ABSTRACT
The direct transformation of cellulose into sugar alcohols (one-pot conversion) over supported nickel catalysts represents an attractive chemical route for biomass valorization, allowing the use of subcritical water in the hydrolysis step. The effectiveness of this process is substantially conditioned by the hydrogenation ability of the catalyst, determined by design parameters such as the active phase loading and particle size. Herein, mechanistic insights into catalyst design to produce superior activity were outlined using the hydrolytic hydrogenation of cellobiose as a model reaction. Variations in the impregnation technique (precipitation in basic media, incipient wetness impregnation, and the use of colloidal-deposition approaches) endowed carbon-nanofiber-supported catalysts within a wide range of Ni crystal sizes (5.8-20.4 nm) and loadings (5-14 wt%). The link between the properties of these catalysts and their reactivity has been established using characterization techniques such as X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma-optical emission spectroscopy (ICP-OES). A fair compromise was found between the Ni surface area (3.89 m2/g) and its resistance against oxidation for intermediate crystallite sizes (â¼11.3 nm) loaded at 10.7 wt%, affording the hydrogenation of 81.2% cellobiose to sorbitol after 3 h reaction at 190°C and 4.0 MPa H2 (measured at room temperature). The facile oxidation of smaller Ni particle sizes impeded the use of highly dispersed catalysts to reduce the metal content requirements.
ABSTRACT
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.
