Promotion of Cobalt Oxide Catalysts by Acid-Etching and Ruthenium Incorporation for Chlorinated VOC Oxidation.

In this work, Ru-promoted cobalt oxide catalysts with a nanotube morphology were prepared by a synthesis route based on the Kirkendall effect followed by an acid treatment and subsequent optimized Ru impregnation. The resulting samples were thoroughly characterized by means of N2 physisorption, X-ray energy-dispersive spectroscopy, X-ray diffraction, scanning electron microscopy techniques, X-ray photoelectron spectroscopy, and temperature-programmed techniques (O2-temperature-programmed desorption, H2-temperature-programmed reduction, and temperature-programmed oxidation) and evaluated in the gas-phase oxidation of 1,2-dichloroethane. It has been demonstrated that Ru addition improves the oxygen mobility as well as the amount of Co2+ and Oads species at the surface by the formation of the Ru-O-Co bond, which in turn governs the performance of the catalysts in the oxidation reaction. Moreover, the acid-etching favors the dispersion of the Ru species on the surface of the catalysts and strengthens the interaction among the noble metal and the cobalt oxide, thereby improving the thermal stability of the Ru-promoted oxides. Thus, the resulting catalysts are not only active, as the chlorinated pollutant is efficiently converted into deep oxidation products at relatively low temperatures, but also quite stable when operating for 120 h.

Viability of Glycolysis for the Chemical Recycling of Highly Coloured and Multi-Layered Actual PET Wastes.

The chemical recycling of poly(ethylene terephthalate) -PET- fractions, derived from actual household packaging waste streams, using solvolysis, was investigated. This recycling strategy was applied after a previous on-line automatic identification, by near-infrared spectroscopy -NIR-, and a subsequent selective sorting of the different PET materials that were present in the packaging wastes. Using this technology, it was possible to classify fractions exclusively including PET, virtually avoiding the presence of both other plastics and materials, such as paper, cardboard and wood, that are present in the packaging wastes, as they were efficiently recognised and differentiated. The simple PET fractions, including clear and monolayered materials, were adequate to be recycled by mechanical means meanwhile the complex PET fractions, containing highly coloured and multi-layered materials, were suitable candidates to be recycled by chemical routes. The depolymerisation capacity of the catalytic glycolysis, when applied to those complex PET wastes, was studied by evaluating the effect of the process parameters on the resulting formation and recovery of the monomer bis(2-hydroxyethyl) terephthalate -BHET- and the achieved quality of this reaction product. Comparable and reasonable results, in terms of monomer yield and its characteristics, were obtained independently of the type of complex PET waste that was chemically recycled.

On the Effect of the Synthesis Route of the Support in Co3O4/CeO2 Catalysts for the Complete Oxidation of Methane.

Six ceria supports synthesized by various synthesis methodologies were used to deposit cobalt oxide. The catalysts were thoroughly characterized, and their catalytic activity for complete methane oxidation was studied. The supports synthesized by direct calcination and precipitation with ammonia exhibited the best textural and structural properties as well as the highest degree of oxidation. The remaining supports presented poorer textural properties to be employed as catalytic supports. The cobalt deposited over the first two supports presented a good dispersion at the external surface, which induced a significant redox effect that increased the number of Co3+ ions on their surface. Consequently, the presence of highly active lattice oxygen species on the surface of these catalysts was favored. Additionally, the optimal active catalyst (Co-DC) revealed a significant resistance to water vapor inhibition, owing to the high hydrophobicity of the ceria support.

Comparative Study of the Efficiency of Different Noble Metals Supported on Hydroxyapatite in the Catalytic Lean Methane Oxidation under Realistic Conditions.

The combustion of lean methane was studied over palladium, rhodium, platinum, and ruthenium catalysts supported on hydroxyapatite (HAP). The samples were prepared by wetness impregnation and thoroughly characterized by BET, XRD, UV-Vis-NIR spectroscopy, H2-TPR, OSC, CO chemisorption, and TEM techniques. It was found that the Pd/HAP and Rh/HAP catalysts exhibited a higher activity compared with Pt/HAP and Ru/HAP samples. Thus, the degree of oxidation of the supported metal under the reaction mixture notably influenced its catalytic performance. Although Pd and Rh catalysts could be easily re-oxidized, the re-oxidation of Pt and Ru samples appeared to be a slow process, resulting in small amounts of metal oxide active sites. Feeding water and CO2 was found to have a negative effect, which was more pronounced in the presence of water, on the activity of Pd and Rh catalysts. However, the inhibiting effect of CO2 and H2O decreased by increasing the reaction temperature.

Synthesis, Characterization and Kinetic Behavior of Supported Cobalt Catalysts for Oxidative after-Treatment of Methane Lean Mixtures.

