New insights on the removal of diclofenac and ibuprofen by CWPO using a magnetite-based catalyst in an up-flow fixed-bed reactor.

This research has been focused on the removal of two anti-inflammatory drugs, diclofenac (DCF) and ibuprofen (IBU), by a continuous catalytic wet peroxide oxidation (CWPO) process using a lab-synthesized nanomagnetic catalyst (Fe3O4/MWCNTs). The central composite rotatable design (CCRD) method was used to study the effect of DCF and IBU concentration (expressed as theoretical oxygen demand (ThOD) between 0 and 52.5 mg L-1) and of the feed stream pH (from 3 to 7) on the removal of total organic carbon (TOC) and the concentration of aromatic compounds (Arm) and total phenolic compounds (TP) by CWPO. It could be observed that DCF was preferably removed from the DCF-IBU aqueous mixture at pH values ranging from 3 to 5. In addition, feed stream pH had a significant effect on the pollutants removal, as well as on TOC, TP and aromatic compounds removal, observing an increasing in the pollutants degradation when feed stream pH decreased from 7 to 3. Quadratic models predicted for response variable, such as TOC, TP and aromatic compounds removal, and their maximum model-predicted removal values were of 90.0, 80.2 and 90.0%, respectively. Finally, as a proof of concept, three environmentally-relevant aqueous matrices, spiked with DCF-IBU mixture, were treated. In this case, relatively high TOC degradation values were found after 20 h reaction time (ca. 57.7, 73.9 and 54.5% in surface water, WWTP effluent and hospital wastewater, respectively). This work deals the first study about DCF-IBU removal in aqueous solution by CWPO, as well as a continuous study using real wastewater that allow to extend the experimental results to a real scenario.

Ni/Fe-supported over hydrotalcites precursors as catalysts for clean and selective oxidation of Basic Yellow 11: reaction intermediates determination.

In this work, Basic Yellow 11 (BY 11) was employed as model compound to study catalytic wet air oxidation as a pre-treatment step to the conventional biological oxidation. Ni and Fe catalysts supported over hydrotalcite (HT) were prepared by incipient wetness and excess impregnation to obtain catalysts with different metal loadings (from 1 to 10 wt.%). HTs were synthesized by co-precipitation and characterized with XRD, X-ray fluorescence (XRF), BET, thermogravimetric analysis and SEM. Results showed that dye conversion increased with Ni and Fe content up to 7 wt.% and that the most effective catalyst were prepared by incipient wetness impregnation. The influence of metal loading in the catalyst, and the preparation method as well as the reaction conditions was investigated. A mechanism and reaction pathways for BY 11 during catalytic liquid phase oxidation have also been proposed.

Catalytic wet air oxidation with Ni- and Fe-doped mixed oxides derived from hydrotalcites.

Catalytic wet air oxidation of Basic Yellow 11 (BY11), a basic dye, was studied in a batch reactor. Layered double hydroxides with the hydrotalcite-like structure containing nickel or iron cations have been prepared by coprecipitation and subsequently calcined leading to Ni- and Fe-doped mixed oxides, respectively. Compared with the results in the wet air oxidation of BY11, these catalysts showed high activity for total organic carbon (TOC), toxicity and dye removal at 120 degrees C and 50 bars after 120 min. It has been demonstrated that the activity depended strongly on the presence of catalyst. The results show that catalysts containing nickel provide a higher extent of oxidation of the dye whereas the reaction carried out with the iron catalyst is faster. The Ni and Fe dispersion determined from the TPR results was higher for the catalysts with a lower Ni or Fe content and decreased for higher Ni or Fe contents. On the basis of activity and selectivity, the Ni containing catalyst with the medium (3%) Ni content was found to be the best catalyst. Finally, a relationship between metal content of the catalyst and reaction rate has been established.

Adsorption of dyes on carbon nanomaterials from aqueous solutions.

