• Bulletin of the Korean Chemical Society
• /
• v.23 no.1
• /
• pp.59-64
• /
• 2002

A facile and precise batch oxidation reaction system allows continuous monitoring of the oxidation rate and cumulated oxygen conversion of xylenes, and the side reactions to carbon monoxide and carbon dioxide may also be studied. The oxidation reaction can be analyzed precisely with the rate and amount of oxygen consumed. The reaction reveals that 4-carboxybenzaldehyde is an unstable intermediate of p-xylene oxidation as the reaction proceeds instantaneously from p-toluic acid to TPA (terephthalic acid). The alkali metals accelerate oxidation, even though they retard the reaction initially. The oxidation rate increases with decreasing water concentration. However, in the later part of reaction, the reactivity decreases a bit if the water concentration is very low. This retarding effect of water can be overcome partly by the addition of potassium. The oxidation of o-xylene, compared with the oxidation of p-xylene and m-xylene, proceeds quite fast initially, however, the oxidation rate of xylene isomers in the later stage of reaction is in the order of p-xylene > mxylene > o-xylene.

• Applied Chemistry for Engineering
• /
• v.2 no.2
• /
• pp.155-164
• /
• 1991

The reaction mechanism and the effects of the oxidation state of vanadium oxide and of support on catalytic activity for the oxidation of o-xylene were investigated. The oxidation of o-xylene simultaneously proceeded through the consecutive and parallel mechanisms. The high valence of vanadium favored selective oxidation to phthalic anhydride, while the low valence caused complete oxidation of phthalic anhydride to CO and $CO_2$. Crystalline $V_2O_5$ showed better selectivity for partial oxidation rather than amorphous one.

• Journal of Korean Society for Atmospheric Environment
• /
• v.23 no.1
• /
• pp.64-73
• /
• 2007

The catalytic activity of transition metals (Cu, Co, Mn, Fe and Ni) supported on ${\gamma}-Al_2O_3$ for the oxidation of toluene was investigated in the microreactor of fixed-bed type. The catalytic activity of transition metals for the oxidation of toluene turned out to be increasing in the order of Ni$Cu/{\gamma}-Al_2O_3$ catalysts for the oxidation of toluene increased with the increasing loadings of copper, reached the maximum activity at 5% loadings of copper, and decreased with higher loadings of copper in the catalysts. The activity of $Cu/{\gamma}-Al_2O_3$ catalysts for the oxidation of toluene decreased with the increasing calcination temperatures. This might result from the decreasing surface area of catalysts due to the sintering of copper oxide as well as ${\gamma}-Al_2O_3$ supports. The 5wt% $Cu/{\gamma}-Al_2O_3$ catalysts calcined at $400^{\circ}C$ for 4 hrs in the air showed the highest activity for the oxidation of toluene. Mutual inhibition was observed for the binary mixture of toluene and xylene. The activity of the easy-to-oxidize toluene was greatly decreased while the difficult-to-oxidize xylene was slightly decreased in the binary mixture of toluene and xylene. It might suggest that the inhibition of toluene and xylene in the binary mixture resulted from the competitive adsorption for the adsorbed oxygen on the catalytic surface.

• Journal of Korean Society for Atmospheric Environment
• /
• v.22 no.6
• /
• pp.799-807
• /
• 2006

The catalytic activity of $Pt/{\gamma}-Al_2O_3$ catalysts for the oxidation of toluene and toluene+xylene mixture was investigated in the microreactor of fixed-bed type. The calcination temperatures and loadings of $Pt/{\gamma}-Al_2O_3$ catalysts played the important role in the activity of catalysts for the oxidation of toluene. The increasing calcination temperatures and loadings of $Pt/{\gamma}-Al_2O_3$ catalysts increased the crystallite size of the platinum to result in the higher oxidation activity of catalysts. The catalytic activity for the toluene oxidation over $Pt/{\gamma}-Al_2O_3$ catalysts turned out to be increasing in the order of $500^{\circ}C\;<\;800^{\circ}C<600^{\circ}C\;<\;700^{\circ}C$ for calcination temperatures and 0.1 wt% < 0.3 wt% < 1.0 wt% for platinum loadings, respectively. The 1.0 wt% $Pt/{\gamma}-Al_2O_3$ catalysts calcined at $700^{\circ}C$ for 3 hrs in the air showed the highest activity for the oxidation of the toluene. The decrease of oxidation activity of $Pt/{\gamma}-Al_2O_3$ catalysts calcined at $800^{\circ}C$ might result from the decrease of active sites by sintering of platinum metals as well as ${\gamma}-Al_2O_3$ supports. The 1.0wt% $Pt/{\gamma}-Al_2O_3$ catalyst showed the activity from the lower temperature at $120^{\circ}C$, reached the light-off temperature ($T_{50%}$) at $180^{\circ}C$, and leveled off its activity at $340^{\circ}C$ with the conversion of 100% 'Mutual promotion' effects were observed for the binary mixture of toluene and xylene. The activity of the easy-to-oxidize toluene was slightly increased with the existence of the xylene. It might suggest the different mechanism for the oxidation of toluene and xylene on the $Pt/{\gamma}-Al_2O_3$ catalysts on different sites, and its reaction of gaseous oxygen.

