Chemical and thermal analysis of lignin streams from Robinia pseudoacacia L. generated during organosolv and acid hydrolysis pre-treatments and subsequent enzymatic hydrolysis

Abstract

Lignin streams produced in biorefineries are commonly used to obtain energy. In order to increase the competitiveness of this industry, new lignin valorization routes are necessary, for which a depth characterization of this biological macromolecule is essential. In this context, this study analyzed lignin streams of Robinia pseudoacacia L. generated during organosolv and acid hydrolysis pre-treatments and during the subsequent enzymatic hydrolysis. These lignins included dissolved lignins from pre-treatment liquors and saccharification lignins from pre-treated materials. Chemical composition and structural features were analyzed by analytical standard methods and Fourier Transform Infrared spectroscopy (FTIR), size exclusion chromatography (SEC), 13C solid state nuclear magnetic resonance (13C NMR) and 1H–13C two-dimensional nuclear magnetic resonance (2D NMR); while thermal characterization included thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). In general, all studied lignins contained a predominance of β-O-4′ aryl ether linkages, followed by resinol (β-β′) and phenylcoumaran (β-5′), with a predominance of syringyl over guaiacyl and hydroxyphenyl units. Nevertheless, the dissolved lignins revealed a removal of linkages, especially β-O-4′, leading to an enrichment of phenolic groups. Moreover, high thermal stability and good thermoplasticity were characteristics of these lignins. Contrary, the saccharification lignins exhibited a more intact structure, but with an important remaining carbohydrates content.