ETD

• 1-Hexanol
• Esterification
• Heterogeneous catalysis
• Hexyl hexanoate
• Hydrogenation/hydrogenolysis
• Mechanochemistry

This thesis is aimed at developing the integrated synthesis of n-hexyl esters (mainly Hexyl Hexanoate - HexHex) and 1-Hexanol (HexOH). HexHex synthesis by acid-catalysed Fisher esterification was optimized, starting from model compounds, then moving towards the conversion of real carboxylic acid-enriched substrates. Crudes originating from “Grape Pomace” and “Organic Fraction of Municipal Solid Waste” anaerobic fermentation, were proposed, given their high contents of short-/medium-chain carboxylic acids. Pre- and in-situ treatments were considered, to properly remove the pristine/formed water, which may hinder the esterification progress. Synthesis of shorter-chain alkyl esters was evaluated, to expand the possibilities for the valorization of these bio-esters in different applications (cosmetics, pharmaceuticals, fragrances, etc.). HexHex hydrogenation/hydrogenolysis to 1-HexOH with ternary copper-based mixed oxides, was investigated. The attention was focused on the most performing catalyst, and four recycling tests were carried out, characterizing each spent catalyst. Finally, the mechanochemical synthesis of the ternary catalyst of optimal composition was pursued, aimed at improving the sustainability of the catalyst synthesis. Different catalysts were synthesized, varying the main synthesis variables, and their characterization was deepened, thus identifying the best candidate, to be tested for the same hydrogenation/hydrogenolysis reaction.