Hydrothermal liquefaction versus catalytic hydrodeoxygenation of a bioethanol production stillage residue to platform chemicals: A comparative study

Biobased chemicals like phenols and aromatics are preferably produced from cheap biomass waste streams. In this work, we have explored the potential of a eucalyptus-derived second generation bioethanol production stillage (BPS) residue for this purpose. A comparative study between a hydrothermal liquefaction (HTL) and a catalytic hydrodeoxygenation (HDO) step, as well as a 2-step HTL-HDO approach is reported, targeting at value-added low molecular weight platform chemicals (mainly alkylphenols and aromatics). HDO was observed to be a more suitable strategy than HTL for the production of organic oils enriched in valuable monomers. The direct HDO of the BPS using a commercial Ru/C catalyst at 450 °C and 100 bar H2 pressure led to an organic product oil (30.7 wt%) with a total monomer yield of 25.2 wt% (13.2 wt% of alkylphenolic+aromatics), compared to a 53.2 wt% of a product oil with 10.0 wt% monomers for the HTL step (305 °C). A 2-step HTL-HDO strategy was compared with the direct HDO approach. Comparable alkylphenolic+aromatic yields were obtained through this approach based on initial BPS intake (13.2 wt% vs 12.3 wt% for the direct HDO and HTL-HDO approach, respectively). Lower HTL temperatures (305 °C) for the first step are preferred to prevent over hydrogenation in the subsequent HDO step. As such, HTL appears a suitable pre-treatment for BPS and can (i) solve the issues related to the feeding of solids in pressurized continuous reactors for HDO and (ii) prevent coke formation during the HDO step, thus improving catalyst stability and durability.