• Applied Chemistry for Engineering
• /
• v.2 no.4
• /
• pp.330-339
• /
• 1991

The acid properties of $V_2O_5-TiO_2/SiO_2$ catalysts and the partial oxidation of o-xylene into phthalic anhydride had been investigated in order to relate the acid property of catalyst to the catalytic activity. $V_2O_5$ had both weak (V=O) and strong (V-O-V) acid sites which gave pyridine desorption peaks at $230^{\circ}C$ and $300^{\circ}C$, respectively, and the amount of weak acid sites at $230^{\circ}C$ decreased with the increase of calcination temperature. On the other hand, the amount of weak acid sites increased considerably by increasing the amount of $TiO_2$ to the $V_2O_5-TiO_2/SiO_5$, and the maximum value was shown at 20 and higher mole % of $TiO_2$ with respect to $SiO_2$. In the oxidation of o-xylene, $V_2O_5-TiO_2/SiO_2$ enhandced more the total conversion and the selectivity to phthalic anhydride than $V_2O_5/SiO_2$, and the higher $TiO_2$ ratio to $V_2O_5$ increased the total conversion but could not change the selectivity to phthalic anhydride. Weak acid sites (V=O) led o-xylene to partial oxidation producing phthalic anhydride by adsorbing o-xylene weakly, while acid sites (V-O-V) led it to total oxidation producing CO and $CO_2$ by adsorbing it strongly.

• Applied Chemistry for Engineering
• /
• v.10 no.8
• /
• pp.1161-1168
• /
• 1999

The redox property of oxide materials of the 3rd period transition metals(Cr~Zn), V, Mo, and W was studied with temperature-programmed reduction/temperature-programmed oxidation(TPR/TPO) experiment. The peak temperatures of TPO spectra were equal to or lower than those of TPR spectra. And the peak shapes of TPO spectra were broader than those of TPR ones. The activation energies of TPR/TPO for the oxides of the 3rd period transition metals showed in the range of 33~149 kJ/mol, while for the oxides of V, Mo, and W, they showed relatively higher values. The change of activation energies of TPR/TPO with various metal oxides showed a similar trend to the change of their metal-oxygen bond strengths. The change of activation energies of o-xylene oxidation for various metal oxides was proportional to the difference (${\Delta}E_a$) between the activation energy of TPR and that of TPO. From these results, we concluded that the oxidation of o-xylene over various metal oxide catalysts follows the Mars-van Krevelen mechanism including the surface reduction-oxidation of the metal oxide itself.

• Journal of Environmental Science International
• /
• v.17 no.11
• /
• pp.1195-1201
• /
• 2008

