Hydrothermal–Membrane Valorization of Coffee Pulp for Xylooligosaccharide Production

Wet coffee pulp residues (WCPRs) are typically underutilized, and their accumulation increases alongside coffee production, generating significant environmental impacts. This study proposes a sustainable valorization approach through hydrothermal treatment followed by membrane filtration for the production of xylooligosaccharides (XOSs). Extractive-free WCPR contained 35.4% structural carbohydrates (20.4% cellulose and 15.0% hemicellulose) and 27.0% lignin. Hydrothermal treatments (180 °C, 3 °C min−1, 15–60 min) were performed with and without citric acid as an organic catalyst. The acid-assisted treatment (T4) enhanced hemicellulose depolymerization and xylose release (16 g·kg−1 dry biomass), whereas milder, non-acidic conditions (T3) promoted the selective formation and recovery of short-chain XOS, reaching cumulative biomass-normalized yields of up to 14 g·kg−1 of xylobiose (X2) and 9 g·kg−1 of xylotriose (X3). Subsequent membrane processing (UF–DF–NF) enabled progressive purification and enrichment of XOS fractions. Diafiltration was identified as the main step governing XOS enrichment, whereas nanofiltration primarily refined separation by directing monomeric sugars to the permeate rather than substantially increasing XOS yields. Additionally, Multiple Factor Analysis (MFA) integrated process and compositional variables, explaining 79.6% of the total variance. Dimension 1 represented process intensity and xylose transport, while Dimension 2 reflected molecular-weight-driven XOS fractionation. The acid-assisted process (T4) exhibited a distinct multivariate signature, characterized by enhanced carbohydrate mobilization and improved XOS recovery with reduced dependence on dilution. Overall, coupling hydrothermal pretreatment with membrane fractionation proved to be an efficient, and environmentally friendly strategy for coffee by-product valorization, consistent with hemicellulose-first biorefinery models and the principles of the circular bioeconomy.