Effective Biomass Fractionation Through Oxygen-Enhanced Alkaline-Oxidative Pretreatment

The high recalcitrance of plant cell walls is an obstacle for effective chemical or biological conversion into renewable chemicals and transportation fuels. Here, we investigated the utilization of both oxygen (O-2) and hydrogen peroxide (H2O2) as co-oxidants during alkaline-oxidative pretreatment to improve biomass fractionation and increase enzymatic digestibility. The oxidative pretreatment of hybrid poplar was studied over a variety of conditions. Employing O-2 in addition to H2O2 as a co-oxidant during the two-stage alkaline pre-extraction/copper-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment process resulted in a substantial improvement in delignification relative to using H2O2 alone during the second-stage Cu-AHP pretreatment, leading to high overall sugar yields even at H2O2 loadings as low as 2% (w/w of the original biomass). The presence of H 2 0 2 , however, was both critical and synergistic. Performing analogous reactions in the absence of H2O2 resulted in approximately 25% less delignification and 30% decrease in sugar yields. The lignin isolated from this dual oxidant second stage had high aliphatic hydroxyl group content and reactivity to isocyanate, indicating that it is a promising substrate for the production of polyurethanes. To test the suitability of the isolated lignin as a source of aromatic monomers, the lignin was subjected to a sequential Bobbitt's salt oxidation followed by a formic acid-catalyzed depolymerization process. Monomer yields of approximately 17% (w/w) were obtained, and the difference in yields was not significant between lignin isolated from our Cu-AHP process with and without O-2 as a co-oxidant. Thus, the addition of O-2 did not lead to significant lignin crosslinking, a result consistent with the two-dimensional heteronuclear single-quantum coherence NMR spectra of the isolated lignin.