AbstractThe structural evolution of Panicum virgatum lignin during hydrothermal depolymerization was investigated. Product distribution from various temperatures was studied using gas chromatography-mass spectrometry (GC-MS ) and gel permeation chromatography (GPC) analysis. The physical-chemical properties of initial lignin, tetrahydrofuran soluble fraction, and char were also comparatively characterized by elemental analysis, scanning electron microscopy (SEM), thermogravimetry (TG), and Fourier transform infrared (FT-IR) spectroscopy. Results showed that both the depolymerization and repolymerization were significantly temperature-dependent. The undesired char formation becomes obvious when the temperature is greater than 180 °C. Further investigation demonstrated that H lignin is the most accessible for hydrothermal depolymerization, whereas S lignin is the most recalcitrant. Moreover, under the thermal effect and the dissolution of the subcritical water, the basic structure of lignin was first collapsed and then further decomposed into low-molecular weight products by the fracture of ether bonds, accompanied by char formation after repolymerization and dehydration.