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

MONTAÑA, MAIA; MÉNDEZ, LETICIA J.; OCSACHOQUE, MARCO A.; CECILIA, JUAN A.; LICK, ILEANA D.; RODRÍGUEZ-CASTELLÓN, ENRIQUE; CASELLA, MÓNICA L.

Encuentro Virtual

Simposio; RSEQ Symposium 2021; 2021

Real Sociedad Española de Química

During the last decade, renewable fuels have become an important focus of research in the energy field, likewise the building block derived from biomass waste search for sustainable alternative due to the increasing world energy demand. In this sense, the valorization of glycerol, generated from biodiesel production, with furfural as molecule derived from lignocellulosic biomass, by the catalytic acetalization reaction to obtain dioxolanes, results interesting. Dioxolane as bio-additives has application for oil and biofuels industry [1,2]. In this work, the acetalization reaction of glycerol with furfural to obtain 2,2-furfuril-1,3-dioxolan-4-il-methanol and 2,2-furfuril-1,3-dioxan-5-ol was investigated. For this, two commercial zeolites, ZSM-5(Si/Al=21,2) and mordenite (Si/Al=10), were modified in the laboratory with ammonium nitrate to obtain the acidic zeolite forms by ion change and calcination at 500°C for 2 h. Both acid zeolites were characterized by several physicochemical techniques (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 condenser and acetonitrile was used as the reaction solvent. The experiments were performed at 100°C, a Gly/FUR=1:1 molar ratio, 10 wt.% of catalyst and the reaction time was varied from 15 to 120 minutes. At the end of each reaction, the liquid products were analyzed by GC-FID and GC-MS to calculate conversion and selectivity. Figure 1 presents the catalytic results for both zeolites. The conversion of furfural increases with reaction time up to 1 hour, then decreases likely due to the presence of water and the polymerization of furfural and the formation of the humic product. In the presence of H-ZSM-5 catalyst, 51% of dioxolane was obtained whereas the H-Mor exhibited a lower conversion, 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%. In conclusion, the most promising performance was obtained for H-ZSM-5 catalyst, achieving a 55% of conversion to dioxolane.