Wet hydrogen peroxide catalytic oxidation (WHPCO) of organic waste in agro-food and industrial streams

This review discusses the use of iron- or copper-based solid catalysts in the wet oxidation using H₂O₂ as oxidant of organic molecules present in agro-food and industrial waste aqueous streams. After an introduction on the advantages and limits of using wet hydrogen peroxide catalytic oxidation (WHPCO) as opposite to wet air catalytic oxidation (WACO), the contribution shortly analyses recent results in the field in order to evidence new trends and open issues. More specific examples discussed regard the performances of Fe/zeolite and Fe-containing pillared clays in the oxidation of selected molecules (p-coumaric acid, propionic acid) of relevance for the treatment of organic waste from agro-food production (with reference especially to olive oil milling wastewater). The application of WHPCO in the treatment of complex effluents from electronic industry is also shortly discussed.     

Use of mesoporous SBA-15 for nanostructuring titania for photocatalytic applications

SBA15–TiO₂ samples prepared by introducing titanium with a grafting method and having TiO₂ loadings below 15 wt.% have been characterized by XRF, XRD, IR, porosimetry, SEM, HRTEM, and UV–Visible diffuse reflectance. Differently from the samples reported in the literature characterized by a high TiO₂ loading, no evidences have been found for the presence of titania particles inside or outside the mesopores of SBA-15. Three different titanium species were instead evidenced to be present. The first two derive from the reaction of titanium with silanol groups in the corona area of inner SBA-15 walls leading to the formation of either TiO₄ tetrahedral sites (by reaction by hydroxyl nests of surface defect sites) and/or pseudo-octahedral surface sites anchored by two (or more) Si or Ti ions through bridging oxygens. The third species derives from the reaction of titanium in the regions with high sylanol density, e.g. in the micropores located in the corona of SBA-15 channels, leading to the formation of TiO₂-like nanoareas (probably Si-doped) with dimensions of around 1–2 nm maximum. The potential interest of these materials as photocatalysts, for the presence of a TiO₂-like nanoareas highly accessible by reactants, is discussed.     

Homogeneous versus heterogeneous catalytic reactions to eliminate organics from waste water using H2O2

Homogeneous (Cu²⁺ ions) and heterogeneous (Cu²⁺-pillared clay) Fenton-like catalysts have been compared in the conversion of p-coumaric acid. The performances of the two classes of catalysts are similar for an analogous amount of copper, but there are some relevant differences in terms of (i) the presence of an induction time, (ii) the turnover frequency, (iii) the efficiency in the use of H₂O₂, (iv) the initial attack of p-coumaric acid (hydroxylation on the aromatic ring or oxidative attack on the double bond of the lateral chain), and (v) the effect of dissolved oxygen on the removal of total organic carbon (TOC). These differences were interpreted in terms of reaction network of generation of radical oxygen species and of organics conversion. The possible formation of a surface peroxo adduct coordinated to a copper binulcear site was also evidenced for the solid heterogeneous catalyst.     

NOx storage-reduction catalysts based on hydrotalcite: Effect of Cu in promoting resistance to deactivation

Novel NO_x storage-reduction (NO_xSR) catalysts prepared by Pt and/or Cu impregnation of Mg–Al (60:40) hydrotalcite (HT)-type compounds show better performances in NO_x storage than Pt–Ba/Al₂O₃ Toyota-type NO_xSR catalysts at reaction temperatures lower than 250 °C. The presence of Pt or Cu considerably enhances the activity, with the former more active. The nature of the HT source, however, also influences performance. The co-presence of Pt and Cu slightly worsens the low temperature activity, but considerably promotes the resistance to deactivation after severe hydrothermal treatment and in the presence of SO₂. This effect is attributed to both the possibility of formation of a Pt–Cu alloy after reduction, and the modification of the HT induced during the deposition of Cu. The overall Pt–Cu/HT performances are thus superior to those of the Pt–Ba/Al₂O₃ Toyota-type NO_xSR catalysts.     

Role and importance of oxidized nitrogen oxide adspecies on the mechanism and dynamics of reaction over copper-based catalysts

The formation of nitrate and NO₂ adspecies over Cu/MFI and copper-on-alumina catalysts and their role in the mechanism of reaction is discussed on the basis of FT-IR results and catalytic tests in unsteady-state conditions. Three specific cases are discussed: (i) reduction of NO by propane/O₂ over Cu/MFI, (ii) conversion of NO by NH₃/O₂ over copper-on-alumina catalysts and (iii) oxygen-promoted reduction of NO in the absence of reductants over Cu/MFI. The formation of nitrate species leads to self-deactivation, but Cu²⁺-NO₂ like adspecies are suggested to be a key intermediate in the reduction of NO to N₂ in all three cases examined.     

Catalytic conversion of MTBE to biodegradable chemicals in contaminated water

The behavior of different acid zeolites in the hydrolysis at room temperature of methyl tert-butyl ether (MTBE) was studied with reference to the possibility of its conversion to more biodegradable products in underground water contaminated by MTBE. The effect of the structure of the zeolite and SiO₂/Al₂O₃ ratio was analyzed. The results indicate that acid H-MFI and H-BEA zeolites are effective in both adsorption and hydrolysis of MTBE and may be applied for both in situ underground water remediation and as protection barrier for wells or leaking tanks. However, other zeolites (mordenite and faujasite) result completely inactive. Furthermore, contrary to what was expected, the increase of the Si/Al ratio promotes the reactivity which is determined by the resistance to diffusion of MTBE in the pores of zeolites and the resistance of back-diffusion of the reaction products.     

Transient Surface Processes of Storage and Conversion of NOx Species on Pt–Me/Al2O3 Catalysts (Me = Ba,Ce, Cu)

The transient reactivity and surface phenomena of storage and conversion of NO _x species on Pt(1%)–Me/Al₂O₃ catalysts, where Me = Ba, Ce and Cu, were studied by the RWF (rectangular wavefront) method. The Me component has a relevant influence on the processes of surface storage and transformation. The reduction of NO _x by propene in the presence of oxygen is promoted by adding Cu to a Pt/Al₂O₃ catalyst, while cerium promotes transient conversion of NO in the absence of propene, but inhibits the reduction of NO _x in the presence of propene. Copper is suggested to be a promising element to add together with Ba for new NO _x storage-reduction catalysts due to its capacity to act both as a storage element and as promoter for NO _x reduction.     

Oxidation Catalysts Based on Antimony Mixed Oxides with Rutile-Type Structures

Several authors have correlated catalyst structure to catalytic behavior in selective oxidation reactions. Sleight [1] reviewed the importance of the scheelite structure for the allylic oxidation and ammonoxidation of olefins; Grasselli and co-workers [2–4] extensively examined the relationship between structure and catalytic activity of bismuth-molybdates, uranium-antirnonates, and bismuth-cerium molybdates. Bordes and Courtine [5] correlated the activity in mild oxidation of 1-butene to the properties of the structure of vanadium-phosphorus oxides. However, little attention has been given in the literature to the role of the rutile structure in allylic oxidation reactions even though the high activity and selectivity of antimony oxides stabilized in matrices with rutile structure (SnO₂ and FeSbO₄) in olefins oxidation and ammonoxidation have been known for several years. Furthermore, Tables 1 and 2 indicate that the kinetic and catalytic behavior of antimony-based catalysts in allylic oxidation reactions are very different from that of molybdate-based catalysts. This suggests that antimony- and molybdate-based catalysts are two distinct classes of catalysts of allylic oxidation, in agreement with a recent suggestion by Grasselli et al. [13].