کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5134640 | 1492953 | 2017 | 11 صفحه PDF | دانلود رایگان |
- Kinetics of the gas-phase degradation suggest radical chain mechanisms.
- Restraint in the bicyclic ring affect the cyclic Grob and pinacol reactions.
- Radical chain pathways from the C- and O-centered radicals are postulated.
- Double bond formation causes fragmentation rather than furans formation.
- Dehydration via the C-centered radicals lead to the hydrocarbon gas formation.
Molecular mechanisms for the gas-phase degradation of levoglucosan, the major intermediate in cellulose gasification, were studied by kinetic analysis at 550-700 °C (residence time: 0.11-0.45 s), and a mixed mechanism including heterolysis and radical chain reactions is suggested. Density functional theory calculations indicated that one of the cyclic Grob reactions can proceed (Ea 57.4 kcal molâ1), which is supported by the selective formation of acrolein and glyoxal at 500 °C. Nevertheless, contributions of these heterolytic reactions were suggested to be smaller than radical chain reactions, which would proceed via the C- and O-centered radicals. Influences of the bicyclic ring and the hydrocarbon/oxygenated gas selectivity are also discussed. These results provide insights into the upgrading of the gasification processes of cellulosic biomass.
Journal: Journal of Analytical and Applied Pyrolysis - Volume 124, March 2017, Pages 666-676