• Korean Journal of Materials Research
• /
• v.31 no.9
• /
• pp.525-531
• /
• 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
• /
• v.34 no.3
• /
• pp.316-326
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.33 no.4
• /
• pp.451-461
• /
• 2022

CFD analysis including optimization process was conducted to design shell and tube CO₂ methanation reactor cooling system. The high-pressure saturated water flowed into the cooling system and was evaporated by heat flux from reacting tubes. The optimization process decided the gap between tubes and reactor diameter to satisfy objective functions related to temperature. The results showed that the gap and diameter reduced about 30% and 3.6% respectively. Averaged surface temperature satisfied the target value and the min-max deviation was minimized.

• Clean Technology
• /
• v.19 no.2
• /
• pp.156-164
• /
• 2013

In this study, we analyzed the operational characteristics of a 0.25 MW methanation pilot plant. Isothermal reactor controled the heat released from methanation reaction by saturated water in shell side. Methanation process consisting of isothermal reactor and adiabatic reactor had advantages with no recycle compressor and more less reactors compared with methanation process with only adiabatic reactors. In case that $H_2$/CO ratio of syngas was under 3, carbon deposition occurred on catalyst in tube side of isothermal reactor and the pressure of reactors increased. In case that $H_2$/CO ratio was maintained around 3, no carbon deposition on catalyst in tube side of isothermal reactor was found by monitoring the differential pressure of reactors and by measuring the differential pressure of several of tubes filled with catalyst before and after operating. It was shown that CO conversion and $CH_4$selectivity were over 99, 97%, respectively, and the maximum $CH_4$productivity was $695ml/h{\cdot}g-cat$.

• Clean Technology
• /
• v.20 no.1
• /
• pp.57-63
• /
• 2014

In this work, we performed the methanation with steam and synthesis gas of a low $H_2/CO$ ratio to develop a process for producing SNG (synthetic natural gas). In this experiment conditions, the water gas shift reaction and the methanation reaction take place at the same time, and insufficient supply of steam might cause the deactivation of the catalyst. Therefore, the reaction characteristics with the amount of steam was performed, and the methanation on syngas containing $CO_2$ of the high concentration were studied. As a result, the temperature in the catalyst bed decreased by the supply of steam, and the methanation and the water gas shift reaction occurred at the same time. Although methane yield slightly decreased at the methanation using syngas containing $CO_2$ of the high concentration, the long-term operation (1,000 h) in the experimental conditions of this study indicates that this condition is suitable for the new commercial scale SNG process.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.11
• /
• pp.1682-1688
• /
• 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 $H_{(1)} CH _{(1)}$.

• Journal of the Korean Institute of Gas
• /
• v.13 no.5
• /
• pp.26-32
• /
• 2009

Ni catalysts on mesoporous silica and commercial silica were prepared for the methanation. XRD and TPR analyses indicated that Ni/mesoporous silica had smaller metal particle size and higher metal dispersion than that of Ni/commercial silica. In addition, Ni/mesoporous silica had stronger metal-support interaction. In methanation, Ni/mesoporous silica showed higher CO conversion and methane yield (65%) than Ni/commercial silica (58%). In the characterization results of catalysts after reaction, Ni/commercial silica was deactivated by the collapse of structure and metal sintering, but Ni/mesoporous silica showed stable catalytic performance.

• Applied Chemistry for Engineering
• /
• v.31 no.3
• /
• pp.323-327
• /
• 2020

The reaction characteristics of Ni/CeO_2-X which is highly efficient at a low temperature was investigated for an application to carbon dioxide methanation process. The CeO_2-X support was obtained by the heat treatment of Ce(NO₃)₃ at 400 ℃ and the catalyst was prepared by impregnation process. The operating parameters of the experiment were the internal pressure of the reactor, the composition of oxygen, methane, and hydrogen sulfide in the inlet gas and the reaction temperature. When Ni/CeO_2-X was used for the carbon dioxide methanation reaction, the CO₂ conversion rate increased by more than 25% as the pressure increased from 1 to 3 bar. The increase was large at a low reaction temperature. When both oxygen and methane were in the inlet gas, the CO₂ conversion rate of the catalyst decreased by up to 16 and 4%, respectively. As the concentration of oxygen and methane increased, the reduction rate of the CO₂ conversion rate tended to increase. In addition, the hydrogen sulfide in the inlet gas reduced the CO₂ conversion rate by up to 7% and caused catalyst deactivation. The results of this study will be useful as basic data for the carbon dioxide methanation process.

• Transactions of the Korean hydrogen and new energy society
• /
• v.22 no.2
• /
• pp.249-256
• /
• 2011

In this study, the Ni-based catalysts for the production of synthetic natural gas were prepared by various preparation methods such as the co-precipitation, precipitation, impregnation and physical mixing methods. The ranges of the reaction conditions were the temperatures of 250~$350^{\circ}C$, $H_2$/CO mole ratio of 3.0, the pressures of 1 atm and the space velocity of 20000 $ml/g_{-cat{\cdot}}{\cdot}h$. It was found that the catalyst prepared by precipitation method had higher CO conversion than the catalyst prepared by co-precipitation method. While the catalyst prepared by precipitation method had the formation of NiO structure, the catalyst prepared by co-precipitation method had the formation of $NiAl_2O_4$ structure. It was confirmed that Ni-based catalyst prepared by the physical mixing method had the lowest CO conversion because it was deactivated by the production of $Ni_3C$ during the methanation. As a result, it was shown clearly that Ni-based catalysts prepared by impregnation method expressed the highest catalytic activity in CO methanation.

• 한국신재생에너지학회:학술대회논문집
• /
• 2011.11a
• /
• pp.75.1-75.1
• /
• 2011

Coal gasification is considered as one of the most prospective technologies in energy field since it can be utilized for various products such as electricity, SNG (Synthetic Natural Gas or Substitute Natural Gas) and other chemical products. Among those products from coal gasification, SNG is emerging as a very lucrative product due to the rising prices of oil and natural gas, especially in Asian countries. The process of SNG production is very similar to the conventional IGCC in that the overall process is highly dependent on the type of gasifier and coal rank. However, there are some differences between SNG production and IGCC, which is that SNG plant requires higher oxygen purity from oxygen plant and more complex gas cleanup processes including water-gas shift reaction and methanation. Water-gas shift reaction is one of the main process in SNG plant because it is a starting point for the latter gas cleanup processes. For the methanation process, syngas is required to have a composition of $H_2$/CO = 3. This study reviewed various considerations for water-gas shift process in a conceptual design on an early stage like a feasibility study for a real project. The factors that affect the design parameters of water-gas shift reaction include the coal properties, the type of gasifier, the overall thermal efficiency of the plant and so on. Water-gas shift reaction is a relatively proven technology compared to the other processes in SNG plant so that it can reduce technological variability when designing a SNG project.