Natural Deep Eutectic Solvent-Assisted Hydrothermal Carbonization of Corn Stover for Producing Lignin-Rich Solid Fuel and Sugar-Rich Intermediates

The sustainable conversion of agricultural waste biomass, particularly crop residues such as corn stover, into high-value products is vital for reducing their open-field burning and mitigating environmental hazards. The hydrothermal carbonization (HTC) process integrated with natural deep eutectic solvents (NADES) presents an alternative approach for valorizing biomass into lignin-rich solid fuels and fermentable sugars for bioethanol production. In this study, corn stover was subjected to HTC using deionized (DI) water, a xylose-based NADES (ChCl:Xy:W), and an oxalic acid-based NADES (ChCl:OA:W) in a 150–300 °C temperature range to optimize both solid fuel and sugar stream yields. Characterization, including fiber analysis, SEM, FTIR, EDS, and bomb calorimetry, was conducted to evaluate structural, compositional, and energetic transformations. The results explored the HTC process, restructuring the biomass, promoting extensive hemicellulose solubilization and cellulose depolymerization, as well as substantially enriching lignin and polymerized compounds with increasing temperature. In addition, the DI water at 300 °C generated a lignin-rich residue, the Xy-based NADES effectively removed ash and extractives, and the OA-based NADES produced the most carbon-dense hydrochar with the highest calorific value. Collectively, these findings demonstrate that solvent-assisted HTC may be employed as a possible strategy for the valorization of agricultural residues into high-energy solid fuels.