Abstract
Kraft lignin was treated with subcritical water at moderate temperatures (120−220 °C) in different gas atmospheres, with the goal of optimizing its depolymerization under mild conditions. Lignin depolymerization was observed and compared using different homogeneous and heterogeneous catalysts in both nitrogen and carbon dioxide atmospheres. The most important treatment parameters for maximum lignin depolymerization and the highest yields of phenolic and other aromatic monomers were optimized. The influence of the process temperature, pressure, and time in both gas atmospheres was defined and optimized for maximum liberation of monomers into the aqueous phase. The yields of total phenols and other aromatics in the nitrogen atmosphere were the highest at 150 °C, whereas treatment in the carbon dioxide atmosphere required higher temperatures (200 °C) for a comparable efficiency. The effects of phenol addition as a capping agent in lignin depolymerization were observed and defined for both gas atmospheres. Phenol addition caused a remarkable increase in the total phenols content in the aqueous phase; however, it did not significantly affect the contents of other aromatics. The antioxidant properties of lignin hydrolysates obtained at different temperatures in different gas atmospheres were compared, correlated with the total phenols contents, and discussed, showing the promising potential of lignin hydrolysates obtained under mild subcritical water conditions.