Selective production of dihydroxyacetone and glyceraldehyde by photo-assisted oxidation of glycerol

Abstract

Glycerol is a by-product during biodiesel production and represents a potential low-cost raw material for obtaining high-cost products like Dihydroxyacetone (DHA) and glyceraldehyde (GCD) amongst others. In this work, Fe-Pillared clay (Fe-PILC) was assessed as catalyst of the selective photo-oxidation of glycerol to obtain DHA and GCD at moderate conditions (298 K and atmospheric pressure). This was conducted in a 100 mL Pyrex glass batch reactor where a Pen-Ray lamp of mercury of 5.5 W UV light (UVP) was placed at the centre. The Fe-PILC was prepared by ion exchange. The pillaring was confirmed by XRD, and a 17% w/w of Fe was determined by Atomic Absorption Spectroscopy. The active phases were established by XPS and found to be FeO and Fe3O4. The specific surface area of the clay (bentonite), determined by N2 physisorption, increased from 34 m2/g to 227 m2/g and the pore volume increased from 0.058 cm3/g to 0.106 cm3/g. The studied variables were catalyst loading and glycerol initial concentration. An experiment with TiO2 Degussa P25 was also performed as reference. It was found that by adding Fe-PILC to the glycerol oxidation system, selectivity towards DHA or GCD can be tuned. A selectivity towards DHA was found to be 87% with 0.1 g/L of Fe-Pillared after 8 h reaction. The in situ production of H2O2 was observed and therefore concluded that the glycerol oxidation occurs via a fenton process, i.e. via free radicals.