• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.356-362
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• 2006

The $SO_2$ reduction using CO and $H_2$ over Sn-Zr based catalysts was performed in this study. Sn-Zr based catalysts with Sn/Zr molar ratio (0/1, 1/4, 1/1, 2/1, 3/1, 1/0) were prepared by the precipitation and co-precipitation method. The effect of the temperature on the reaction characteristics of the $SO_2$ reduction with a reducing agent such as $H_2$ and CO was investigated under the conditions of space velocity of $10,000ml/g_{-cat.}h$, $([CO(or\;H_2)]/[SO_2])$ of 2.0. As a result, the activity of Sn-Zr based catalysts were higher than $SnO_2$ and $ZrO_2$. The reactivity for the $SO_2$ reduction with CO was higher than that with $H_2$, and sulfur yield in the $SO_2$ reduction by $H_2$ was higher than that by CO. The reactivity for the $SO_2$ reduction with $H_2$ was increased with the reaction temperature regardless of Sn-Zr based catalyst with a Sn/Zr molar ratio. $SnO_2-ZrO_2$ (Sn/Zr=1/4) had highest activity at $550^{\circ}C$, in the $SO_2$ reduction with $H_2$ and $SO_2$ conversion of 94.4％ and sulfur yield of 66.4％ were obtained at $550^{\circ}C$. On the other hand, in the $SO_2$ reduction by CO, the reactivity was decreased with the increase over $325^{\circ}C$. At the optimal temperature of $325^{\circ}C$, $SO_2$ conversion and sulfur yield were about 100％ and 99.5％, respectively, in the $SO_2$ reduction over $SnO_2-ZrO_2$ (Sn/Zr=3/1). Also, the $SO_2$ reduction using syngas with $CO/H_2$ ratio over $SnO_2-ZrO_2$ (Sn/Zr=2/1) was performed in order to investigate the application possibility of the simulated coal gas as the reductant in DSRP. As a result, the reactivity of the $SO_2$ reduction using syngas with $CO/H_2$ ratio was increased with increasing the CO content of syngas. Therefore, it could be known that DSRP using the simulated coal gas over Sn-Zr based catalyst is possible to be realized in IGCC system

• 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 the Korea Academia-Industrial cooperation Society
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• v.19 no.8
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• pp.378-384
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• 2018

$C_9H_7NHCrO_3Cl$ was synthesized by reacting $C_9H_7NH$ with chromium (VI) trioxide. The structure of the product was characterized by FT-IR (Fourier transform infrared) spectroscopy and elemental analysis. The oxidation of benzyl alcohol by $C_9H_7NHCrO_3Cl$ in various solvents showed that the reactivity increased with increasing dielectric constant(${\varepsilon}$) in the following order: DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. The oxidation of alcohols was examined by $C_9H_7NHCrO_3Cl$ in DMF. As a result, $C_9H_7NHCrO_3Cl$ was found to be an efficient oxidizing agent that converts benzyl alcohol, allyl alcohol, primary alcohols, and secondary alcohols to the corresponding aldehydes or ketones (75%-95%). The selective oxidation of alcohols was also examined by $C_9H_7NHCrO_3Cl$ in DMF. $C_9H_7NHCrO_3Cl$ was the selective oxidizing agent of benzyl, allyl and primary alcohol in the presence of secondary ones. In the presence of DMF with an acidic catalyst, such as $H_2SO_4$, $C_9H_7NHCrO_3Cl$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, and $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. The Hammett reaction constant (${\rho}$) was -0.69 (308K). The observed experimental data were used to rationalize hydride ion transfer in the rate-determining step.

• Journal of Korean Society of Environmental Engineers
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• v.35 no.4
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• pp.247-256
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• 2013

In this study, alginate beads containing birnessite (Bir-AB), a highly reactive oxidative catalyst for the transformation of phenolic compounds, was prepared and its 1-naphthol (1-NP) removal efficiency was investigated in a batch test. Based on scanning electron microscopy image, it can be inferred that the alginate gel cluster acts as a bridge which bind the birnessite particles together. Kinetic experiment with Bir-AB of different mixing ratios of birnessite to alginate (Bir : AG=0.25 : 1~1 : 1 w/w) indicate that pseudo-first order kinetic constants, $k(hr^{-1})$ for the 1-NP removals increased about 1.5 times when the birnessite mixing ratio was doubled. The removals of 1-NP was found to be dependent on solution pH and the pesudo-first order rate constants were increased from 0.331 $hr^{-1}$ at pH 10 to 0.661 $hr^{-1}$ at pH 4. The analysis of total organic carbon for the reaction solutions showed that a higher removal of dissolved organic carbon was achieved with Bir-AB as compared to birnessite. HPLC chromatographic analysis of the methanol extract after reaction of 1-NP with Bir-AB suggest that the reaction products could be removed through incorporation into the aliginate beads as a bound residue. Mn ions produced from the oxidative transformation of 1-NP by birnessite were also removed by sorption to Bir-AB. The Bir-AB was recovered quantitatively by simple filtration and was reused twice without significant loss of the initial reactivity.

