• Korean Chemical Engineering Research
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• 제51권4호
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• pp.443-454
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• 2013

Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically $V^{5+}$, $Co^{2+}$, and $Ni^{2+}$-incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated.

• Korean Journal of Materials Research
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• 제31권9호
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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.

• Applied Chemistry for Engineering
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• 제18권6호
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• pp.618-624
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• 2007

thermochemical methane reforming consisting of two steps on Cu/Fe/Zr mixed oxide media was carried out using a fixed bed infrared reactor. In the first step, the metal oxide was reduced with methane to produce CO, $H_2$ and the reduced metal oxide in the temperature of 1173 K. In the second step, the reduced metal oxide was re-oxidized with steam to produce $H_2$ and the metal oxide in the temperature of 973 K. The reaction characteristics on the added amounts of Cu in Cu/Fe/Zr mixed oxide media and the cyclic tests were evaluated. With the increase of the added amount of Cu in Cu/Fe/Zr mixed oxide media, the conversion of $CH_4$, the selectivity of $CO_2$ and the $H_2/CO$ molar ratio were increased, while the selectivity of CO was decreased in the first step. On the other hand, the evolved amount of $H_2$ was decreased with increasing the added amount of Cu in the second step. The $Cu_xFe_{3-x}O_4/ZrO_2$ medium added with Cu of x = 0.7 showed good regeneration properties in the 10th cyclic tests indicating that the medium had high durability. In addition, the gasification of the deposited carbon in the water splitting step was promoted with the addition of Cu in the media.

• Applied Chemistry for Engineering
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• 제5권4호
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• pp.580-587
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• 1994

The oxidative coupling of methane was studied kinetically using $Na^+(50wt%)/MgO$ catalyst at 710, 730, 750, 770 and $790^{\circ}C$ in a fixed bed flow reactor at the atmospheric pressure under differential conversion conditions. Through curve fitting, it was found that the Langmuir-Hinshelwood type mechanism was fitted to this reaction rather than Rideal-Redox type or Eley-Rideal type mechanism. Therefore, it was proposed that the $O_2{^-}$ or $O_2{^{2-}}$ species on the surface was related to the production of $CH_3{\cdot}$. The estimated activation energy of $CH_3{\cdot}$ production was about 39.3kcal/mol. Moreover, as the result of curve fitting, the stoichiometric coefficient of $O_2$ for the production of $CH_3{\cdot}$ to produce $CO_x$was approximately 1.5. Accordingly, it could be concluded that the $CH_3O_2{\cdot}*$ was prouduced through the partial oxidation of $CH_3{\cdot}$ with the surface oxygen.

• Journal of Hydrogen and New Energy
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• 제31권5호
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• pp.419-428
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• 2020

The kinetics of direct methanation over activated charcoal-supported molybdenum catalyst at 30 bar was studied in a cylindrical fixed-bed reactor. When the temperature was not higher than 400℃, the CO conversion increased with increasing temperature according to the Arrhenius law of reaction kinetics. While XRD and Raman analysis showed that Mo was present as Mo oxides after reduction or methanation, TEM and XPS analysis showed that Mo₂C was formed after methanation depending on the loading of Mo precursor. When the temperature was as high as 500℃, the CO conversion was dependent not only on the Arrhenius law but also on the catalyzed reaction by nanoparticles, which came off from the reactor and thermocouple by metal dusting. These nanoparticles were made of Ni, Fe, Cr and alloy, and attributed to the formation of carbon deposit on the wall of the reactor and on the surface of the thermocouple. The carbon deposit consisted of amorphous and disordered carbon filaments.

