2‐step lignin‐first catalytic fractionation with bifunctional Pd/ß‐zeolite catalyst in a flow‐through reactor

This work demonstrates an additive and hydrogen‐free 2‐step lignin‐first fractionation in flow‐through. First, solvolytic delignification renders lignin liquors with its native chemical structure largely intact; and second, ß‐zeolite catalytic depolymerization of these liquors leads to similar monomer yields as the corresponding 1‐step fractionation process. Higher delignification temperatures lead to slightly lower ß−O−4 content in the solvated lignin, but does not affect significantly the monomer yield, so a higher temperature was overall preferred as it promotes faster delignification. Deposition of Pd on ß‐zeolite resulted in a bifunctional hydrogenation/dehydration catalyst, tested during the catalytic depolymerization of solvated lignin with and without hydrogen addition. Pd/ß‐zeolite displays synergistic effects (compared to the Pd/γ‐Al2O3 and ß‐zeolite tested individually and as a mixed bed), resulting in higher monomer yield. This is likely caused by increased acidity and the proximity between the metallic and acid active sites. Furthermore, different ß‐zeolite with varying SAR and textural properties were studied to shed light onto the effect of acidity and porosity in the stabilization of lignin monomers. While some of the catalysts showed stable performance, characterization of the spent catalyst reveals Al leaching (causing acidity loss and changes in textural properties), and some degree of coking and Pd sintering. This work demonstrates a 2‐step lignin‐first fraction strategy using a bifunctional catalyst consisting of Pd supported on ß‐zeolite. Furthermore, crucial insights for process optimization are explored: Effect of delignification temperature, comparison of ß‐zeolite performance of varying compositional and morphological properties, synergistic effects of bifunctional Pd/ß‐zeolite and catalyst stability studies.