of Co could decrease the particle size of active metal, increase active sites on the surface of methanation catalyst, improve the chemisorption of CO and enhance the reducibility of methanation catalysts. Additionally, the special interaction between Co species and Ni species is likely favorable for the dissociation of adsorbed CO on the surface of catalyst, and this may also contribute to the high activity of 5Co-Ni/SiC catalyst for CO methanation reaction. For 5Cu-Ni/SiC catalyst and 5Zn-Ni/SiC catalyst, Cu and Zn species could cover partial nickel particles and decrease the chemisorption amount of CO. These could be responsible for the low methanation activity. In addition, a 150h stability test under 2 MPa and $300^{\circ}C$ showed that 5Co-Ni/SiC catalyst was very stable for CO methanation reaction.

• Journal of Environmental Science International
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• v.28 no.1
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• pp.65-73
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• 2019

The catalytic activity of Ni-0.2%YSZ (Yttria-Stabilized Zirconia) with different promoters was evaluated for $CO_2$ methanation. The catalysts were weighed for mixing and they were dried at $110^{\circ}C$ for molding into disks. The concentration of $CO_2$ and $CH_4$ for conducting of $CO_2$ methanation were analyzed by gas chromatography and the physical characteristics of the disk-type catalyst formed were analyzed by X-ray diffraction, scanning electron microscope and energy dispersive x-ray spectrometer. The addition of $CeO_2$ as a promoter for Ni-0.2%YSZ (denoted as Ni-5%Ce-0.2%YSZ) resulted in the highest $CO_2$ methanation. It also showed catalytic activity at a low temperature($200^{\circ}C$). Following this, $ZrO_2$, $SiO_2$, $Al_2O_3$ and $TiO_2$ were added to Ni-5%Ce-0.2%YSZ to compare the $CO_2$ methanation, and the highest efficiency was found for. Ni-1%Ti-5%Ce-0.2%YSZ Then, the concentration of Ti was increased to 10% and the catalytic activity was estimated using seven different types of commercial $TiO_2$. In conclusion, ST-01 $TiO_2$ showed the highest efficiency for $CO_2$ methanation.

• Korean Chemical Engineering Research
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• v.56 no.2
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• pp.269-274
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• 2018

All the $Ni-Co-Ce-ZrO_2$ mixed oxides are prepared by co-precipitations methods. Methanation of CO and $H_2$ reaction is screened tested over different fractions of cerium (2, 4, 7 and 12 wt.%) over $Ni-Co/ZrO_2$ bimetallic catalysts are investigated. The mixed oxides are characterized by XRD, CO-Chemisorption, TGA and screened methanation of CO and $H_2$ at $360^{\circ}C$ for 3000 min on stream at typical ratio $CO:H_2=1:1$. In $Ni-Co/CeZrO_2$ series 2 wt.% Ce loading catalyst shows most promising catalyst for $CH_4$ selectivity than $CO_2$, which directs more stability with less coke formation. The high activity is attributed to the better bimetallic synergy and the well-developed crystalline phases of NiO, $ZrO_2$ and $Ce-ZrO_2$. Other bimetallic mixed oxides NCoZ, $NCoC^{4-12}Z$ has faster deactivation with low methanation activity. Finally, 2 wt.% Ce loading catalyst was found to be optimal coke resistant catalyst.

• Applied Chemistry for Engineering
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• v.23 no.6
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• pp.572-576
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• 2012

This study presents the $CO_2$ methanation reaction on Pt catalysts for reducing the amount of $CO_2$, one of greenhouse gases. The AlO(OH) of $Al_2O_3$precusor was used as a support via a thermal treatment and the Pt was used as an active metal. In XRD results, it was confirmed that the Pt was well dispersed and the support existed as the gamma $Al_2O_3$phase. The $Pt/Al_2O_3$ catalyst calcined at $600^{\circ}C$ showed the highest conversion efficiency and selectivity.

• Journal of the Korean Institute of Gas
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• v.13 no.5
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• pp.33-38
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• 2009

Synthetic natural gas was producd by the reaction of carbon monoxide and hydrogen via methanation. Ni-Co bimetallic catalyst supported on $Al_2O_3$ for methanation was prepared using deposition-precipitation method. For the comparison, Ni, Co monometallic catalyst was prepared using the same method. The prepared catalysts were characterized by TEM, XRD and TPR and applied to methanation reaction. The catalysts prepared using deposition-precipitation method showed the high metal dispersion. The activity of Ni-Co bimetallic catalyst was higher than that of Ni, Co monometallic catalyst. TPR measurements indicated that Ni-Co bimetallic catalyst had more active hydrogen species than Ni, Co monometallic catalyst due to the synergetic effect in the presence of Ni and Co.

