• Journal of the Korean Chemical Society
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• v.42 no.6
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• pp.618-628
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• 1998

Pure CaO, Mn-doped CaO, Mn/CaO, and K/CaO catalysts were prepared and tested as catalysts for the oxidative coupling of methane in the temperature range of 600 to 800$^{\circ}C$ to investigate the effects of Mn- and K-addition on the catalytic activity of calcium oxide. To characterize the catalysts, X-ray powder diffraction(XRD), XPS, SEM, DSC, and TG analyses were performed. The catalytic reaction was carried out in a single-pass flow reactor using on-line gas chromatography system. Normalized reaction conditions were generally $p(CH_4)/p(O_2)=250$ Torr/50 Torr, total feed flow rate=30 mL/min, and 1 atm of total pressure with He being used as diluent gas. Among the catalysts tested, 6.3 mol% Mn-doped CaO catalyst showed the best $C_2$ yield of 8.0% with a selectivity of 43.2% at 775$^{\circ}C$. The $C_2$ selectivity increased on lightly doped CaO catalysts, while decreased on heavily doped CaO([Mn] > 6.3 mol%) catalysts. 6 wt.% Mn/CaO and 6 wt.% K/CaO catalysts showed the $C_2$ selectivities of 13.2% and 30.9%, respectively, for the reaction. Electrical conductivities of CaO and Mn-doped CaO were measured in the temperature range of 500 to 1000$^{\circ}C$ at Po2's of $10^{-3}\; to\;10^{-1}\;atm.$ The electrical conductivity was decreased with Mn-doping and increased with increasing $P0_2$in the range of $10^{-3}\;to\;10^{-1}\;atm,$ indicating the specimens to be p-type semiconductors. It was suggested that the interstitial oxygen ions formed near the surface can activate methane and the formation of interstitial oxygen ions was discussed on the basis of solid-state chemistry.

• Journal of Korean Society of Environmental Engineers
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• v.22 no.12
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• pp.2263-2273
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• 2000

Catalytic wet air oxidation of acetic acid over Mn-Ce based catalysts deposited on various supports ($SiO_2$, $TiO_2$, $ZrO_2$), $ZrSiO_4$, $ZrO_2(10wt%)/TiO_2$) have been carried out in high pressure microreactors. Also, promotional effects by small addition(O.5~1.0 wt%) of p-type semiconductors (CoO, $Ag_2O$, SnO) have been investigated. From the screening tests for initial activity ranking, both Mn(2.8)-Ce(7.2 wt%) and Ru(O.4)Mn(2.7)-Ce(6.9 wt%) supported on $TiO_2$ were selected as the promising reference candidates. In $Mn-Ce/TiO_2$ reference catalyst, addition of small amount of each p-type semiconductor (Co, Sn and Ag) resulted in activity promotional effect and the degree of the increase was in the following order: Co> Ag > Sn. Especially, $Mn-Ce/TiO_2$ promoted with 0.5 wt% Co gave the 2.6 folds activity increase compared to the reference case attributing to the surface area increase as well as synergy effect. In $Ru-Mn-Ce/TiO_2$ reference catalyst, only Co(1.0 wt%) promoted case showed a little reaction rate increase.

• Journal of the Korean Institute of Gas
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• v.27 no.3
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• pp.19-26
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• 2023

Hydrogen, a clean energy source free of COx emissions, is poised to replace fossil fuels, with its usage on the rise. Despite its high energy content per unit mass, hydrogen faces limitations in storage and transportation due to its low storage density and challenges in long-term storage. In contrast, ammonia offers a high storage capacity per unit volume and is relatively easy to liquefy, making it an attractive option for storing and transporting large volumes of hydrogen. While NH₃ decomposition is an endothermic reaction, achieving excellent low-temperature catalytic activity is essential for process efficiency and cost-effectiveness. The study examined the effects of different zeolite types (5A, NaY, ZSM5) on NH₃ decomposition activity, considering differences in pore structure, cations, and Si/Al-ratio. Notably, the 5A zeolite facilitated the high dispersion of Ni across the surface, inside pores, and within the structure. Its low Si/Al ratio contributed to abundant acidity, enhancing ammonia adsorption. Additionally, the presence of Na and Ca cations in the support created medium basic sites that improved N₂ desorption rates. As a result, among the prepared catalysts, the 15 wt%Ni/5A catalyst exhibited the highest NH₃ conversion and a high H₂ formation rate of 23.5 mmol/g_cat·min (30,000 mL/g_cat·h, 600 ℃). This performance was attributed to the strong metal-support interaction and the enhancement of N₂ desorption rates through the presence of medium basic sites.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.1
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• pp.101-108
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• 2005

Because the stone cultural properties located outdoors, they have been altered and deteriorated in external appearance due to environmental factors such as acid rain, extreme change in temperature, and salts. Damage to stone cultural properties is accelerated particularly due to recent industrial development and environmental pollution. An experimental study was conducted to evaluate the effect of environmental contaminants on the weathering of granite. And as part of the developing of conservation method, $TiO_2$ catalyst was prepared and tested. When fresh granite was dipped into the salt and acid solutions, dissolution rate of eight minerals (Si, Mg, Ca, Na, K, Fe, Mn, Al) are abruptly increased at initial stage of reaction and then increased steadily until 100 cycles. After salt and acid solution experiments, the mineral compositions of the granite surface were lower then that of the fresh granite and density of the weathered granite was steadily decreased from $2.60\;g/cm^3$ to $2.56\;g/cm^3$, but Poissions ratio and absorption ratio were slightly increased. It was expected at stone cultural assets could be weathered by salts and acid rain. In the case of $TiO_2$ was coated to the granite, the dissolution rate of minerals and absorption ratio of $TiO_2$ coated granite were decreased. Therefore, the $TiO_2$ coating method tested in this study considered to be a viable method to assist in the conservation of stone cultural properties from environmental contaminants.

• Korean Chemical Engineering Research
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• v.48 no.3
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• pp.304-310
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• 2010

The FTS(Fischer-Tropsch synthesis) was carried out over precipitated iron-based catalysts with or without $SiO_2$ in a fixed-bed reactor at $250^{\circ}C$ and 1.5 MPa. The catalysts with $SiO_2$ showed much higher catalytic activity for the FTS than those without $SiO_2$, displaying excellent stability during 144 h of reaction. The X-ray diffraction and $N_2$ physisorption revealed that the catalysts with $SiO_2$ showed enhanced dispersion of $Fe_2O_3$ compared with those without $SiO_2$. Also, the results of temperature-programmed reduction by $H_2$ showed that the addition of $SiO_2$ markedly promoted the reduction of $Fe_2O_3$ into $Fe_3O_4$ and FeO at low temperatures below $260^{\circ}C$. In contrast, surface basicity of the catalysts, which was analyzed by temperature-programmed desorption of $CO_2$, decreased as a result of $SiO_2$ addition. We attribute the high and stable performance of the catalysts with $SiO_2$ to the improved dispersion and reducibility by the $SiO_2$ addition.