Holistic investigation of structural evolution in corn stover lignin under pretreatment with varying -valerolactone concentrations

Until now, research on green and sustainable gamma-valerolactone (GVL) pretreatment has predominantly centered on component separation efficiency, with limited attention given to the lignin structure. Nonetheless, the lignin's structure is considerably affected by the fractionation, consequently influencing its potential valorization. Herein, we conducted a holistic investigation of the structural evolution of two fractions of lignin in corn stover, obtained under pretreatment with varying GVL concentrations: GVL lignin (GVLL) originated from pretreatment liquor and cellulolytic enzyme lignin (CEL) separated from pretreated residue. Our findings indicated a general positive correlation between the molecular weight and polydispersity index of both GVLL and CEL with the increasing GVL concentration. This phenomenon is attributed to the enhanced lignin dissolution and relocation as the GVL concentration increases. Moreover, higher GVL concentrations also increased the acidity of reaction system, leading to degradation of beta-O-4 linkages from 45.2 to 34.9 and 57.6 to 37.9 per 100 aromatic units in GVLL and CEL, respectively. Compared to CEL, GVLL exhibited a more remarkable phenolics yield (33.7% vs. 22.2%) during hydrodeoxygenation due to its superior purity and lower degree of polymerization. Recycling studies demonstrated the stability of GVL at lower concentrations. These findings provide valuable insights for optimizing GVL pretreatment systems.