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The 'lignin-first' approach has recently gained attention as an alternative whole biomass pretreatment technology with improved yield and selectivity of aromatics compared with traditional upgrading processes using technical lignins. Metal triflates are effective co-catalysts that considerably speed up the removal of lignin fragments from the whole biomass. As their cost is too high in a scaled-up process, we explored here the use of HCl, H 2 SO 4 , H 3 PO 4 and CH 3 COOH as alternative acid co-catalysts for the tandem reductive fractionation process. HCl and H 2 SO 4 were found to show superior catalytic performance over H 3 PO 4 and CH 3 COOH in model compound studies that simulate lignin-carbohydrate linkages (phenyl glycoside, glyceryl trioleate) and lignin intralinkages (guaiacylglycerol-β-guaiacyl ether). HCl is a promising alternative to the metal triflates as a co-catalyst in the reductive fraction of woody biomass. Al(OTf) 3 and HCl, respectively, afforded 46 wt% and 44 wt% lignin monomers from oak wood sawdust in tandem catalytic systems with Pd/C at 180 °C in 2 h. The retention of cellulose in the solid residue was similar.

Selective production of mono-aromatics from lignocellulose over Pd/C catalyst: the influence of acid co-catalysts