• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.398-402
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• 2012

The catalytic performance of some metal oxides in the vapor phase selective oxidation of $H_2S$ in the stream containing ammonia and water was investigated. Among the catalysts tested $Fe_2O_3/SiO_2$ was the most promising catalyst for practical application. It showed higher than 90% $H_2S$ conversion and very small amount of $SO_2$ emission over a temperature range of $240{\sim}280^{\circ}C$. The effects of reaction temperature, $O_2/H_2S$ ratio, amount of ammonia and water vapor on the catalytic activity of $Fe_2O_3/SiO_2$ were discussed to better understand the reaction mechanism. The $H_2S$ conversion showed a maximum at $260^{\circ}C$ and it decreased with increasing temperature over $280^{\circ}C$. With an increase of $O_2/H_2S$ ratio from 0.5 to 4, the conversion was slightly increased, but the selectivity to elemental sulfur was remarkably decreased. The increase of ammonia amount favored the conversion and the selectivity to elemental sulfur with a decrease in $SO_2$ production. The presence of water vapor decreased both the activity and the selectivity to sulfur, but increased the ATS selectivity.

• Transactions of the Korean hydrogen and new energy society
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• v.23 no.6
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• pp.640-646
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• 2012

The effect of Ce promotion over 1wt% $Pt/{\gamma}-Al_2O_3$ catalysts on the CO conversion and $CO_2$ selectivity was investigated in preferential CO oxidation (PrOx) to reduce the CO concentration less than 10 ppm in excess $H_2$ stream for polymer electrolyte membrane fuel cell (PEMFC). Ce-promoted 1wt% $Pt/{\gamma}-Al_2O_3$ catalysts were prepared by incipient wetness impregnation method and the loading amount of Pt was fixed at 1wt%. The content of Ce promoter which has excellent oxygen storage and transfer capability due to the redox property was adjusted from 0 to 1.5wt%. Ce-promoted 1wt% $Pt/{\gamma}-Al_2O_3$ catalysts exhibit high CO conversion and $CO_2$ selectivity at low temperatures below $150^{\circ}C$ due to the improvement of reducibility of surface PtOx species compared with the 1wt% $Pt/{\gamma}-Al_2O_3$ catalyst without Ce addition. When Ce content was more than 1wt%, the catalytic activity was decreased at over $160^{\circ}C$ in PrOx because of competitive $H_2$ oxidation. As a result, 0.5wt% Ce is optimal content not only to achieve high catalytic activity and good stability at low temperatures below $150^{\circ}C$ in the presence of $CO_2$ and $H_2O$ but also to minimize the $H_2$ oxidation at high temperatures.

• Applied Chemistry for Engineering
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• v.19 no.2
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• pp.157-160
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• 2008

The generation of high-purity hydrogen from hydrocarbon fuels is essential for efficient operation of fuel cell. In general, most feasible strategies to generate hydrogen from hydrocarbon fuels consist of a reforming step to generate a mixture of $H_2$, CO, $CO_2$ and $H_2O$ (steam) followed by water gas shift (WGS) and CO clean-up steps. The WGS reaction that shifts CO to $CO_2$ and simultaneously produces another mole of $H_2$ was carried out in a two-stage catalytic conversion process involving a high temperature shift (HTS) and a low temperature shift (LTS). In a typical operation, gas emerges from the reformer is taken through a high temperature shift catalyst to reduce the CO concentration to about 3~5%. The HTS reactor was designed and tested in this study to produce hydrogen-rich gas with CO to a range of 2~4%. The iron based catalysts (G-3C) was used for the HTS to convert the most of CO in the effluent from the partial oxidation (POX) to $H_2$ and $CO_2$ at a relatively high rate. Parametric screening studies were carried out for variations of the following variables: reaction temperature, steam flow rate, components ratio ($H_2/CO$), and reforming gas flow rate.

• Korean Chemical Engineering Research
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• v.50 no.5
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• pp.843-849
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• 2012

When we use NiO based particle as an oxygen carrier in a chemical looping combustion system, the fuel conversion and the $CO_2$ selectivity decreased with increasing reaction temperature within high temperature range (> $900^{\circ}C$) due to the increment of exhaust CO concentration from reduction reactor. To improve reduction reactivity at high temperature, the applicable metal oxide component was selected by calculation of the equilibrium CO concentration of metal oxide components. After that, feasibility of reduction reactivity improvement at high temperature was checked by using solid mixture of the selected metal oxide particle and NiO based oxygen carrier. The reactivity was measured and investigated using batch type fluidized bed. The solid mixture of $Co_3O_4/CoAl_2O_4$(10%) and OCN706-1100(90%) showed higher fuel conversion, higher $CO_2$ selectivity and lower CO concentration than OCN706-1100(100%) cases. Consequently, we could conclude that improvement of reduction reactivity at high temperature range by adding some $Co_3O_4$ based oxygen carrier was feasible.