The removal of methylene blue (MB), a cationic dye and orange II (OII), an anionic dye, from aqueous solution by using carbon nanomaterials as multiwalled carbon nanotubes (MWNTs) and carbon nanofibers (CNF) as adsorbents was studied in batch experiments. The effect of pH, temperature and surface modification of adsorbent on the removal of MB and OII was also investigated. The removals of OII and MB by adsorption on MWNT were maximum at pH 3.0 and pH 7.0, respectively. However, in the case CNF was employed as adsorbent, the optimum values of pH were 9.0 and 5.0 for OII and MB, respectively. Langmuir and Freundlich isotherms are applied to fit the adsorption data of both dyes. Equilibrium data were well described by the typical Langmuir adsorption isotherm. Overall, the study demonstrated that MWNTs and CNFs can effectively remove cationic and anionic dyes as MB and OII from aqueous solutions under these experimental conditions.

Wet air and catalytic wet air oxidation of several azodyes from wastewaters: the beneficial role of catalysis.

Degradation of several azo dyes, Acid Orange 7 (AO7), Acid Orange 74 (AO74), Direct Blue 71 (DB71), Reactive Black 5 (RB5) and Eriochrome Blue Black B (EBBB), well-known non-biodegradable mono, di and tri azo dyes has been studied using, wet-air oxidation (WAO) and catalytic wet air oxidation (CWAO). The efficiency of substrate decolorization and mineralization in each process has been comparatively discussed by evolution concentration, chemical oxygen demand, total organic carbon content and toxicity of dyes solutions. The most efficient method on decolorization and mineralization (TOC) was observed to be CWAO process. Mineralization efficiency with wet air and catalytic wet air oxidation essays was observed in the order of mono-azo > di-azo > tri-azo dye. Final solutions of CWAO applications after 180 min treatment can be disposed safely to environment.

Comparison of adsorption equilibrium and kinetics of four chlorinated organics from water onto GAC.

This study deals with the adsorption of four chlorinated pollutants onto GAC (F-400); two pesticides (lindane and alachlor) and two PCB congeners: 2-PCB (MPCB) and 2,2',5,5'-PCB (TPCB). Equilibrium and kinetic parameters have been obtained for the adsorption of alachlor and each PCB. whereas the kinetic results for lindane presented elsewhere (Proc. First World Water Congr. Int. Water Assoc., Texts of Posters, CD-ROM, AGHTM, Paris, 2000) are reanalyzed in this work. A model assuming a bidisperse structure (macro- and micropores). each region having a different adsorption isotherm, is used to study the adsorption kinetics in a batch system in the period dominated by macropore diffusion. Both the saturation capacity and the rate of internal transport of TPCB are much lower than those of the other solutes. This difference is attributed to a chemisorption mechanism for this compound, which is favored by its very low solubility.

Novel heterogeneous catalysts in the wet peroxide oxidation of phenol.

Catalytic wet peroxide oxidation (CWPO) of diluted aqueous solutions of phenol has been studied over a series of heterogeneous catalysts at 100 degrees C under 1 MPa air pressure. Several catalysts were prepared and tested including zeolitic materials exchanged with metallic ions such as Fe and Cu and different mixed oxides. Likewise, a Fe-TS-1 zeolite was synthesised by isomorphous substitution of Si atoms by Fe and Ti into the MFI zeolitic framework through hydrothermal synthesis of wetness-impregnated Fe2O3-TiO2-SiO2 xerogels. This material showed a complete phenol removal and TOC reduction of up to 68% under the reaction conditions, with a low leaching of iron species as compared to Fe-exchanged zeolitic materials. Perovskite of type LaTi(0.45)Cu(0.55)O3 was also tested, showing copper leaching of 22%, with a TOC conversion of 93% and total phenol removal. The capacity of Fe and Cu containing catalysts to promote free radicals in the presence of H2O2 as well as the thermal decomposition of the oxidant under the reaction conditions have also been studied. In the absence of hydrogen peroxide, Fe and Cu catalysts were not effective in order to decrease TOC content.