Chemicals from lignin by diol-stabilized acidolysis: reaction pathways and kinetics

Abstract

The product selectivity, production rates and the required process conditions are important for technology development. Selective lignin depolymerisation on the prime β-O-4 motif provides an opportunity to obtain valuable functionalized phenolic monomers. Diol-stabilized acidolysis of lignin with sulfuric acid, triflic acid or triflate salts is a proven β-O-4 cleavage methodology that forms acetals by trapping of released reactive aldehydes. For future scale-up, a better understanding of the prime reaction pathways and how these can be controlled upon changing reaction parameters is required. By using β-O-4 model compounds and ytterbium(III) triflate as catalyst, starting material conversion and product formation including two key intermediates, the diol adducts (in this study, ethylene glycol as the diol) and the vinyl ethers, were accurately monitored, allowing for detailed kinetic modelling. Over the selected temperature range (80–150 °C), higher temperatures led to higher overall carbon balance and selectivity for the main desired acetal product. The kinetic modelling allowed for establishing a detailed reaction network with activation energies and rate constants. These collectively led to new insights into the key steps involved in the diol-stabilized β-O-4 motif acidolysis and how the reaction selectivity can be manipulated by controlling the reaction temperature, and the ethylene glycol and water content. The elucidation on reaction kinetics and networks constitutes a further step in the design of a diol-stabilized lignin acidolysis process.