• Korean Chemical Engineering Research
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• v.51 no.2
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• pp.208-213
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• 2013

Zirconium hydroxide was synthesized by varying the aging time of the zirconyl chloride octahydrate at $100^{\circ}C$ in aqueous solution and the resulting hydroxides were calcined at $700^{\circ}C$ for 6 h to obtain the crystalline $ZrO_2$. The materials used in this study were characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), $N_2$-sorption, transmission electron microscopy (TEM), $NH_3$ temperature-programmed desorption ($NH_3$-TPD), $CO_2$-TPD and iso-propanol TPD analyses to correlate with catalytic activity for the dehydration of iso-propanol. The pure tetragonal $ZrO_2$ phase was obtained after 24 h aging of zirconium hydroxide and successive calcination at $700^{\circ}C$. The increase of aging time showed the production of smaller particle size $ZrO_2$ resulting that the higher specific surface area and total pore volume. $NH_3$-TPD results revealed that the relative acidity of the catalysts increased along with the increase of aging time. On the other hand, the results of $CO_2$-TPD showed the reverse trend of $NH_3$-TPD results. The best catalytic activity for the dehydration of iso-propanol to propylene was shown over $ZrO_2$ catalyst aged for 168 h which had the highest $S_{BET}$ ($178\;m^2\;g^{-1}$). The catalytic activity could be correlated with high surface area, relative acidity and easy desorption of iso-propanol.

• Korean Chemical Engineering Research
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• v.53 no.3
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• pp.391-396
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• 2015

To investigate the effect of the catalyst synthesis method on the oxidative dehydrogenation (ODH) of nbutenes, $BiFe_{0.65}MoP_{0.1}$ oxide catalysts were prepared with various synthesis methods such as co-precipitation, citric acid method, hydrothermal method, and surfactant templated method. The catalysts were characterized by X-ray Diffraction (XRD), $N_2$ sorption, and $NH_3/1$-butene-temperature programmed desorption ($NH_3/1$-butene-TPD) to correlate with catalytic activity in ODH reaction. Among the catalysts studied here, $BiFe_{0.65}MoP_{0.1}$ oxide catalyst prepared with co-precipitation method marked the highest activity showing 1-butene conversion, 79.5%, butadiene selectivity, 85.1% and yield, 67.7% after reaction for 14 h. From the result of $NH_3$-TPD, the catalytic activity is closely related to the acidity of the $BiFe_{0.65}MoP_{0.1}$-x oxide catalyst and acidity of the $BiFe_{0.65}MoP_{0.1}$ oxde catalyst prepared with co-precipitation method was higher than that of other catalysts. In addition, combined with the 1-butene TPD, the higher catalytic activity is closely related to the amount of weakly adsorbed intermediate (< $200^{\circ}C$) and the desorbing temperature of strongly adsorbed intermediates (> $200^{\circ}C$).

• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.512-518
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• 2008

The present work studied the selective catalytic reduction (SCR) of NO to $N_2$ by $NH_3$ over $V/TiO_2$ focusing on NOx control for the stationary sources. The SCR process depends mainly on the catalyst performance. The reaction characteristics of SCR with $V/TiO_2$ catalysts were closely examined at low and high temperature. In addition, adsorption and desorption characteristics of the reactants on the catalyst surface were investigated with ammonia. Seven different $TiO_2$ supports containing the same loading of vanadia were packed in a fixed bed reactor respectively. The interaction between $TiO_2$ and vanadia would form various non-stoichiometric vanadium oxides, and showed different reaction activities. There were optimum calcination temperatures for each samples, indicating different reactivity. It was finally found from the $NH_3-TPD$ test that the SCR activity was nothing to do with $NH_3$ adsorption amount.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.265-265
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• 2012

