Production of bio-addittive: acetalization of glycerol with furfural assisted by solid acid catalyst to obtain dioxolane

MONTAÑA, MAIA; LETICIA MENDEZ; OCSACHOQUE, MARCO ANTONIO; CECILIA, JUAN ANTONIO; LICK, ILEANA DANIELA; RODRÍGUEZ-CASTELLÓN, ENRIQUE; CASELLA, MÓNICA LAURA

Simposio; RSEQSymposium 2021; 2021

Real Sociedad Española de Química

During the last decade, renewable fuels have become an important focus of research in the energyfield, likewise the building block derived from biomass waste search for sustainable alternative dueto the increasing world energy demand. In this sense, the valorization of glycerol, generated frombiodiesel production, with furfural as molecule derived from lignocellulosic biomass, by the catalyticacetalization reaction to obtain dioxolanes, results interesting. Dioxolane as bio-additives hasapplication for oil and biofuels industry [1,2]. In this work, the acetalization reaction of glycerol withfurfural to obtain 2,2-furfuril-1,3-dioxolan-4-il-methanol and 2,2-furfuril-1,3-dioxan-5-ol wasinvestigated. For this, two commercial zeolites, ZSM-5(Si/Al=21,2) and mordenite (Si/Al=10), weremodified in the laboratory with ammonium nitrate to obtain the acidic zeolite forms by ion changeand calcination at 500°C for 2 h. Both acid zeolites were characterized by several physicochemicaltechniques (XRD, FTIR spectroscopy, SEM, N2 and CO2 adsorption-desorption, solid state-NMR,potentiometric titration). The reaction was carried out in a round-bottom flask with a reflux condenserand acetonitrile was used as the reaction solvent. The experiments were performed at 100°C, aGly/FUR=1:1 molar ratio, 10 wt.% of catalyst and the reaction time was varied from 15 to 120minutes. At the end of each reaction, the liquid products were analyzed by GC-FID and GC-MS tocalculate conversion and selectivity. Figure 1 presents the catalytic results for both zeolites. Theconversion of furfural increases with reaction time up to 1 hour, then decreases likely due to thepresence of water and the polymerization of furfural and the formation of the humic product. In thepresence of H-ZSM-5 catalyst, 51% of dioxolane was obtained whereas the H-Mor exhibited a lowerconversion, ca. 34%. This result can be associated with the higher acidity of the H-ZSM-5. Besides,both catalysts presented a similar selectivity to 1,3-dioxolane and 1,3-dioxolan, between 45-55%. Inconclusion, the most promising performance was obtained for H-ZSM-5 catalyst, achieving a 55% ofconversion to dioxolane.