Effects of Extraction Methods on Structure and Valorization of Corn Stover Lignin by a Pd/C Catalyst

With the significant development of efficient pretreatments of lignocellulosic biomass towards using carbohydrate compositions for biofuel production, the valorization of associated lignin products into valuable chemicals has gained much attention. Four lignins obtained by pretreatment of corn stover with emerging ionic liquid‐based mixed organic electrolytes (ILOE) and alkaline twin‐screw extrusion (ATSE) pretreatment technologies were characterized by gel permeation chromatography (GPC), FTIR, HSQC, 31P NMR spectroscopy, and SEM. These lignins were valorized by using Pd/C under various conditions, followed by an elucidation of the relationship between the lignin structure and valorization efficiency and selectivity. The pretreatment/separation methods have a significant effect on lignin structure and subsequent valorization efficiency. HSQC spectra revealed that corn stover lignin consisted of β‐O‐4, β‐5, β‐1 linkages, and cinnamyl alcohol end groups. The extracted lignins (EL) showed less carbohydrates and β‐O‐4 units than those of enzymatic hydrolytic lignins (EHL). The yields of bio‐oils were 61.7 % and 57.9 % for ATSE‐EL and ILOE‐EL, and 34.2 % and 45.1 % for ATSE‐EHL and ILOE‐EHL under optimal and comparative conditions, respectively. Part of the syringyl (S) units were converted into guaiacyl or p‐hydroxyphenyl (H) units by release of methoxyl groups on the aromatic ring through hydrogenolysis, which led to a decreased proportion of S units and an increased proportion of H units in oil compared with in lignin.

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