The adsorption of molecular $NH_3$ on rutile $TiO_2(110)-1{\times}1$ surfaces was investigated using a temperature-programmed desorption (TPD) technique combined with a molecular beam apparatus. A quantitative investigation into the TPD spectra of $NH_3$ was made for $NH_3$ adsorbed on two kinds of rutile $TiO_2(110)-1{\times}1$ surfaces with the oxygen vacancy ($V_O$) concentration of ~0% (p-$TiO_2(110)$) and ~5% (r-$TiO_2(110)$), respectively. On both surfaces, non-dissociative adsorption of $NH_3$ was inferred from a quantitative analysis on the amount of adsorbed $NH_3$ and those desorbed. With increasing coverage, the monolayer desorption feature shifted from 400 K toward lower temperatures until it saturates at 160 K, suggesting a repulsive nature in the interaction between $NH_3$ molecules. At the very low coverage regime, the desorption features were found to extend up to 430 K and 400 K on p-$TiO_2(110)$ and p-TiO(110), respectively. As a result, the saturation coverage of monolayer of $NH_3$ was higher on the p-$TiO_2(110)$ surface than on the p-TiO(110) by about 10%. The desorption energy ($E_d$) of $NH_3$ obtained by inversion of the Polanyi-Wigner equation indicated that the difference between the $E_d$'s of $NH_3$ (that is, $E_d(on\;p-TiO_2(110)$) - $E_d$(on p-TiO(110)) was 14 kJ/mol at ${\theta}(NH_3)=0$ and decreased to 0 as the coverage approached to a monolayer. The observed adsorption behavior of $NH_3$ was interpreted using an interaction model between $NH_3$ and surface defects on $TiO_2$ such as VO's and $Ti^{3+}$ interstitials.

• Clean Technology
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• v.22 no.1
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• pp.9-15
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• 2016

xAl-yZr mixed oxide catalysts with different molar ratios of Al/(Al+Zr) were prepared by a co-precipitation method and its catalytic performance was compared in the iso-propanol dehydration as a model reaction. The catalysts were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), N₂ adsorprion-desorption, NH₃ temperature programmed desorption (NH₃-TPD), and iso-propanol TPD analyses. The addition of Al into ZrO₂ promoted the formation of relatively small particles with large surface areas and retarded the transformation of teragonal phase to monoclnic phase. NH₃-TPD results revealed that the relative acidity of the catalysts increased along with the increase of Al molar ratio. The catalytic activity for the dehydration of iso-propanol to propylene was also increased with the same tendency. The catalytic activity could be correlated with high surface area, acidity and easy desorption of iso-propanol.

• Applied Chemistry for Engineering
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• v.28 no.3
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• pp.355-359
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• 2017

Zeolite X with Si/Al molar ratio = 1.08~1.20 was produced using a hydrothermal synthesis method. Ion-exchanged zeolite X samples were then prepared by using metal nitrate solutions containing $Mg^{2+}$ or $Cu^{2+}$. For all zeolite X samples, X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS) were used to identify the change in crystal structure. The analysis of ammonia adsorption capability of zeolite X samples was conducted through the ammonia temperature-programmed desorption ($NH_3$-TPD) method. From XRD results, the prepared zeolite X samples maintained the Faujasite (FAU) structure regardless of cation contents in zeolite X, but the crystallinity of zeolite X containing $Mg^{2+}$ and $Cu^{2+}$ cations decreased. The distribution of cation contents in zeolite X was identified via EDS analysis. $NH_3$-TPD analysis showed that the $NH_3$ adsorption capacity of $Mg^{2+}$- and $Cu^{2+}$-zeolite X were 1.76 mmol/g and 2.35 mmol/g, respectively while the $Na^+$-zeolite X was 3.52 mmol/g ($NH_3/catalyst$). $Na^+$-zeolite X can thus be utilized as an adsorbent for the removal of ammonia in future.

