Valorization of By-Products from Biomass Processing through Bio-Catalytic Oxidation

ADRIÁN PARODI; PAULA SAPPIA; MAYRA FALCO; JULIO ZYGADLO; MARÍA LUJÁN FERREIRA; IVANA MAGARIO

Buenos Aires

Conferencia; 2nd RCN Conference on Pan American Biofuels & Bioenergy Sustainability; 2016

American Institute of Chemical Engineers

The oxidation of biomass-derivedhydrocarbons or aliphatic alcohols into ketones, aldehydes and carboxylic acidsmay confer enhanced bioactivity properties as e.g. bactericide, antifungal or insecticides. Due to the increaseof the biodiesel industry, based on sustainability politics for renewable resources utilization,glycerol as the main by-productis being supplied at levels much higher than demanded thus being poorly commerciallyexploited. On the other side, terpenes are renewable natural hydrocarbons,which are readily available in plants. Among them, limonene is nowadays one ofthe 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, themarket of the oxidation products of glycerol but also of limonene was notdeveloped because of high production costs although all of them play asvery valuable intermediates in fine chemistry. This study focalizes in the valorisationof glycerol and limonene by catalytic oxidation and the characterization of theoxidized products in terms of its insecticide action. Not only pure standards ofboth substances but also raw samples of industries, from which are by-producedare considered to be tested for the oxidation reaction. Special attention is caredto the use of environmental-friendly processing free of toxic solvents andoxidants without the need of cofactors. In addition to their potential highselectivity and simplicity, two types of catalytic systems were pre-selectedfor screening studies: pure oxidases and metallic complexes based on Mn and Fe.Preliminary results relates to the use of a natural iron porphyrin ?named ashematin- as the oxidazing catalyst in first oxidation trials, optimization ofreaction kinetics and analytics establishments. Hematin possess the ability tomimicking the action of peroxidases and catalases thus co-catalazing thedecomposition of the oxidant, H2O2. The radicals formedby this route may cooperate in the oxidation of organic matter. Therefore acareful selection of reaction conditions in terms of solvent mixture, pH,temperature and molar ratio of reducing substrate to oxidant was required inorder to afford a complete activity check.