• 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.

• Applied Chemistry for Engineering
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• v.3 no.1
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• pp.53-63
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• 1992

M/BM -series catalysts, $MoO_3$ supported on ${\alpha}-Bi_2Mo_3O_{12}$ were also prepared by impregnation method. BM/M-series catalysts, ${\alpha}-Bi_2Mo_3O_{12}$ supported on $MoO_3$ were also prepared by coprecipitation. Structure and catalytic properties of the two phase catalysts were studied by means of using nitrogen adsorption, X-ray diffraction, and scanning electron microscopy. The reaction test for the selective oxidation of propylene to acrolein over Bi-molybdate catalysts was studied using a fixed-bed reactor system. In M/BM-series catalysts, $MoO_3$ was dispersed on ${\alpha}-Bi_2Mo_3O_{12}$, and the crystal structure of ${\alpha}-Bi_2Mo_3O_{12}$ remains unchanged by the presence of excess $MoO_3$. However the surface morphology and bulk structure of BM/M-series catalysts were altered probably because the precipitated $Bi(OH)_3$ reacted with $MoO_3$ during the calcination to form ${\alpha}-Bi_2Mo_3O_{12}$ phase. The results of propylene oxidation on both series catalysts showed that the reaction took place over the surface of ${\alpha}-Bi_2Mo_3O_{12}$ particle and the role of excess $MoO_3$ was to supply oxygen to ${\alpha}-Bi_2Mo_3O_{12}$. These increasing effects on activity were also observed in the mechanical mixtures of ${\alpha}-Bi_2Mo_3O_{12}$ and $MoO_3$.

• Journal of the Korean Applied Science and Technology
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• v.7 no.1
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• Journal of the Korean Vacuum Society
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• v.17 no.1
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• pp.51-57
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• 2008

we have demonstrated structural evolution and optical properties of Si-nanowires (NWs) synthesized on Si (111) substrates with nanoscale Au-Si islands by rapid thermal chemical vapor deposition (RTCVD). The Au-Si nano-islands (10-50nm in diameter) were employed as a liquid-droplet catalysis to grow Si-NWs via vapor-liquid-solid mechanism. The Si-NWs were grown by a mixture gas of SiH4 and H2 at a pressure of 1.0 Torr and temperatures of $500{\sim}600^{\circ}C$. Scanning electron microscopy measurements showed that the Si-NWs are uniformly sized and vertically well-aligned along <111> direction on Si (111) surfaces. The resulting NWs are ${\sim}60nm$ in average diameter and ${\sim}5um$ in average length. High resolution transmission microscopy measurements indicated that the NWs are single crystals covered with amorphous SiOx layers of ${\sim}3nm$ thickness. In addition, the optical properties of the NWs were investigated by micro-Raman spectroscopy. The downshift and asymmetric broadening of the Si main optical phonon peak were observed in Raman spectra of Si-NWs, which indicates a minute stress effects on Raman spectra due to a slight lattice distortion led by lattice expansion of Si-NW structures.

• Korean Chemical Engineering Research
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• v.44 no.4
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• pp.363-368
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• 2006

This study selected the optimal catalyst for the process of producing $C_9$-alcohol by hydrogenating $C_9$-aldehyde, and carried out an experiment in order to establish the operating condition for maximizing the yield of $C_9$-alcohol. The BET surface area and the specific area of copper were most excellent in $CuO/ZnO/Al_2O_3$ (60:30:10 wt％) catalyst produced using acetate as a precursor of copper and $Na_2CO_3$ as a precipitant, and the catalyst also showed the highest performance in $C_9$-aldehyde hydrogenation. Using a trickle bed reactor loaded with optimized catalyst, we attained 94.1 wt％ yield of $C_9$-alcohol under the condition of $175^{\circ}C$, 800 psi and $WHSV=3hr^{-1}$. According to the result of comparing with other catalysts used in the hydrogenation of aldehyde, the catalyst showed similar performance to that of Ni/kieselghur and higher than that of $Cu-Ni-Cr-Na/Al_2O_3$ and $Ni-Mo/Al_2O_3$. According to the result of examining the stability of the catalyst through a long-term catalysis test, the yield of $C_9$-alcohol decreased slowly after around 72 hours due to the increasing production of high boiling-point byproducts.

• Journal of the Korean Vacuum Society
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• v.16 no.4
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• pp.279-285
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• 2007

We have demonstrated structural evolution and optical properties of the Si-NWs on Si (111) substrates with synthesized nanoscale Au-Si islands by rapid thermal chemical vapor deposition(RTCVD). Au nano-islands (10-50nm in diameter) were employed as a liquid-droplet catalysis to grow Si-NWs via vapor-liquid-solid mechanism. Si-NWs were grown by a mixture gas of $SiH_4\;and\;H_2$ at pressures of $0.1{\sim}1.0$Torr and temperatures of $450{\sim}650^{\circ}C$. SEM measurements showed the formation of Si-NWs well-aligned vertically for Si (111) surfaces. The resulting NWs are 30-100nm in diameter and $0.4{\sim}12um$ in length depending on growth conditions. HR-TEM measurements indicated that Si-NWs are single crystals convered with about 3nm thick layers of amorphous oxide. In addition, optical properties of NWs were investigated by micro-Raman spectroscopy. The downshift and asymmetric broadening of the Si optical phonon peak with a shoulder at $480cm^{-1}$ were observed in Raman spectra of Si-NWs.