• Resources Recycling
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• v.15 no.6 s.74
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• pp.10-15
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• 2006

As a basic study on recovery of valuable metals such as vanadium and nickel from metal oxide obtained from waste orimulsion ash, we conducted selectively leaching of vanadium and nickel using $Na_2CO_3$ leaching and ammoniacal leaching, respectively. The 97% of vanadium was selectively leached at an optimum experimental condition, 50g/L $Na_2CO_3$, pulp density 50g/L, and 35% $H_2O_2$ 50ml/L, $25^{\circ}C$... for 1 hr, whereas no nickel was leached. In ammoniacal leaching study, 95% of nickel was selectively leached at the optimal experimental condition, $NH_4OH\;2M,\;(NH_4){_2}SO_4$ 1.5M, pulp density 50g/L, 25, for 4 hr along with 3% of vanadium.

• Clean Technology
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• v.12 no.2
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• pp.87-94
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• 2006

The reduction of $SO_2$ to elemental sulfur by CO over a series of iron niobate with nominal Nb/Fe atomic ratios of 1/0, 10/1, 5/1, 1/1, 1/5, 1/10 and 0/1 was studied with a flow fixed-bed reactor. Strong synergistic phenomena in catalytic activity and selectivity were observed for the iron niobate catalysts, and the best catalytic performance was observed for the catalyst with Fe/Nb atomic ratio of 1/1. The active phase of the activated iron niobate catalysts was identified to be $FeS_2$ using XRD and XPS. Selective reduction of $SO_2$ by CO was followed by the COS intermediate mechanism.

• Applied Chemistry for Engineering
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• v.1 no.2
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• pp.215-223
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• 1990

The effects of sulfur on the catalytic reaction between CO and NO on polycrystalline Pt surface, which is very important in the development of catalyst for automobile exhaust gas control, have been studied using thermal desorption spectrometry(TDS) under ultra-high vacuum(UHV) conditions. Sulfur weakened both the adsorptions of CO and NO by direct site blocking and indirect electronic effect. S(a) desorbing below 800 K gave little effect on reaction activity whereas S(a) desorbing above 800 K, which adsorbs as an atomic state, gave much effect on it. The adsorbed sulfur existed on the surface of platinum in the form of islands, and also reduced the adsorption energies of adsorbates by the long-ranged electronic effect. The platinum catalyst in the reaction between CO and NO was poisoned selectively by S(a), poisoning firstly the active sites of this reaction.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.894-905
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• 1992

Dioxygen binding and homogeneous catalytic oxidation of hydrazobenzene were investigated by employing tetradentate Schiff base Cobalt(II) complexes such as Co(II)(SED)$(Py)_2$, Co(II)(SOPD)$(Py)_2$ and Co(II)(SND)$(Py)_2$ in saturated oxygen methanol solvent. The major product of hydrazobenzene ($H_2$AB) oxidation by catalysts of superoxo type [Co(III)(SED)(Py)$O_2$] and [Co(III)(SOPD)(Py)$O_2$] complexes are trans-azobenzene (t-AB) and rate constants k for oxidation reaction was 7.692 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SED)(Py)$O_2$] and 5.076 ${\times}$ $10^{-2}$ M/sec for [Co(III)(SOPD)(Py)$O_2$]. But cis-azobenzene (c-AB) are obtained as a major product with ${\mu}$-peroxo type [Co(III)(SED)(Py)]$_2O_2$ catalyst, and rate constant k is 1.266 ${\times}$ $10^{-2}$ M/sec. The rate constants of oxidation reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a intermediate activated complexes of catalyst, hydrazobenzene and oxygen has been proposed. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED and SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$ ${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$H_2$AB + 2Py ${\longrightarrow}^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.

• 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%.

• Journal of the Korean Applied Science and Technology
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• v.30 no.4
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• pp.649-655
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• 2013

Methanol was directly produced by the partial oxidation of methane with perovskite and mixed oxide catalysts. Perovskite ($ABO_3$) catalysts were prepared by the malic acid method with changing A and B site components. Three-component mixed oxide catalysts that have Mo and Bi as a main component were prepared by the co-precipitation method. Among the perovskite catalysts, $SrCrO_3$ showed the highest methanol selectivity of 11% at $400^{\circ}C$. For the three-component mixed oxide catalysts, there were no remarkable changes in methane conversion. Among the mixed oxide catalysts, Mo-Bi-Cr mixed oxide catalyst showed the highest methanol selectivity of 15.3% at $400^{\circ}C$. The catalytic activity and methanol selectivity of the three-component mixed oxide catalysts were directly proportional to the surface area of the catalysts.