Valorisation of metal-contaminated biomass by hydrothermal liquefaction: The case study of tannery sludge

Around 600 million m3 of wastewater and 6 million tonnes of leather solid wastes, are generated annually worldwide, with a chromium content of 1 to 4 %. In this context, the thermochemical valorisation of tannery sludge (TS) by hydrothermal liquefaction (HTL) process represents a promising route both for the reduction of the material to dispose in landfill and for the production of an energy carrier. HTL process produces bio-crude from wet biomasses in a hot pressurised water environment, thus avoiding the energy-intensive drying step commonly associated to other thermochemical processes. Moreover, HTL, not aiming at the complete oxidation of the organic component, potentially avoids the oxidation of Cr in its harmful hexavalent form. In this study, a TS was investigated as solid waste for HTL carried out in a 500 mL batch reactor to obtain a bio-crude for energy purposes. Results show that, under the best operating HTL condition (350 °C and 10 min), the H/C ratio of bio-crude was similar to that of starting biomass while the O/C ratio was about three times smaller than in the parent TS. The bio-crude yield was about 25–30 % on dry and ash-free basis, with an associated energy recovery of about 40–45 %. NMR analysis of bio-crude revealed that it is a complex mixture mainly constituted by aliphatic units. Moreover, ICP-MS, atomic absorption and UV–visible spectroscopy analyses proved that inorganic elements are mainly retrieved in the solid residue, and that Cr was present in its starting trivalent form.