Isolation of Highly Crystalline Cellulose via Combined Pretreatment/Fractionation and Extraction Procedures within a Biorefinery Concept.

Sustainable production of bio-based materials and chemicals requires integrated approaches which utilize all fractions of lignocellulosic biomass. In this work, highly crystalline cellulose was isolated via combined pretreatment/fractionation and extraction processes from beechwood sawdust. The proposed approach was based on the selective recovery of hemicellulose components in the first step, followed by enhanced delignification in the second step, permitting the efficient recovery of the remaining cellulose via bleaching in the final step. Hydrothermal pretreatment under tailored conditions in neat water or dilute acid resulted in almost complete hemicellulose removal (80-96 wt %) in the liquid fraction. In the second step, the formed surface lignin was isolated via mild extraction while enhanced removal of both native/structural and surface lignin (71 wt %) was achieved by applying the organosolv treatment using dilute sulfuric acid as catalyst. Dilute sulfuric acid pretreatment followed by acid catalyzed organosolv pretreatment proved to be the most efficient combined approach, leading to 80 wt % hemicellulose removal as xylose monomer, and 71 wt % delignification. High crystallinity cellulose (<88%), with an overall cellulose recovery of 68-91 wt % based on native cellulose in parent biomass was isolated in the last step via bleaching of all pretreated biomass solids. The proposed integrated biorefinery procedures that aim to whole "waste" biomass valorization, replacing fossil resources, with the use of green solvents (water, ethanol) at relatively mild temperature/pressure conditions, are in line with the scope of several United Nations Sustainable Development Goals, such as UN SDG 8, 11, 12, and 13.