The almond industry leaves behind substantial amounts of by-products, with almond hulls being the primary residue generated. Given that one way to improve food security is by decreasing waste to reduce environmental impacts, developing sustainable processes to manage this by-product is necessary. Herein, we report on the hydrothermal hydrogenation of almond hulls over a carbon-neutral Ru supported on carbon nanofibres (Ru/CNF) catalyst, addressing the temperature, H2 pressure, time and catalyst loading. These variables controlled the distribution of the reaction products: gas (0-5%), liquid (49-82%) and solid (13-51%), and ruled the composition of the liquid effluent. This aqueous fraction comprised oligomers (46-81 wt%), saccharides (2-7 wt%), sugar alcohols (2-15 wt%), polyhydric alcohols (1-8 wt%) and carboxylic acids (7-31 wt%). The temperature and reaction time influenced the extension of hydrolysis, depolymerisation, deamination, hydrolysis, hydrogenation and dehydration reactions. Additionally, the initial H2 pressure and catalyst loading kinetically promoted these transformations, whose extensions were ruled by the amount of H2 effectively dissolved in the reaction medium and the prevalence of hydrogenations over dehydration/decarboxylation reactions or vice versa depending on the catalyst loading. Process optimisation revealed that it is feasible to convert up to 67% of almond hulls into merchantable oligomers at 230 °C, 35 bar initial H2, using 1 g catalyst/g biomass (0.4 g Ru/g biomass) for 360 min. Additionally, decreasing the temperature to 187 °C without modifying the other parameters could convert this material into oligomers (31 wt%) and small oxygenates (17 wt% carboxylic acids, 11 wt% sugar alcohols and 6 wt% polyhydric alcohols) concurrently. The theoretical energy assessment revealed that the total and partial combustion of the spent solid material could provide the required energy for the process and allow catalyst recovery and reutilisation. This environmental friendliness and holistic features exemplify a landmark step-change to valorising unavoidable food waste.
Keywords: Almond hulls; Carbon nanofibres; Hydrothermal hydrogenation; Ruthenium; Value-added liquids.
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