Gas-phase pyrolysis of methyl glucosides and levoglucosan

Levoglucosan, the major intermediate in cellulose pyrolysis, is stable up to around 500?°C in the gas phase. To study whether this stability is a characteristic property of levoglucosan, the gas-phase reactivity was compared with those of methyl α- and β-glucosides at 200–500?°C (residence time 1.2–2.0 s). The methyl glucosides decomposed even at 200 and 300?°C to form levoglucosan exclusively. This selective transglycosylation was explained with a concerted mechanism. Fragmentation of the glucosides forming C1–C3 carbonyl compounds started at 400?°C, a temperature lower than that of levoglucosan (500?°C). Thus, levoglucosan is a special carbohydrate that is stable in the gas phase, and the stability is explained by the steric hindrance of the bicyclic ring. Formation of the anhydrofuranose isomer and furans was negligible from the gas-phase pyrolysis of these compounds, suggesting that these are produced mainly from the molten-phase pyrolysis. These results show the roles of gas- and molten-phase reactions during carbohydrate pyrolysis, providing insights for upgrading biomass pyrolysis/gasification processes.