Effects of Pretreatment with Ionic Liquids on Cellulose Hydrolysis under Hydrothermal Conditions.

Abstract

Hydrothermal hydrolysis in hot pressurized liquid water (HPLW) is attractive for biomass conversion into valuable products because it achieves high reaction rates without catalysts and additives. The hydrothermal hydrolysis of high crystalline cellulose requires higher reaction temperature than polysaccharides having low crystallinity. It can be expected to increase the reaction rate or decrease temperature by decreasing the crystallinity. In the present study ashless filter paper as a fibrous pure cellulose sample was pretreated with ionic liquids (ILs) such as imidazolium chloride ILs containing alkyl side chains ranging from two to six carbons, and with an aqueous solution of bis(ethylenediamine ammonium) copper (BEDC). Herein, the pretreatment with ILs was to regenerate filter paper: dissolving in ILs at 373 K for 120 min or in an aqueous BEDC solution at room temperature, precipitating by adding water, washing the solid, and then drying. Subsequently, the pretreated filter paper samples were hydrolyzed at 533 K and 5.0 MPa in HPLW in a small semi-batch reactor, and the effects of the pretreatment with ILs or BEDC on reaction rates and product yields were examined. While the crystallinity indexes with all ILs and BEDC after the pretreatments decreased to 44 to 47 from the original sample of 87, the reaction rates and product yields were significantly affected by the IL species. At 533 K and 5.0 MPa, the dissolution rate with [AMIM][Cl] was nine times as fast as that for untreated sample.