• Clean Technology
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• v.20 no.3
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• pp.212-217
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• 2014

In order to regenerate the sulfidated desulfurization sorbent, oxygen is used as the oxidant agent on the regeneration process. The small amount of oxygen un-reacted in regeneration process is flowed into direct sulfur recovery process. However, the reactivity for $SO_2$ reduction can be deteriorated with the un-reacted oxygen by various reasons. In this study, the deactivation effects of un-reacted oxygen contained in the off-gas of regeneration process flowed into direct sulfur recovery process of hot gas desulfurization system were investigated. Sn-Zr based catalysts were used as the catalyst for $SO_2$ reduction. The contents of $SO_2$ and $O_2$ contained in the regenerator off-gas used as the reactants were fixed to 5.0 vol% and 4.0 vol%, respectively. The catalytic activity tests with a Sn-Zr based catalyst were for $SO_2$ reduction performed at $300-450^{\circ}C$ and 1-20 atm. The un-reacted oxygen oxidized the elemental sulfur produced by $SO_2$ catalytic reduction and the conversion of $SO_2$ was reduced due to the production of $SO_2$. However, the temperature for the oxidation of elemental sulfur increased with increasing pressure in the catalytic reactor. Therefore, it was concluded that the decrease of reactivity at high pressure is occurred by catalytic deactivation, which is the re-oxidation of lattice oxygen vacancy in Sn-Zr based catalyst with the un-reacted oxygen on the catalysis by redox mechanism. Meanwhile the un-reacted oxygen oxidized CO supplied as the reducing agent and the temperature in the catalyst packed bed also increased due to the combustion of CO. It was concluded that the rapidly increasing temperature in the packed bed can induce the catalytic deactivation such as the sintering of active components.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2003.11a
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• pp.17-20
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• 2003

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2006.05a
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• pp.170-175
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• 2006

• Applied Chemistry for Engineering
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• v.7 no.4
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• pp.645-652
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• 1996

Selective catalytic oxidation of $H_2S$ to elemental sulfur using $TiO_2/SiO_2$ catalysts was investigated in this study. The reaction test with pure $TiS_2$ and $Ti(SO_4)_2$ and cyclic temperature operation revealed that $TiO_2$ had a good resistance to sulfation and sulfidation, which are known as the main cause of catalytic deactivation in sulfur recovery process. With the increase of $TiO_2$ loading amount in $TiO_2/SiO_2$ catalysts, the conversion of $H_2S$ increased and the selectivity of elemental sulfur was very slightly decreased. As the ratio of $O_2/H_2S$ increased, the selectivity to elemental sulfur was drastically decreased. In the presence of 10 vol.% water vapor to a stoichiometric mixture of $H_2S$ and $O_2$($H_2S$= 5 vol.% O=2.5 vol.% ), both activity and selectivity of 10 wt.% $TiO_2/SiO_2$ catalyst are decreased, but it still showed more than 80% of sulfur yield.

• Applied Chemistry for Engineering
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• v.18 no.2
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• pp.155-161
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• 2007

In this study, the reactivity of a $SnO_2-ZrO_2$(Sn/Zr = 2/1) catalyst for $SO_2$ reduction by CO was investigated in order to optimize the various reaction conditions such as temperature, gas hourly space velocity (GHSV), and [CO]/[$SO_2$] molar ratio. The reaction temperature in the range of $300{\sim}550^{\circ}C$, space velocity in the range of $5000{\sim}30000cm^3/[g_{-cat}{\cdot}h]$ and [CO]/[$SO_2$] molar ratio in the range of 1.0~4.0 were employed. The optimum temperature, GHSV, and [CO]/[$SO_2$] molar ratio were determined to be $325^{\circ}C$, $10000cm^3/[g_{-cat}{\cdot}h]$, and 2.0, respectively; under these conditions, $SO_2$ conversion was over 99% and sulfur selectivity was over 95%. In addition, the effect of $H_2O$ content on the $SO_2$ reduction by CO was also investigated. As the $H_2O$ content increased from 2 vol% up to 6 vol%, the reactivity and sulfur selectivity decreased. In case of 2 vol% $H_2O$ content, the reaction temperature and [CO]/[$SO_2$] molar ratio were varied in the range of $300{\sim}400^{\circ}C$ and 1.0~3.0. The optimum temperature and [CO]/[$SO_2$] molar ratio were $340^{\circ}C$ and 2.0, respectively under which $SO_2$ conversion and sulfur selectivity were about 90% and 87%, respectively.

• Clean Technology
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• v.13 no.4
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• pp.266-273
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• 2007

The adsorption properties of the activated carbon-based adsorbents were studied to remove COS emitted from $SO_2$ catalytic reduction process on the integrated gasification combined cycle (IGCC) system in this work. Transition metal supported catalysts and mixed metal oxide catalysts were used for the $SO_2$ catalytic reduction. The mechanism of COS produced from the $SO_2$ reduction and the COS concentration s according to the reaction temperature were investigated. In this study, an activated carbon and a modified activated carbon doped with KOH were used to remove the very low concentration of COS effectively. The adsorption rate and the breakthrough time of COS were measured by a thermo gravity analyzer (TGA, Cahn Balance) and a fixed bed flow reactor equipped with GC-pulsed flammable photometric detector (PFPD), respectively. It was confirmed that the COS breakthrough time of the activated carbon doped with KOH was longer than that of an activated carbon. In conclusion, the modified-activated carbon having a high surface area showed a high adsorption rate of COS produced from the $SO_2$ reduction.

• 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