Olive trees constitute one of the largest agroindustries in the Mediterranean area, and their cultivation generates a diverse pool of biomass by-products such as olive tree pruning (OTP), olive leaves (OL), olive stone (OS), and extracted olive pomace (EOP). These lignocellulosic materials have varying compositions and potential utilization strategies within a biorefinery context. The aim of this work was to carry out an integral analysis of the aqueous extractives fraction of these biomasses. Several analytical methods were applied in order to fully characterize this fraction to varying extents: a mass closure of >80% was reached for EOP, >76% for OTP, >65% for OS, and >52% for OL. Among the compounds detected, xylooligosaccharides, mannitol, 3,4-dihydroxyphenylglycol, and hydroxytyrosol were noted as potential enhancers of the valorization of said by-products. The extraction of these compounds is expected to be more favorable for OTP, OL, and EOP, given their high extractives content, and is compatible with other utilization strategies such as the bioconversion of the lignocellulosic fraction into biofuels and bioproducts.

This work addresses for the first time the study of olive stone (OS) biomass pretreatment by reactive extrusion technology using NaOH as the chemical agent. It is considered as a first step in the biological conversion process of the carbohydrates contained in the material into bio-based products. OS is a sub-product of the olive oil extraction process that could be used in a context of a multi-feedstock and multi-product biorefinery encompassing all residues generated around the olive oil production sector. OS biomass is pretreated in a twin-screw extruder at varying temperatures—100, 125 and 150 °C and NaOH/biomass ratios of 5% and 15% (dry weight basis), in order to estimate the effectiveness of the process to favour the release of sugars by enzymatic hydrolysis. The results show that alkaline extrusion is effective in increasing the sugar release from OS biomass compared to the raw material, being necessary to apply conditions of 15% NaOH/biomass ratio and 125 °C to attain the best carbohydrate conversion rates of 55.5% for cellulose and 57.7% for xylan in relation to the maximum theoretical achievable. Under these optimal conditions, 31.57 g of total sugars are obtained from 100 g of raw OS.