The valorization of industrial lignin essentially requires
fractionation
resulting in lower structural heterogeneity and polydispersity. So
far, extensive fractionation approaches based on extraction with solvents,
gradient acid precipitation, and membrane-based filtration have been
developed to reduce the polydispersity and heterogeneity of technical
lignins. However, most reports tend to overlook the lignin fraction
that bonded with carbohydrates or the so-called lignin carbohydrate
complex (LCC), which always coexists in the initial lignin sample
and can significantly affect the properties of lignin, including its
homogeneity and solubility. In this study, we evaluated the ability
of 13 organic solvents to separate lignin bonded with carbohydrates.
It was found that carbohydrates could only be detected when the hydrogen
bonding capacity (δH) of solvent was no less than 8.0 (the δH
of tetrahydrofuran, THF). Based on this result, eight lignin fractions
with trace/large amounts of carbohydrates and decreased heterogeneity
were obtained using an elaborate sequential solvent extraction approach.
The following properties of each lignin fraction were compared: elemental
composition, carbohydrate content, molar mass, hydroxyl group content,
and thermal properties. In addition, we also studied the ability of
these lignin fractions to form lignin nanoparticles and confirmed
that fractions with trace amounts of carbohydrates were able to form
uniform spherical lignin nanoparticles (LNPs) than those with large
amounts of carbohydrates bonded fractions. In short, this study provided
a profound understanding of the role of the carbohydrates bonded to
lignin on the fractionation of lignin by organic solvents, further
demonstrating how carbohydrates influence the characteristics of lignin.