Once a biorefinery is ready to operate, the main processed materials need to be completely evaluated in terms of many different factors, including disposal regulations, technological limitations of installation, the market, and other societal considerations. In biorefinery, glycerol is the main by-product, representing around 10% of biodiesel production. In the last few decades, the large-scale production of biodiesel and glycerol has promoted research on a wide range of strategies in an attempt to valorize this by-product, with its transformation into added value chemicals being the strategy that exhibits the most promising route. Among them, C3 compounds obtained from routes such as hydrogenation, oxidation, esterification, etc. represent an alternative to petroleum-based routes for chemicals such as acrolein, propanediols, or carboxylic acids of interest for the polymer industry. Another widely studied and developed strategy includes processes such as reforming or pyrolysis for energy, clean fuels, and materials such as activated carbon. This review covers recent advances in catalysts used in the most promising strategies considering both chemicals and energy or fuel obtention. Due to the large variety in biorefinery industries, several potential emergent valorization routes are briefly summarized.
In this work, primidone, a high persistent pharmacological drug typically found in urban wastewaters, was degraded by different ozone combined AOPs using TiO2 P25 and commercial WO3 as photocatalyst. The comparison of processes, kinetics, nature of transformation products, and ecotoxicity of treated water samples, as well as the influence of the water matrix (ultrapure water or a secondary effluent), is presented and discussed. In presence of ozone, primidone is rapidly eliminated, with hydroxyl radicals being the main species involved. TiO2 was the most active catalyst regardless of the water matrix and the type of solar (global or visible) radiation applied. The synergy between ozone and photocatalysis (photocatalytic ozonation) for TOC removal was more evident at low O3 doses. In spite of having a lower band gap than TiO2 P25, WO3 did not bring any beneficial effects compared to TiO2 P25 regarding PRM and TOC removal. Based on the transformation products identified during ozonation and photocatalytic ozonation of primidone (hydroxyprimidone, phenyl-ethyl-malonamide, and 5-ethyldihydropirimidine-4,6(1H,5H)-dione), a degradation pathway is proposed. The application of the different processes resulted in an environmentally safe effluent for Daphnia magna.