Supercritical Carbon Dioxide Extraction of Lignocellulosic Bio-Oils: The Potential of Fuel Upgrading and Chemical Recovery

Bio-oils derived from the thermochemical processing of lignocellulosic biomass are recognized as a promising platform for sustainable biofuels and chemicals. While significant advances have been achieved with regard to the production of bio-oils by hydrothermal liquefaction and pyrolysis, the need for improving their physicochemical properties (fuel upgrading) or for recovering valuable chemicals is currently shifting the research focus towards downstream separation and chemical upgrading. The separation of lignocellulosic bio-oils using supercritical carbon dioxide (sCO₂) as a solvent is a promising environmentally benign process that can play a key role in the design of innovative processes for their valorization. In the last decade, fundamental research has provided knowledge on supercritical extraction of bio-oils. This review provides an update on the progress of the research in sCO₂ separation of lignocellulosic bio-oils, together with a critical interpretation of the observed effects of the extraction conditions on the process yields and the quality of the obtained products. The review also covers high-pressure phase equilibria data reported in the literature for systems comprising sCO₂ and key bio-oil components, which are fundamental for process design. The perspective of the supercritical process for the fractionation of lignocellulosic bio-oils is discussed and the knowledge gaps for future research are highlighted.