Valorization of By-Products from Biomass Processing through Bio-Catalytic Oxidation
The oxidation of biomass-derived hydrocarbons or aliphatic alcohols into ketones, aldehydes and carboxylic acids may confer enhanced bioactivity properties as e.g. bactericide, antifungal or insecticides. Due to the increase of the biodiesel industry, based on sustainability politics for renewable resources utilization, glycerol as the main by-product is being supplied at levels much higher than demanded thus being poorly commercially exploited. On the other side, terpenes are renewable natural hydrocarbons, which are readily available in plants. Among them, limonene is nowadays one of the most abundant and easily available since it is contained in citrus peels, which are the waste product of juice industries. With the exception of di-hydroxyacetone, the market of the oxidation products of glycerol but also of limonene was not developed because of high production costs although all of them play as very valuable intermediates in fine chemistry. This study focalizes in the valorisation of glycerol and limonene by catalytic oxidation and the characterization of the oxidized products in terms of its insecticide action. Not only pure standards of both substances but also raw samples of industries, from which are by-produced are considered to be tested for the oxidation reaction. Special attention is cared to the use of environmental-friendly processing free of toxic solvents and oxidants without the need of cofactors. In addition to their potential high selectivity and simplicity, two types of catalytic systems were pre-selected for screening studies: pure oxidases and metallic complexes based on Mn and Fe. Preliminary results relates to the use of a natural iron porphyrin ânamed as hematin- as the oxidazing catalyst in first oxidation trials, optimization of reaction kinetics and analytics establishments. Hematin possess the ability to mimicking the action of peroxidases and catalases thus co-catalazing the decomposition of the oxidant, H2O2. The radicals formed by this route may cooperate in the oxidation of organic matter. Therefore a careful selection of reaction conditions in terms of solvent mixture, pH, temperature and molar ratio of reducing substrate to oxidant was required in order to afford a complete activity check.