The present work addresses the influence of the support on the catalytic behavior of Co3O4-based catalysts in the combustion of lean methane present in the exhaust gases from natural gas vehicular engines. Three different supports were selected, namely γ-alumina, magnesia and ceria and the corresponding catalysts were loaded with a nominal cobalt content of 30 wt. %. The samples were characterized by N2 physisorption, wavelength dispersive X-ray fluorescence (WDXRF), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction with hydrogen and methane. The performance was negatively influenced by a strong cobalt-support interaction, which in turn reduced the amount of active cobalt species as Co3O4. Hence, when alumina or magnesia supports were employed, the formation of CoAl2O4 or Co-Mg mixed oxides, respectively, with a low reducibility was evident, while ceria showed a lower affinity for deposited cobalt and this remained essentially as Co3O4. Furthermore, the observed partial insertion of Ce into the Co3O4 lattice played a beneficial role in promoting the oxygen mobility at low temperatures and consequently the catalytic activity. This catalyst also exhibited a good thermal stability while the presence of water vapor in the feedstream induced a partial inhibition, which was found to be completely reversible.

Surface Characterization of Mesoporous CoOx/SBA-15 Catalyst upon 1,2-Dichloropropane Oxidation.

The active combustion catalyst that is based on 30 wt % cobalt oxide on mesoporous SBA-15 has been tested in 1,2-dichloropropane oxidation and is characterized by means of FT-IR (Fourier transform infrared spectroscopy) and ammonia-TPD (temperature-programmed desorption). In this work, we report the spectroscopic evidence for the role of surface acidity in chloroalkane conversion. Both Lewis acidity and weakly acidic silanol groups from SBA support are involved in the adsorption and initial conversion steps. Moreover, total oxidation reaction results in the formation of new Bronsted acidic sites, which are likely associated with the generation of HCl at high temperature and its adsorption at the catalyst surface. Highly dispersed Co oxide on the mesoporous support and Co-chloride or oxychloride particles, together with the presence of several families of acidic sites originated from the conditioning effect of reaction products may explain the good activity of this catalyst in the oxidation of Chlorinated Volatile Organic Compounds.

Inverse gas chromatography as a technique for the characterization of the performance of Mn/Zr mixed oxides as combustion catalysts.

Adsorption of different volatile organic compounds (trichloroethylene, TCE; 1,2-dichloroethane, DCE; n-hexane) over different manganese-zirconia mixed oxides (Mn(x)Zr(1-x)O(2)) - widely used as combustion catalysts - was studied by inverse gas chromatography. Adsorption isotherms (calculated in the Henry region), adsorption enthalpies (DeltaH(ads)), and dispersive (gamma(S)(D)) and specific (I(sp)) components of the surface energy have been determined at infinite dilution for the investigated compounds. Both the adsorption enthalpy and the specificity of the interaction of TCE and DCE over Mn(x)Zr(1-x)O(2) catalysts depend strongly on manganese content. Thus, the adsorption strength of the reactants over the active sites is closely related with both the surface acidity and the accessibility of the lattice oxygen. A great influence of the specific interaction on the catalytic pattern has been also noticed. Since I(sp) depends on the redox properties, it has been proved that the specific interaction is determined by the presence of bulk Mn(3)O(4), which hinders the mobility of the oxygen lattice, and MnO(x), with the contrary effect. Finally, the selectivity to oxidation products has been correlated with both the enthalpy of adsorption and the specific interaction parameter, decreasing the selectivity to HCl with the increase of the enthalpy of adsorption.

Role of water and other H-rich additives in the catalytic combustion of 1,2-dichloroethane and trichloroethylene.

In several practical applications gas streams containing chlorinated volatile organic compounds with variable chemical nature (namely, 1,2-dichloroethane and trichloroethylene) and a significant moisture content (15000ppm) must be addressed. In this paper the control of such emissions by catalytic oxidation over Ce/Zr mixed oxides was analysed. Results in terms of activity and selectivity were compared with those obtained when other H-rich additives (1000ppm), such as hexane or toluene, were fed. High activity was found from mixed oxides featuring a suitable combination of a large population of acid sites, easily accessible oxygen species, and hydrophobic nature attributable to cerium content. The presence of additional H-rich compounds in the feed stream (water, toluene or hexane) tended to decrease the catalytic activity due to the blockage and/or competition for actives sites. However, the increased presence of hydrogen atoms in the stream notably promoted the selectivity to hydrogen chloride instead of molecular chlorine.

Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons.

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.

Characterization of ceria-zirconia mixed oxides as catalysts for the combustion of volatile organic compounds using inverse gas chromatography.

Inverse gas chromatography (IGC) has been used in this work for characterizing the adsorption of different volatile organic compounds (VOCs) (1,2-dichloroethane (DCE), trichloroethylene (TCE), and n-hexane) over ceria-zirconia mixed oxides (Ce(x)Zr(1-x)O2, with x = 0, 0.15, 0.5, 0.68, 0.8 and 1). These materials have shown to be very active catalysts for the deep oxidation of the studied VOCs in previous papers. The enthalpies of adsorption (-deltaH(ads)), adsorption isotherms (corresponding to the Henry region), and dispersive (gamma(s)(D)) and specific (I(sp)) components of the surface energy for the adsorption of the investigated compounds are determined using IGC at infinite dilution. These chromatographic data and other surface parameters (surface area, oxygen storage capacity, surface acidity, and reducibility) are correlated with the activity and selectivity of these catalysts. As a result, for n-hexane, the catalytic activity is mainly correlated with the adsorption capacity of the solids, whereas the activity for chlorinated compounds oxidation (as well as the selectivity to oxidation products) depends on both oxygen storage capacity and specific interaction of the chlorinated compound with the surface.