From cellulose to levulinic acid 2.1. Mechanism and kinetics According to the generally accepted mechanism, acid-catalyzed hydrolysis of cellulose proceeds viaprotonation of the glycosidic oxygen in order to cleave the b-1,4-glycosidic bond into water-soluble cello-oligomers and ultimately to glucose (Scheme 1). Because of its crystalline form and intense intra- and intermo-lecular hydrogen bonding, cellulose breakdown in aqueous reaction media is a very slow reaction, implying the need of elevated temperatures and acid catalysis. Subsequent formation of LA occurs through a series of acid-catalyzed reactions, including dehydration of the formed hexoses to 5-hydroxy-methylfurfural (5-HMF), followed by rehydration-induced ring cleavage to yield LA along with an equivalent of formic acid. Enolization of D-glucose is identified as the key step in the formation of 5-HMF. Likewise, a similar mechanism allows rationalizing furfural formation in the acid-catalyzed decompo-sition of C5 sugars such as xylose or arabinose.
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