This paper describes the activation and catalytic performance of a multifunctional catalyst consisting of mixed oxides of vanadium and molybdenum supported on an acidic ZSM-5 zeolite. The zeolite was wet-impregnated with an aqueous solution containing a mixture of NH 4 VO 3 and (NH 4 ) 6 Mo 7 O 24 precursors at a V/(Mo+V) molar ratio of 0.6. Evolution of the phases during activation (by calcination under 20% O 2 /He) was followed by synchrotron X-ray diffraction (XRD), but detection of mixed oxides of Mo x V y O z was difficult, due to the high degree of dispersion on the zeolite surface. On the other hand, X-ray absorption spectroscopy (XAS) performed simultaneously at the Mo and V K-edges enabled confirmation of formation of the MoV 2 O 8 phase on the acidic ZSM-5 zeolite. The combination of the MoV 2 O 8 phase and the zeolite acid sites produced a highly active catalyst for gas phase glycerol dehydration-oxidation coupled reactions in which acrylic acid was the main product. The multifunctional catalyst presented only 6% of deactivation during a period of 8 h under glycerol stream, while the activities of the bulk mixed oxide and the pure ZSM-5 zeolite decreased by almost 20 and 31%, respectively.

The gas-phase alkylation of m-cresol with methanol was studied at 523 K on Al-MCM-41 and zeolites ZnY, HBEA, HZSM5 and HMCM22. The acidity was determined by ammonia TPD and FTIR of adsorbed pyridine. On acid sites of moderate strength (Al-MCM-41), initially the O-alkylation rate was higher than the C-alkylation rate. In contrast, formation of dimethylphenols by C-alkylation was highly favored on ZnY and HMCM22 which have both strong acidity although different nature; Lewis (ZnY) and Brønsted and Lewis (HMCM22). High selectivity of 2,5-DMP was observed on HZSM5, probably due to diffusional constraint. All catalysts, except Al-MCM-41, showed deactivation by coke formation.

In this paper, glycerol esterification with acetic acid (AA) was studied on several solid acid catalysts: AlO, Al-MCM-41, HPA/SiO, HBEA, Amberlyst 15 and Amberlyst 36 with the aim of determining the reaction conditions and the nature of the surface acid sites required to produce selectively triacetylglycerol (triacetin). The acidity of the catalysts (nature, density and strength of acid sites) was characterized by temperature-programmed desorption of NH and FTIR of adsorbed pyridine. AlO (Lewis acidity) did not show any activity in the reaction. In contrast, highest activity and selectivity to the triacetylated product (triacetin) were obtained on catalysts with Brønsted acidity: Amberlyst 15 and Amberlyst 36. The effect of temperature and molar ratio of AA to glycerol was studied, and the results showed that both parameters have a significant impact on the production of the desired product. Glycerol conversion rate and selectivity to triacetin increased when temperature or AA to glycerol molar ratio were increased, reaching a triacetin yield on Amberlyst 36 of 44% at 393 K and AA to glycerol molar ratio of 6. Deactivation and reusability of Amberlyst 36 were evaluated by performing consecutive catalytic tests. The presence of some irreversible deactivation due to sulfur loss was observed. In addition, the feasibility of using crude glycerol from biodiesel production as reactant was also investigated. Conversion of crude pretreated glycerol yielded values of triacetin and diacetin similar to those obtained with the commercial pure glycerol although at a lower rate.

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