Assesment of technical lignins for uses in biofuels and biomaterials: Structure-related properties, proximate analysis and chemical modification

• Structural and thermal characterization of isolated lignins.
• Evaluation of lignins for biomaterials and biofuel applications.
• Chemical modification of lignins to improve reactivity.
• Introduction of vinyl groups to use as macromonomer.

The potential of organosolv and kraft eucalyptus and spruce lignin as feedstock for polymeric materials and biofuel applications was assessed. Proximate analysis was used to predict the heating values and char formation. Chemical modification, based on the esterification reaction with methacryloyl chloride, was applied to introduce vinyl groups into the lignin macromolecules for enhanced reactivity. Kraft eucalyptus and spruce lignins had a more condensed structure than organosolv lignins, which resulted in greater thermal stability for these lignins. For different species within the same process, the thermal parameters showed a correlation with certain structural and compositional parameters (ash and sugars content, molecular weight and degree of condensation). Organosolv spruce lignin produced the highest heating value of 24 MJ/Kg, which is suitable for biofuel applications. The content of phenolic OH groups was higher for kraft lignins and especially higher for softwood lignins, both organosolv and kraft. The degree of methacrylation, estimated from the content of vinyl groups per C9 lignin unit, was significantly greater for organosolv lignins than for kraft lignins despite the higher OH-groups content in the latter.