Fractionation and purification of a high-impurity, alkaline-pretreated, corn stover lignin with simple renewable solvents

Corn stover has been identified as a key resource in the transition from petrochemicals to sustainably sourced energy and materials; however, the as-recovered lignin from alkaline pretreatment contains unusually high levels of residual impurities, which must be removed to maximize potential application. Thus, the Aqueous Lignin Purification using Hot Agents (ALPHA) process was applied to a corn stover lignin containing similar to 10 % carbohydrates and similar to 3 % ash. Lignin fractions similar to 100 times cleaner than the feed lignin and of controlled molecular weight (i.e., as low as one-fifth and as high as triple the absolute molecular weight (Mw) of the feed) were obtained. The ALPHA solvent was a hot (60 or 75 degrees C) solution of 80 % ethanol combined with the feed lignin at an unusually low, 3:1 solvent-to-feed lignin ratio - conditions that create the liquid-liquid equilibrium (LLE) phase split needed to practice ALPHA. Lignin fractionation then commenced by adding water to the original solution, decreasing the ethanol content in increments of 3-4 wt%. Surprisingly, the highest Mw fractions did not precipitate until the solution contained just below 50 % ethanol, by which point almost half of the starting lignin of near-average Mw had already precipitated. Another unexpected result was that the lignin waste stream from the initial purification step could be increased from 40 to 98 % lignin in a single equilibrium stage simply by re-processing that waste with another 80 % ethanol solution at the conditions given above. In summary, the efficacy of ALPHA for purifying and fractionating an impurities-laden corn stover lignin to ultraclean levels in a scalable manner requiring only aqueous bioethanol solutions has been demonstrated.