Catalytic fast pyrolysis of lignin isolated by hybrid organosolv—steam explosion pretreatment of hardwood and softwood biomass for the production of phenolics and aromatics

Abstract

Lignin, one of the three main structural biopolymers of lignocellulosic biomass, is the most abundant natural source of aromatics with a great valorization potential towards the production of fuels, chemicals, and polymers. Although kraft lignin and lignosulphonates, as byproducts of the pulp/paper industry, are available in vast amounts, other types of lignins, such as the organosolv or the hydrolysis lignin, are becoming increasingly important, as they are side-streams of new biorefinery processes aiming at the (bio)catalytic valorization of biomass sugars. Within this context, in this work, we studied the thermal (non-catalytic) and catalytic fast pyrolysis of softwood (spruce) and hardwood (birch) lignins, isolated by a hybrid organosolv–steam explosion biomass pretreatment method in order to investigate the effect of lignin origin/composition on product yields and lignin bio-oil composition. The catalysts studied were conventional microporous ZSM-5 (Zeolite Socony Mobil–5) zeolites and hierarchical ZSM-5 zeolites with intracrystal mesopores (i.e., 9 and 45 nm) or nano-sized ZSM-5 with a high external surface. All ZSM-5 zeolites were active in converting the initially produced via thermal pyrolysis alkoxy-phenols (i.e., of guaiacyl and syringyl/guaiacyl type for spruce and birch lignin, respectively) towards BTX (benzene, toluene, xylene) aromatics, alkyl-phenols and polycyclic aromatic hydrocarbons (PAHs, mainly naphthalenes), with the mesoporous ZSM-5 exhibiting higher dealkoxylation reactivity and being significantly more selective towards mono-aromatics compared to the conventional ZSM-5, for both spruce and birch lignin.