Glycerol dehydration to acrolein was studied with three catalysts using zeolite-Y. This zeolite in its protonic form (HY), with La (LaY) and Pd with La (Pd/LaY), was characterized by X-ray diffraction (XRD), Fourier-transform-infrared spectroscopy (FTIR) with pyridine, BET, Scanning Electron Microscope (SEM)–Energy-Dispersive Spectroscopy X-ray (EDS) and the catalytic activity tests were carried out under H2 atmosphere. It was found that La ions exchanged in the zeolite-Y resulted in the improvement of both glycerol conversion and yield to acrolein, also a relatively constant glycerol conversion was achieved up to three hours, due to the presence of Pd on the catalyst and H2 in the feed. The comparison of the calculated and experimental yields obtained from the catalytic tests of the Pd/LaY catalyst indicates a greater activity for the reaction to acrolein than for the reaction to acetol. The calculated equilibrium yields of the dehydration reaction from glycerol to acrolein, acetol, ethanal, methanol, and water and the experimental yields of a Pd/LaY catalyst were compared. Thermodynamically, a complete conversion of glycerol can be achieved since the general system remains exothermic and promotes the path to acetol below 480 K. Above this temperature the system consumes energy and favors the production of acrolein, reaching its maximum concentration at 600 K.
The study of the deactivation of HY zeolites in the dehydration reaction of glycerol to acrolein has represented a challenge for the design of new catalysts. HY zeolites with SiO2/Al2O3 molar ratios between 3.5 and 80 were studied. The solids were characterized by XRD, N2 physisorption, SEM-EDXS, Raman and UV-vis spectroscopies, infrared spectroscopy of pyridine (FTIR-Py) and catalytic activity tests from 250 °C to 325 °C. It was found that the total amount of acid sites per unit area of catalyst decreased as the SiO2/Al2O3 molar ratio increased from 3.5 to 80, resulting in the decrease in the initial glycerol conversion. The initial acrolein selectivity was promoted with the increase of the Brønsted/Lewis acid sites ratio at any reaction temperature. The deactivation tests showed that the catalyst lifetime depended on the pore structure, improving with the presence of large surface areas as evidenced by the deactivation rate constants. The characterization of the deactivated catalysts by XRD, N2 physisorption and thermogravimetric analysis indicated that the deposition of coke resulted in the total obstruction of micropores and the partial blockage of mesopores. Moreover, the presence of large mesopores and surface areas allowed the amount of coke deposited at the catalyst surface to be reduced.
This work reports the results of the ultrasound-assisted hydrothermal synthesis of two sets of V2O5 dispersed on SBA-15 and Zr doped SBA-15 catalysts used for the oxidation of dibenzothiophene (DBT) in a model diesel via the combination of oxidation, catalysis, and extraction technical route. These catalysts contained Lewis acidity as major and Brønsted acidity as minor. The amount of acidity varied with the content of vanadia and zirconium doping. It was found that DBT conversion is very sensitive to the Lewis acidity. DBT conversion increased by increasing the vanadium content and correlated well with the amount of surface Lewis acidity. Under the optimal experimental condition (Reaction temperature: 60 °C, reaction time 40 min, catalyst concentration: 1 g/L oil; H2O2/DBT mole ratio = 10), the 30% V2O5/SBA-15 and 30% V2O5/Zr-SBA-15 catalysts could convert more than 99% of DBT. Two reaction pathways of DBT oxidation involving vanadia surface structure, Lewis acidity, and peroxometallic complexes were proposed. When the vanadia loading V2O5 ≤ 10 wt%, the oxidative desulfurization (ODS) went through the Pathway I; in the catalysts with moderate vanadia content (V2O5 = 20–30 wt%), ODS proceeded via the Pathways II or/and the Pathway I.
A set of Y-type zeolites with Si/Al atomic ratios between 7–45 were studied as catalysts in the aminocyclization reaction between acrolein and ammonia to produce pyridine and 3-picoline. The catalytic activity tests at 360 °C revealed that the acrolein conversion increased in the order Z45 < ZY34 < ZY7 < ZY17, in agreement with the increase of the total acidity per gram of catalyst. In all cases, pyridine bases and cracking products (acetaldehyde and formaldehyde) were detected in the outflow from the reactor. The total yield of pyridines was inversely proportional to the total acidity for the catalysts, which presented large surface areas and micro- and mesoporosity. The selectivity towards 3-picoline was favored when using catalysts with a Brønsted/Lewis acid sites ratio close to 1. The formation of pyridine occurred more selectively over Lewis acid sites than Brønsted acid sites. The deactivation tests showed that the time on stream of the catalysts depended on the textural properties of zeolites, i.e., large pore volume and large BET area, as evidenced by the deactivation rate constants and the characterization of the spent catalysts. The physicochemical properties of the catalysts were determined by XRD, UV-vis, and Raman spectroscopies, infrared spectroscopy with adsorbed pyridine, N2 physisorption, and SEM-EDXS. After the reaction, the spent catalysts were characterized by XRD, Raman spectroscopy, TGA, and SEM-EDXS, indicating that the uniform deposition of polyaromatic species on the catalyst surface and within the porous system resulted in the loss of activity.
A comparison was made of the effectiveness of the functionalization reactions of pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (PCU) using sulphated zirconia in protection-deprotection reactions and Mg/Al hydrotalcite in a cyanosilylation reaction, under classical thermal conditions and imposing microwave radiation; improved yields and reaction times were considered.