Fractionation of lignocellulosic biomass to produce uncondensed aldehyde-stabilized lignin

Lignin is one of the most promising sources of renewable aromatic hydrocarbons. Current methods for its extraction from lignocellulosic biomass—which include the kraft, sulfite, and organosolv processes—result in the rapid formation of carbon–carbon bonds, leading to a condensed lignin that cannot be effectively depolymerized into its constituent monomers. Treatment of lignocellulosic biomass with aldehydes during lignin extraction generates an aldehyde-stabilized lignin that is uncondensed and can be converted into its monomers at near-theoretical yields. Here, we outline an efficient, reproducible, and scalable process for extracting and purifying this aldehyde-stabilized lignin as a solid, which can easily be re-dissolved in an organic solvent. Upon exposure to hydrogenolysis conditions, this material provides near-theoretical yields of aromatic monomers (~40–50% of the Klason lignin for a typical hardwood). Cellulose and hemicellulose are also efficiently fractionated. This protocol requires 6–7 h for the extraction of the stabilized lignin and a basic proficiency in synthetic chemistry.