Depolymerisation of <i>γ</i> ‐Valerolactone Organosolv Lignins with Unsupported Molybdenum‐Based Catalysts

Lignin is an attractive feedstock for a wide variety of applications ranging from aromatic chemicals and transportation fuels to resins and coatings. Emerging biorefinery concepts, like the organosolv process, enable the separation of all the lignocellulose components, and moreover, produce lignins of high quality and purity susceptible to valorisation by depolymerisation. In this work, we focus on the depolymerisation of lignins obtained by γ-valerolactone (GVL) organosolv fractionation of four biomass feedstocks, eucalyptus, white birch, sugarcane bagasse and Scots pine. We demonstrate that lignins extracted with the GVL process are depolymerised using unsupported molybdenum-based catalysts under reductive conditions in supercritical ethanol. As a result, over 90% yields of low-molecular-weight lignin oils are obtained with minimal char formation, yields of the aromatic monomers being 7-16 wt%. Furthermore, the design of experiments method is used to analyse the effect of depolymerisation conditions, catalyst, hydrogen loading and temperature, on the yields and properties of the product fractions. Notably, we show that the properties of the lignin oils and monoaromatics can be tuned towards the targeted application by modifying the depolymerisation conditions.