Effect of ball milling on the hydrolysis of microcrystalline cellulose in hot‐compressed water

Ball milling leads to a considerable reduction in cellulose particle size and crystallinity, as well as a significant increase in the specific reactivity of cellulose during hydrolysis in hot‐compressed water (HCW). Cryogenic ball milling for 2 min also results in a significant size reduction but only little change in cellulose crystallinity and specific reactivity during hydrolysis. Therefore, crystallinity is the dominant factor in determining the hydrolysis reactivity of cellulose in HCW while particle size only plays a minor role. Ball milling also significantly influences the distribution of glucose oligomers in the primary liquid products of cellulose hydrolysis. It increases the selectivities of glucose oligomers at low conversions. At high conversions, the reduction in chain length plays an important role in glucose oligomer formation as cellulose samples become more crystalline. An extensive ball milling completely converts the crystalline cellulose into amorphous cellulose, substantially enhancing the formation of glucose oligomers with high degrees of polymerization. © 2010 American Institute of Chemical Engineers AIChE J, 2011