Influence of Pretreatment Severity Factor and Hammett Acidity on Softwood Fractionation by an Acidic Protic Ionic Liquid

[Image: see text] The impact of pretreatment severity in the acidic protic ionic liquid (IL) N,N-dimethylbutylammonium hydrogen sulfate, [DMBA][HSO(4)] using pine softwood was investigated using a modified severity factor that considers the IL solution acidity based on Hammett acidity. A Box–Behnken experimental design was employed to evaluate pretreatment severity with temperature, pretreatment time, and IL concentration as factors and degree of delignification as the response variable. The optimal pretreatment conditions were found to be at 170 °C, 30 min, and 80 wt % IL, which yielded nearly 90% of delignification and 95% of glucose yield in enzymatic saccharification. The modified severity factor showed an improved correlation with the fractionation indicators relative to the classical pretreatment severity factor, indicating that it can better predict the pretreatment outcomes, particularly for delignification and hemicellulose removal. The fate of hemicellulose, its conversion to humins, and its impact on the precipitated lignin properties were also investigated and correlated to the modified pretreatment severity factor. It was found that such parameters alone cannot be used to predict the fate of dissolved hemicellulose sugars in the IL medium. Furthermore, IL acidity greatly impacts the degradation of the dissolved hemicellulose sugars and the formation of humins.