Lignin extraction from Mediterranean agro-wastes: Impact of pretreatment conditions on lignin chemical structure and thermal degradation behavior

Three different types of Mediterranean, agro-industrial wastes (olive kernels, grape pomace/seeds, peach kernels), were subjected to two pretreatment processes, a chemical/organosolv and a physicochemical one. The organosolv process included lignocellulosic biomass treatment with formic acid/acetic acid/water (30/50/20, v/v%), for 3 h at 107 °C, while the physicochemical method was conducted by immersing the biomass in a water/ethanol (8/92, v/v%), H2SO4 0.32 M, solvent and further exposing the slurry to microwave irradiation (maximum 250 W) for 1/2 h at 150 °C. Both processes were evaluated regarding the achieved delignification and the purity of the extracted lignins. The effect of the pretreatment processes onto the structure and thermal decomposition behavior of the extracted lignins was investigated via FT-IR and TGA analysis, respectively. The objective of the research work was to investigate potential valorization routes for these biomass agro-residues in the context of a biorefinery, focusing on lignin extraction. The pretreatment results showed that the obtained lignins, derived from both procedures, were of high purity (>82 wt%). Under the organosolv procedure, peach kernel delignification showed the maximum value (∼16 wt%), while under microwave pretreatment, olive kernel delignification showed the maximum value (∼35 wt%). Grape pomace/seeds appeared to be the most resistant in both treatments.