• Applied Chemistry for Engineering
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• v.17 no.3
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• pp.321-326
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• 2006

Thermal degradation of styrene dimer fraction (SDF, main compound: 47 wt% of 1,3-diphenylpropane), 5~15% of total products produced during decomposition of waste expanded polystyrene (WEPS) was investigated. Reaction condition of $360^{\circ}C$, and 152 kPa to 202 kPa was an optimum for high pressure degradation. Under this operating condition, the yield of oil was 73.8% and the selectivities to Ben, Tol, EB, SM, and AMS were 0.4, 30.9, 15.0, 19.6, and 4.2%, respectively. Non-catalytic fixed bed continuous degradation was conducted at reaction temperatures of $510{\sim}610^{\circ}C$ and contact time ranges of 2~24 min, where the yield was increased by increasing of reaction temperature and contact time. A $Cr_2O_3$ catalyst showed the highest activity and SM yield among acid, base, and redox catalysts. The conversion of 74.6% and the yield of Ben, Tol, EB, SM, and AMS were 0.4, 21.6, 9.7, 17.9, and 3.5%, respectively at $560^{\circ}C$ and contact time of 24 min. It is thought that styrene is converted to EB and other secondary products throughout the formation of diradicals of styrene.

• Applied Chemistry for Engineering
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• v.10 no.2
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• pp.247-251
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• 1999

Tungsten oxide supported on zirconia was prepared by drying powdered $Zr(OH)_4$ with ammonium metatungstate aqueous solution, followed by calcining in air at high temperature. Upon the addition of only small amount of tungsten oxide (1 wt % $WO_3$) to $ZrO_2$, both the acidity and acid strength of catalyst increased remarkably, showing the presence of $Br{\ddot{o}}nsted$ and Lewis acid sites on the surface of $WO_3$/$ZrO_2$. The high acid strength and large amount of acid sites on $WO_3$/$ZrO_2$ were due to the presence of the W=O bond nature of complex formed by the interaction between $WO_3$ and $ZrO_2$. The catalyst containing 20 wt % $WO_3$, calcined at 973 K, showed the highest catalytic activity for the 2-propanol dehydration, while the catalyst containing 15 wt % $WO_3$, calcined at 1023 K, exhibited the highest catalytic activity for the cumene dealkylation. For the 2-propanol dehydration the catalytic activities of $WO_3$/$ZrO_2$ catalysts were roughly correlated with their acidities.

• Applied Chemistry for Engineering
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• v.5 no.2
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• pp.327-336
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• 1994

The synergistic effects in mechanical mixture catalysts of Mo-V-O and metal oxide were investigated for the selective oxidation of acrolein. The metal oxides used are $SnO_2$, ${\alpha}-Sb_2O_4$, $WO_3$, ${\alpha}-Al_2O_3$, CuO, $MnO_2$, $Cu_2O$, MgO, CoO, and ZnO. Mechanical mixtures of Mo-V-O plus $SnO_2$ or ${\alpha}-Sb_2O_4$ had resulted in higher conversion of acrolein and higher yield of acrylic acid than Mo-V-O. The origin of the synergy is attributed to the cooperation of Mo-V-O and $SnO_2$ or ${\alpha}-Sb_2O_4$, in which $SnO_2$ or ${\alpha}-Sb_2O_4$ forms dissociated oxygens at their oxygen vacancies and transports them to Mo-V-O. $Cu_2O$, MgO, CuO, and $MnO_2$, increased conversion of acrolein but decreased yield of acrylic acid. CoO and ZnO inhibited the catalytic performance of Mo-V-O. The different role of these metal oxides is explained in terms of their oxidation-reduction properties.

• Applied Chemistry for Engineering
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• v.23 no.1
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• pp.1-7
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• 2012

In this article, I will introduce recent developments of environmental-friendly materials fabricated using atomic layer deposition (ALD). Advantages of ALD include fine control of the thin film thickness and formation of a homogeneous thin fim on complex-structured three-dimensional substrates. Such advantages of ALD can be exploited for fabricating environmental-friendly materials. Porous membranes such as anodic aluminum oxide (AAO) can be used as a substrate for $TiO_2$ coating with a thickness of about 10 nm, and the $TiO_2$-coated AAO can be used as filter of volatile organic compound such as toluene. The unique structural property of AAO in combination with a high adsorption capacity of amorphous $TiO_2$ can be exploited in this case. $TiO_2$ can be also deposited on nanodiamonds and Ni powder, which can be used as photocatalyst for degradation of toluene, and $CO_2$ reforming of methane catalyst, respectively. One can produce structures, in which the substrates are only partially covered by $TiO_2$ domains, and these structures turns out to be catalytically more active than bare substrates, or complete core-shell structures. We show that the ALD can be widely used not only in the semiconductor industry, but also environmental science.