• New & Renewable Energy
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• v.6 no.4
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• pp.30-40
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• 2010

Syngas from gasification of coal can be converted to SNG(Synthesis Natural Gas) through gas cleaning, water gas shift, $CO_2$ removal, and methanation. One of the key technologies involved in the production of SNG is the methanation process. In the methanation process, carbon oxide is converted into methane by reaction with hydrogen. Major factors of methanation are hydrogen-carbon oxide ratio, reaction temperature and space velocity. In order to understand the catalytic behavior, temperature programmed surface reaction (TPSR) experiments and reaction in a fixed bed reactor of carbon monoxide have been performed using two commercial catalyst with different Ni contents (Catalyst A, B). In case of catalyst A, CO conversion was over 99% at the temperature range of $350{\sim}420^{\circ}C$ and CO conversions and $CH_4$ selectivity were lower at the space condition over 3000 1/h. In case of catalyst B, CO conversion was 100% at the temperature over $370^{\circ}C$ and CO conversions and $CH_4$ selectivity were lower at the space condition over 4700 1/h. Also, conditions to satisfy $CH_4$ productivity over 500 ml/h.g-cat were over 2000 1/h of space velocity in case of catalyst A and over 2300 1/h of space velocity in case of catalyst B.

• Transactions of the Korean hydrogen and new energy society
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• v.29 no.2
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• pp.170-180
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• 2018

After $MoS_2$ catalyst was prepared at 1, 30, and 70 atm, the hydrothermal pressure effect over preparation of $MoS_2$ was investigated in terms of catalyst characterization and direct methanation. Multifaceted characterization techniques such as XRD, BET, SEM, TPR, EDS, and XPS were used to analyze and investigate the effect of high pressure over the preparation of surface and bulk $MoS_2$ catalyst. Result from XRD, SEM, and BET demonstrated that $MoS_2$ was more dispersed as preparation pressure was increased, which resulted finer $MoS_2$ crystal size and higher surface area. EDS result confirmed that bulk composition was $MoS_2$ and XPS result showed that S/Mo mole ratio of surface was about 1.3. TPR showed that $MoS_2$ prepared at 30 atm possessed higher active surface sites than $MoS_2$ prepared at 1 atm and these sites could contribute to higher CO yield during methanation. Direct methanation was used to evaluate the CO conversion of the both catalysts prepared at 1 atm and 30 atm and reaction condition was at feed mole ratio of $H_2/CO=1$, GHSV=4800, 30 atm, temperature($^{\circ}C$) of 300, 350, 400, and 450. $MoS_2$ prepared at 30 atm showed more stable and higher CO conversion than $MoS_2$ prepared at 1 atm. Faster deactivation was occurred over $MoS_2$ prepared at 1 atm, which indicated that preparation pressure of $MoS_2$ catalyst was the dominant factor to improve the yield of direct methanation.

• Korean Journal of Materials Research
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• v.31 no.9
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• pp.525-531
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• 2021

Carbon-encapsulated Ni catalysts are synthesized by an electrical explosion of wires (EEW) method and applied for CO₂ methanation. We find that the presence of carbon shell on Ni nanoparticles as catalyst can positively affect CO₂ methanation reaction. Ni@5C that is produced under 5 % CH₄ partial pressure in Ar gas has highest conversions of 68 % at 350 ℃ and 70 % at 400 ℃, which are 73 and 75 % of the thermodynamic equilibrium conversion, respectively. The catalyst of Ni@10C with thicker carbon layer shows much reduced activity. The EEW-produced Ni catalysts with low specific surface area outperform Ni catalysts with high surface area synthesized by solution-based precipitation methods. Our finding in this study shows the possibility of utilizing carbon-encapsulated metal catalysts for heterogeneous catalysis reaction including CO₂ methanation. Furthermore, EEW, which is a highly promising method for massive production of metal nanoparticles, can be applied for various catalysis system, requiring scaled-up synthesis of catalysts.

• Transactions of the Korean hydrogen and new energy society
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• v.34 no.3
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• pp.316-326
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• 2023

Development of carbon-neutral fuel production technologies to solve climate change issues is progressing worldwide. Among them, methane can be produced through the synthesis of hydrogen produced by renewable energy and carbon dioxide captured through a CO₂ methanation reaction, and the fuel produced in this way is called synthetic methane or e-methane. The CO₂ methanation reaction can be conducted via biological or thermochemical methods. In this study, a 30 Nm³/h thermochemical CO₂ methanation process consisting of an isothermal reactor and an adiabatic reactor was used. The CO₂ conversion rate and methane concentration according to the temperature measurement results at the center and outside of the adiabatic reactor were analyzed. The gas flow into the adiabatic reactor was found to reach equilibrium after about 1.10 seconds or more by evaluating the residence time. Furthermore, experimental and analysis results were compared to evaluate performance of the reactor.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1682-1688
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• 2005

Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for $CO_2$ methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for $CO_2$ dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of $CH_4$ the intermediate complex are 1.21 $\AA$, 1.31 $\AA$ for the C${\cdot}{\cdot}{\cdot}H_{(1)}$, and 2.82 $\AA$ for the height, with angles of 105${^{\circ}}$ for ∠ $H_{(1)}$CH and 98${^{\circ}}$ for $H_{(1)} CH _{(1)}$.