Esterification of Levulinic Acid to Methyl Levulinate over Zr-MOFs Catalysts

DAIANA A. BRAVO FUCHINECO; ANGÉLICA C HEREDIA; SANDRA M. MENDOZA; ENRIQUE RODRIGUEZ-CASTELLÓN; MÓNICA E. CRIVELLO

ChemEngineering

MDPI

Año: 2022

At present, the trend towards partial replacement of petroleum-derived fuels by those fromthe revaluation of biomass has become of great importance. An effective strategy for processingcomplex biomass feedstocks involves prior conversion to simpler compounds (platform molecules)that are more easily transformed in subsequent reactions. This study analyzes the metal?organicframeworks (MOFs) that contain Zr metal clusters formed by ligands of terephthalic acid (UiO-66)and aminoterephthalic acid (UiO-66-NH2 ), as active and stable catalysts for the esterification oflevulinic acid with methanol. An alternative synthesis is presented by means of ultrasonic stirringat room temperature and 60 ◦C, in order to improve the structural properties of the catalysts. Theywere analyzed by X-ray diffraction, scanning electron microscopy, infrared spectroscopy, X-rayphotoelectron spectroscopy, microwave plasma atomic emission spectroscopy, acidity measurement, and N2 adsorption. The catalytic reaction was carried out in a batch system and under pressure in an autoclave. Its progress was followed by gas chromatography and mass spectrometry. Parameters such as temperature, catalyst mass, and molar ratio of reactants were optimized to improve the catalytic performance. The MOF that presented the highest activity and selectivity to the desired product was obtained by synthesis with ultrasound and 60 ◦C with aminoterephthalic acid. The methyl levulinate yield was 67.77% in batch at 5 h and 85.89% in an autoclave at 1 h. An analysis of the kinetic parameters of the reaction is presented. The spent material can be activated by ethanol washing allowing the catalytic activity to be maintained in the recycles.