Co-hydrothermal carbonization with process water recirculation as a valuable strategy to enhance hydrochar recovery...

This study aims at valorizing the residual aqueous phase from hydrothermal carbonization (HTC) of Sicilian agro-wastes in order to enhance the hydrochar recovery, positively affecting the process energy balance. Process waters (PW) obtained from HTC and co-HTC using orange peel waste and fennel plant residues were used as recycled solvent in experiments carried out at the temperatures of 180 and 230 °C. The results showed that an additional hydrochar formation was promoted during recirculation of solvent, leading to average increments of solid mass yield of 10.5 wt% for tests conducted at 180 °C and 3.9 wt% for 230 °C. After five consecutive recirculation phases in co-HTC runs, the hydrochar yield increased up to 18.2 wt%. The low H/C and O/C atomic ratios values, found after recirculation, indicate that organic acids, accumulated in the PW, may catalyze the process and promote the biomass deoxygenation by boosting dehydration and decarboxylation. The recovered PWs from conversion steps with deionized water were also carbonized in absence of the solid feedstock in order to quantify their contribution in hydrochar formation during recirculation and thus the synergistic interactions. After recirculation, energy recovery averagely augmented by more than threefold, showing that the proposed strategy could significantly improve the sustainability of HTC.