Comparative study of solvolysis of technical lignins in flow reactor

The solvolysis of technical lignins was evaluated using water/ethanol solvent mixture with the aim of producing monomeric aromatic compounds in a continuous flow bench reactor. Four lignins issued from various biomasses (softwood, wheat straw) and extracted using different pulping processes (kraft, soda, organosolv) were engaged in the study. Before being converted, these lignins (two kraft, a soda, and an organosolv) were characterized by a multitechnique approach coupling compositional analysis, NMR, IR, GC, and SEC. Data thus obtained allowed us to point out the main differences in terms of structure and chemical composition. Based on its high solubility in water and water/ethanol mixture, alkaline lignin (i.e., from the kraft process) was used to optimize the reaction parameters. Thus, we found out that working at 225 °C under 8 MPa nitrogen using a 1-wt% basic solution of lignin allowed to operate the reactor without difficulties (no foam formation, no char) when a 1/1 water/ethanol mixture was used. Under these conditions, alkaline lignin was converted up to 76%. Other lignins were then evaluated leading to conversions between 46 and 74%. The reaction mixture obtained was fractioned to PM (precipitated matter), OP (organic products), and AP (aqueous phase soluble products) to allow careful analyses of the products. Analytical data obtained showed particularly that the number of β-O-4 linkages in the remaining solid material (PM) decreases significantly (up to − 95%) that correlated with the formation of monomeric organic compounds in OP, however in low amount due to over reactions leading to compounds evolving in the aqueous phase. Generally, whatever the lignin, guaiacol is the main aromatic compound observed under all reaction conditions evaluated.