Enhancing with non-metallic elemental nitrogen(N) is one of several methods that have been proposed to modify the electronic properties of bulk titanium dioxide($TiO_2$), in order to make $TiO_2$ effective under visible-light irradiation. Accordingly, current study evaluated the feasibility of applying visible-light-induced $TiO_2$ enhanced with N element to cleanse aromatic compounds, focusing on xylene isomers at indoor air quality(IAQ) levels. The N-enhanced $TiO_2$ was prepared by applying two popular processes, and they were coated by applying two well-known methods. For three o-, m-, and p-xylene, the two coating methods exhibited different photocatalytic oxidation(PCO) efficiencies. Similarly, the two N-doping processes showed different PCO efficiencies. For all three stream flow rates(SFRs), the degradation efficiencies were similar between o-xylene and m,p-xylene. The degradation efficiencies of all target compounds increased as the SFR decreased. The degradation efficiencies determined via a PCO system with N-enhanced visible-light induced $TiO_2$ was somewhat lower than that with ultraviolet(UV)-light induced unmodified $TiO_2$, which was reported by previous studies. Nevertheless, it is noteworthy that PCO efficiencies increased up to 94% for o-xylene and 97% for the m,p-xylene under lower SFR(0.5 L $min^{-1}$). Consequently, it is suggested that with appropriate SFR conditions, the visible-light-assisted photocatalytic systems could also become important tools for improving IAQ.

• Journal of Environmental Science International
• /
• v.27 no.11
• /
• pp.967-974
• /
• 2018

In this study, we evaluated the photocatalytic oxidation efficiency of aromatic volatile hydrocarbons by using $WO_3$-doped $TiO_2$ nanotubes (WTNTs) under visible-light irradiation. One-dimensional WTNTs were synthesized by ultrasonic-assisted hydrothermal method and impregnation. XRD analysis revealed successful incorporation of $WO_3$ into $TiO_2$ nanotube (TNT) structures. UV-Vis spectra exhibited that the synthesized WTNT samples can be activated under visible light irradiation. FE-SEM and TEM images showed the one-dimensional structure of the prepared TNTs and WTNTs. The photocatalytic oxidation efficiencies of toluene, ethylbenzene, and o-xylene were higher using WTNT samples than undoped TNT. These results were explained based on the charge separation ability, adsorption capability, and light absorption of the sample photocatalysts. Among the different light sources, light-emitting-diodes (LEDs) are more highly energy-efficient than 8-W daylight used for the photocatalytic oxidation of toluene, ethylbenzene, and o-xylene, though the photocatalytic oxidation efficiency is higher for 8-W daylight.

• Korean Journal of Chemical Engineering
• /
• v.35 no.11
• /
• pp.2172-2184
• /
• 2018

The production of isophthalic acid (IPA) from the oxidation of m-xylene (MX) by air is catalyzed by $H_3PW_{12}O_{40}$ (HPW) loaded on carbon and cobalt. We used $H_2O_2$ solution to oxidize the carbon to improve the catalytic activity of HPW@C catalyst. Experiments reveal that the best carbon sample is obtained by calcining the carbon at $700^{\circ}C$ for 4 h after being impregnated in the 3.75% $H_2O_2$ solution at $40^{\circ}C$ for 7 h. The surface characterization displays that the $H_2O_2$ modification leads to an increase in the acidic groups and a reduction in the basic groups on the carbon surface. The catalytic capability of the HPW@C catalyst depends on its surface chemical characteristics and physical property. The acidic groups play a more important part than the physical property. The MX conversion after 180 min reaction acquired by the HPW@C catalysts prepared from the activated carbon modified in the best condition is 3.81% over that obtained by the HPW@C catalysts prepared from the original carbon. The IPA produced by the former is 46.2% over that produced by the latter.

• Analytical Science and Technology
• /
• v.19 no.5
• /
• pp.422-432
• /
• 2006

The volatile organic compounds(VOCs) have been recognized as a major contributor to air pollution. The catalytic oxidation is one of the most important processes for VOCs destruction due to getting high efficiency at low temperature. In this study, monometallic Pt and bimetallic Pt-Ru, Pt-Ir were supported to ${\gamma}-Al_2O_3$. Xylene, toluene and MEK were used as reactants. The monometallic or bimetallic catalysts were prepared by the excess wetness impregnation method and were characterized by XRD, XPS, TEM and BET analysis. As a result, Pt-Ru, Pt-Ir bimetallic catalysts showed higher conversion than Pt monometallic catalyst. Pt-Ir bimetallic catalyst showed the highest conversion on the ${\gamma}-Al_2O_3$ support. In the VOCs oxidation, Pt-Ru, Pt-Ir bimetallic catalyst had multipoint active sites, so it improved the range of Pt metal state. Therefore, bimetallic catalysts showed higher conversion of VOCs than monometallic ones. In this study, the use of small amount of Ru, Ir to Pt promoted oxidation conversion of VOCs.