The complexity and heterogeneity of lignin requires a detailed understanding in order to decide about more efficient lignin valorization approaches. This study deals with the characterization of lignins from Populus alba L. generated as by-products in different transformation processes: kraft pulping, organosolv and dilute acid hydrolysis. In addition to the composition, the chemical and structural features of the different lignins were investigated by Fourier Transform infrared spectroscopy (FTIR), solid-state 13C nuclear magnetic resonance (13C NMR), two-dimensional nuclear magnetic spectrometry (2D NMR), size exclusion chromatography (SEC), and thermal analysis. Organosolv lignin showed noticeably different characteristics compared to kraft and acid hydrolysis lignins; higher molar mass, higher amount of side-chain linkages (mainly aryl-β ether and resinol) together with lower phenolic content. On the contrary, kraft and acid hydrolysis lignins presented an extensive elimination of lateral chains and therefore a higher phenolic content, which suggests a much stronger lignin depolymerization (lower molar mass) during these processes. Moreover, thermal analysis results revealed that the thermal stability of kraft and acid hydrolysis lignins was higher than that of organosolv lignin, especially in the case of acid hydrolysis lignin. According to all these characteristics, several valorization pathways for studied lignin are discussed.
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