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.

A Preliminary Study on the Use of Highly Aromatic Pyrolysis Oils Coming from Plastic Waste as Alternative Liquid Fuels.

In this work, the low-temperature pyrolysis of a real plastic mixture sample collected at a WEEE-authorised recycling facility has been investigated. The sample was pyrolysed in a batch reactor in different temperature and residence time conditions and auto-generated pressure by following a factorial design, with the objective of maximising the liquid (oil) fraction. Furthermore, the main polymers constituting the real sample were also pyrolysed in order to understand their role in the generation of oil. The pyrolysis oils were characterised and compared with commercial fuel oil number 6. The results showed that in comparison to commercial fuel oil, pyrolysis oils coming from WEEE plastic waste had similar heating values, were lighter and less viscous and presented similar toxicity profiles in fumes of combustion.

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.