Role of Deep Eutectic Solvent Precursors as Hydrotropes: Unveiling Synergism/Antagonism for Enhanced Kraft Lignin Dissolution

Abstract

Lignin holds significant potential as a feedstock for generating valuable aromatic compounds, fuels, and functional materials. However, achieving this potential requires the development of effective dissolution methods. Previous works have demonstrated the remarkable capability of hydrotropes to enhance the aqueous solubility of lignin, an amphiphilic macromolecule. Notably, deep eutectic solvents (DESs) have exhibited hydrotropic behavior, significantly increasing the aqueous solubility of hydrophobic solutes, making them attractive options for lignin dissolution. This study aimed at exploring the influence of hydrogen bond acceptors (HBAs) and hydrogen bond donors (HBDs) on the performance of DESs as hydrotropes for lignin dissolution, while possible dissolution mechanisms in different water/DES compositions were discussed. The capacity of six alcohols (glycerol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol) and cholinium chloride to enhance the solubility of Kraft lignin in aqueous media was investigated. A correlation between solubility enhancement and the alkyl chain length of the alcohol was observed. This was rationalized upon the competition between hydrotrope–hydrotrope and solute–hydrotrope aggregates with the latter being maximized for 1,4-butanediol. Interestingly, the hydrotropic effect of DESs on lignin solubility is well represented by the independent sum of the dissolving contributions from the corresponding HBAs and HBDs in the diluted region. Conversely, in the concentrated region, the solubility of lignin for a certain hydrotrope concentration was always found to be higher for the pure hydrotropes rather than their combined HBA/HBD counterparts.