• Applied Chemistry for Engineering
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• v.31 no.2
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• pp.200-207
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• 2020

In this study, the effect of calcination temperature on the production of RuTi catalyst in NH₃-SCO (selective catalytic oxidation) was investigated. The RuTi catalyst was prepared using the wet impregnation method, and calcined at 400~600 ℃ for 4 h in air condition. The catalysts were named RuTi x00 where x00 means the calcination temperature. According to XRD (X-Ray diffraction), TEM (transmission electron microscope), H₂-TPR (H₂-temperature programmed reduction) analyses, RuTi x00 catalysts displayed that the dispersion of active metal decreased via increasing the calcination temperature. The catalysts with low dispersion showed a decrease in the surface adsorption oxygen species (O_β) and NH₃ adsorption amount via XPS, and NH₃-TPD analyses. Therefore, the RuTi 400 catalyst was well dispersed in the active metal on TiO₂ surface, and also, the NH₃ removal efficiency was excellent.

• Clean Technology
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• v.26 no.4
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• pp.321-328
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• 2020

This experiment compared V/W/TiO2 and V/Mo/TiO2 catalysts that were used for commercial catalysts. The effects of SCR reactions on low-temperature activity were studied. NH3-TPD, DRIFT, and H2-TPR analysis, alongside O2-on/off experiments, were conducted to identify the effects of NH3 acid sites and oxygen participating in the SCR reaction, which had a significant impact on the NH3-SCR reaction. The effect on activity was analyzed at 250 ℃, a high temperature of reaction activity, and 180 ℃, which showed significant activity degradation. In NH3 involved in the SCR reaction at 250 ℃, B and L acid sites contributed to the reaction. In particular, the B acid site was found to have significantly participated in the reaction and affected the NH3-SCR activity, which was reduced at 180 ℃ to affect the activity degradation. Also, atmospheric oxygen contributed to the SCR reaction, causing the active property to facilitate reaction activity at 250 ℃. However, oxygen did not comprise the reaction at 180 ℃, indicating a drop inactivity. Therefore, the B acid site was reduced, and the activity was judged to be degraded due to failure to share in the reaction and low effects by atmospheric oxygen.

• Applied Chemistry for Engineering
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• v.31 no.5
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• pp.560-567
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• 2020

In this study, we investigated that the effect of alkali metals [Na(Sodium) and K(Potassium)], known as representative deactivating substances among exhaust gases of various industrial processes, on the NH₃-SCR (selective catalytic reduction) reaction of V/W/TiO₂ catalysts. NO, NH₃-TPD (temperature programmed desorption), DRIFT (diffuse reflectance infrared fourier transform spectroscopy analysis), and H₂-TPR analysis were performed to determine the cause of the decrease in activity. As a result, each alkali metal acts as a catalyst poisoning, reducing the amount of NH₃ adsorption, and Na and K reduce the SCR reaction by reducing the L and B acid points that contribute to the reaction activity of the catalyst. Through the H₂-TPR analysis, the alkali metal is considered to be the cause of the decrease in activity because the reduction temperature rises to a high temperature by affecting the reduction temperature of V-O-V (bridge oxygen bond) and V=O (terminal bond).

• Applied Chemistry for Engineering
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• v.33 no.1
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• pp.64-70
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• 2022

In this study, an experiment was performed by adding Sb during NH3-selective catalytic reduction (NH₃-SCR) while varying calcination temperatures from 400 to 700 ℃ to improve the low temperature denitrification efficiency of VWTi catalyst. As a result, VWSbTi(500) and VWSbTi(600) catalysts corresponding to Sb calcination temperatures of 500~600 ℃ showed the best denitrification performance at low temperatures below 300 ℃. BET, XRD, Raman, XPS, H₂-TPR, and NH₃-TPD analyses were performed In order to confirm physicochemical properties according to the calcination temperature. In the case of VWSbTi(500) and VWSbTi(600), an acid site increased with the generation of W=O species, and superb activity at low temperatures was exhibited due to the excellent redox characteristics and increase in electron density of tungsten. Furthermore, in the case of VWSbTi(700), as the crystalline V₂O₅ structure was formed, the denitrification efficiency decreased. Thus the optimum calcination temperature during Sb addition process was confirmed.