• 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 the Korean Chemical Society
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• v.36 no.2
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• pp.261-272
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• 1992

Tetradentate Schiff base Cobalt(II)(3MeOSED)$(H_2O)_2$ complexe was synthesized and allowed to react with dry oxygen to form oxygen adducts of Cobalt(III) complexes such as ${\mu}$-peroxo type [Co(III)(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$in DMF and DMSO or superoxo type [Co(III)(3MeOSED)(Py)]$O_2$ in pyridine. The oxygen adducted complex was investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMF (-DMSO,-Py) as supporting electrolyte solution. As a result the reduction reaction process occurred to four steps including prewave Of $O_2^-$in 1 : 1 oxygen adducted superoxo type [Co(III)(3MeOSED)(Py)]$O_2$complex and three steps not including prewave of $O_2^-$ in 1 : 2 oxygen adducted ${\mu}$-peroxo type [Co(III)-(3MeOSED)(DMF)]$_2O_2$ and [Co(III)(3MeOSED)(DMSO)]$_2O_2$. A superoxo type [Co(III)(3MeOSED)(L)]$O_2\;(L: CH_3OH)$ was generated with oxygen in methanol. Selectively oxidized hydrazobenzene $(H_2AB)$ to trans-azobenzene(t-AB) and the rate constant k for oxidation reaction of the following equation is $(2.96 {\pm} 0.2)$${\times}$ $10^{-1}$M/sec. $H_2AB$ + Co (II)(3MeOSED)$(L_2)+O_2\;{\rightleftarrow^K}$ [Co(III)(3MeOSED)(L)]$O_2{\cdot}H_2AB{\longrightarrow^K}$ Co(II(3MeOSED)$(L)_2$+t-AB+$H_2O_2 $.

• The Journal of the Convergence on Culture Technology
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• v.8 no.6
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• pp.927-933
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• 2022

We synthesized (C₁₀H₈N₂H)₂Cr₂O₇, The structure of the product was characterized with FT-IR(infrared) and elemental analysis. The oxidation of benzyl alcohol by (C₁₀H₈N₂H)₂Cr₂O₇ in organic solvents showed that the reactivity increased with the increase of the dielectric constant. The oxidation of alcohols was examined by (C₁₀H₈N₂H)₂Cr₂O₇ in DMF, acetone. As a resuit, (C₁₀H₈N₂H)₂Cr₂O₇ was found as efficicent oxidizing agent that converted benzyl alcohol, allyl alcohol, primary alcohol and secondary alcohols to the corresponding aldehydes or ketones(65%~95%). The selective oxidation of alcohols was also examined by (C₁₀H₈N₂H)₂Cr₂O₇ in DMF, acetone. (C₁₀H₈N₂H)₂Cr₂O₇ was selective oxidizing agent(15%~95%) of benzyl alcohol, allyl alcohol and primary alcohol in the presence of secondary ones. In the presence of DMF solvent with acidic catalyst such as H₂SO₄. (C₁₀H₈N₂H)₂Cr₂O₇ oxidized benzyl alcohol(H) and its derivatives. The Hammett reaction constant(ρ) was -0.69(308K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

• 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 Korea Academia-Industrial cooperation Society
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• v.18 no.5
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• pp.708-715
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• 2017

Recently, in order to meet the stricter emission regulations, the proportion of after-treatments for vehicles and vessels has been increasing gradually. The objective of this study is to investigate the improvement of $CH_4$ reduction ability of natural gas oxidation catalyst (NGOC), which reduces toxic gases emitted from CNG buses. Thirteen NGOCs were prepared, and the conversion performance of noxious gases according to the type of supports, the loading amount of noble metal, and surfactant and aging were determined. Support Zeolite supported on No. 3 $NGOC(1Pt-1Pd-3MgO-3CeO_2/(46TiO_2+23Al_2O_3+23Zeolite)$ is an anionic alkali metal/earth metal component that improved the oxidation reactivity between CO and NO and noble metal dispersion, and thus enhanced the $CH_4$ reduction ability. As the loading amount of Pd, a noble metal with a high selectivity to $CH_4$, was increased, the number of reaction sites was increased and the ability to reduce $CH_4$ was improved. No. 11 $NGOC(1Pt-1Pd-3MgO-3CeO_2/(Z20+Al80)$(pH=8.5), to which nitrate surfactant had been added, exhibited well dispersed catalyst particles with no agglomeration and improved the $CH_4$ reduction ability by 5-15%. The $NGOC(2Pt-2Pd-3Cr-3MgO/90Al_2O_3)$(48h aging), which was mildly thermal aged for 48h, increased the $CH_4$ reduction ability to about 10% or less as compared with No. 12 NGOC(Fresh).

• 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%.