Total oxidation of chlorinated VOCs on supported oxide catalysts

Biomass-fed cogeneration units and waste incinerators have the advantages of producing efficiently heat and power and of reducing the amount of CO2 emitted per produced energy. However, they produce toxic polychlorinated VOCs (dioxins), CO and NOx. This thesis aims at developing a catalytic system for the total oxidation of chlorinated VOCs that: i) convert efficiently chlorinated VOCs below 250 °C and ii) resist to the exhaust co-pollutants (H2O, CO, NOx). Moreover, this thesis aims at having a complete understanding of the catalytic mechanism. Part I demonstrated that VOx/TiO2 based catalysts are very efficient in the total oxidation of chlorobenzene (taken as a model molecule). In particular, they proved to be highly resistant against deactivation. Moreover, Part I established that the addition of secondary phases producing VOx-WOx/TiO2 or VOx-MoOx/TiO2 induces a synergetic effect that improves the performances. Furthermore, the replacement of a classical TiO2 by a sulfated one improves the catalytic activity. In Part II, the investigation of the co-pollutants influence on the catalysts performances demonstrated their quite good resistance. Indeed, the presence of CO does not induce any deactivation of the catalysts while NOx induces a huge improvement of the catalysts ability to destroy chlorinated VOCs. This beneficial effect is explained by the in situ production of a strong oxidant (NO2) that speeds up the reoxidation of the reduced VOx sites. Nevertheless, H2O vapor can affect negatively the catalyst activity when present in a high concentration. Part III, by revisiting catalytic and characterization results exposed in Part I and II, demonstrated that the catalytic mechanism proceeds in four steps: i) adsorption of chlorinated VOCs on Brønsted sites, ii) VOx redox sites give some of their lattice oxygen atoms to oxidize the aromatic ring producing H2O and COx, iii) reoxidation of the VOx reduced sites thanks to the gas stream oxidant (O2) and iv) retrieving of the chlorine from the surface. The second and third steps compose a Mars and van Krevelen mechanism and the third one is the mechanism rate limiting step. Our work shows that the performances can be improved by tuning the redox properties of the VOx phases: i) improvement of the reducibility and ii) stabilization of the vanadium oxidation level above a limit value, estimated around 4.87.