Solvent consumption in non-catalytic alcohol solvolysis of biorefinery lignin

Abstract

Lignin solvolysis in supercritical alcohols provides a method for producing a deoxygenated liquid bio-oil. Solvent consumption is however inevitable and due to the high cost of alcohols, relative to a bio-oil product, it can hinder commercial viability. In order to investigate the reactions of solvent consumption we studied solvolysis of biorefinery lignin in several primary alcohols. Lignin solvolysis in methanol, ethanol, 1-propanol and 1-butanol performed similarly with respect to bio-oil composition; however, methanol gave much lower bio-oil yield. Solvent consumption increases with reaction temperature for all alcohols and from 10 wt% at 300 °C to 35 wt% at 400 °C when using ethanol. The mechanism for solvent consumption was found mainly to take place through three different reactions: direct decomposition to gas through decarbonylation, formation of light condensation products and incorporation of the alcohol into the bio-oil through covalent bonding. Incorporation of the alcohol into the depolymerised oil product by covalent bonding may be a desirable effect which contributes to increased oil yield, inhibition of repolymerisation, reduced oxygen content and elimination of acidity.