• Journal of Environmental Science International
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• 제28권1호
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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.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2005년도 춘계학술대회
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• pp.476-481
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• 2005

2004년말 현재 국내에서 발생되는 음식물쓰레기의 재활용량은 전체 발생량의 $87.7\%$인 10,015톤/일이며, 전체 재활용량의 $6.47\%$인 640톤/일 정도가 혐기성소화 방법에 의해 처리 및 자원화 되고 있다. 국내에서 적용되고 있는 음식물쓰레기 혐기성소화 기술의 대부분은 습식소화(Wet digestion) 공법이며, 처리 방법별로 2상 혐기성소화(Two-phase anaerobic digestion)와 하수슬러지 흑은 축산분뇨와 함께 혼합처리 하는 통합소화(Co-digestion) 공정으로 구분되고 있다. 음식물쓰레기의 자원화 방법에 있어 혐기성소화는 사료화, 퇴비화에 비하여 폐기물의 효과적인 감량화와 자원화 효과뿐만 아니라 유용 에너지원인 메탄가스의 회수가 가능하기에 최근에 주목을 받는 biotechnology중의 하나로 자리매김 하고 있으며, 또한 유기성폐기물의 자원순환형 관리 시스템 구현에 있어 적절한 대안으로 고려되고 있다.

• Applied Chemistry for Engineering
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• 제19권6호
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• pp.624-628
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• 2008

Nitrous oxide ($N_2O$), known as one of the major greenhouse gases, is an important component of the earth's atmosphere, and gives rise to precursor of acid rain and photochemical smog. For the removal of $N_2O$ and other nitrogen oxides, the SCR reaction system with various reductants is widely used. This study is based on the results of experimental and theoretical examinations on the catalytic decomposition of sole nitrous oxide ($N_2O$) and selective catalytic reduction of $N_2O$ with $CH_4$ in the presence of oxygen using mixed metal oxide catalysts obtained from hydrolatcite-type precursors. When $CH_4$ is fed together with a reductant, it affects positively on the $N_2O$ decomposition activity. At an optimum ratio of $CH_4$ to $O_2$ mole ratio, the $N_2O$ conversion activity is enhanced on the SCR reaction with partial oxidation of methane.

• Microbiology and Biotechnology Letters
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• 제37권4호
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• pp.293-305
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• 2009

Methane, as a greenhouse gas, is some 21~25 times more detrimental to the environmental than carbon dioxide. Landfills generally constitute the most important anthropogenic source, and methane emission from landfill was estimated as 35~73 Tg per year. Biological approaches using biocover (open system) and biofilter (closed system) can be a promising solution for older and/or smaller landfills where the methane production is too low for energy recovery or flaring and installation of a gas extraction system is inefficient. Methanotrophic bacteria, utilizing methane as a sole carbon and energy source, are responsible for the aerobic degradation (oxidation) of methane in the biological systems. Many bench-scale studies have demonstrated a high oxidation capacity in diverse filter bed materials such as soil, compost, earthworm cast and etc. Compost had been most often employed in the biological systems, and the methane oxidation rates in compost biocovers/boifilters ranged from 50 to $700\;g-CH_4\;m^{-2}\;d^{-1}$. Some preliminary field trials have showed the suitability of biocovers/biofilters for practical application and their satisfactory performance in mitigation methane emissions. Since the reduction of landfill methane emissions has been linked to carbon credits and trading schemes, the verified quantification of mitigated emissions through biocovers/biofilters is very important. Therefore, the assessment of in situ biocovers/biofilters performance should be standardized, and the reliable quantification methods of methane reduction is necessary.

• Journal of the Korea Academia-Industrial cooperation Society
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• 제22권2호
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• pp.644-650
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• 2021

This study characterized the reforming of methane with carbon dioxide, which is a major cause of global warming. The methane decomposition reaction with carbon dioxide was carried out using transition metal catalysts. The reactivity of tin was lower than that of a transition metal, such as nickel and iron. Most of the decomposition reaction occurred in the solid state. The melting point of tin is 505.03 K. Tin reacts in a liquid phase at the reaction temperature and has the advantage of separating carbon produced by the decomposition of methane from the liquid tin catalyst. Therefore, deactivation due to the deposition of carbon in the liquid tin can be prevented. Methane decomposition with carbon dioxide produced carbon monoxide and hydrogen. Ni was used to promote the catalyst performance and enhance the activity of the catalyst and lifetime. In this study, catalysts were synthesized using the excess wet impregnation method. The effect of the reaction temperature, space velocity was measured to calculate the activity of catalysts, such as the activation energy and regeneration of catalysts. The carbon-deposited tin catalyst regeneration temperature was 1023 K. The reactivity was improved using a nickel co-catalyst and a water supply.