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Gas‐Phase Reactions of Glyceraldehyde and 1,3‐Dihydroxyacetone as Models for Levoglucosan Conversion during Biomass Gasification
Author(s) -
Fukutome Asuka,
Kawamoto Haruo,
Saka Shiro
Publication year - 2016
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201501612
Subject(s) - levoglucosan , dihydroxyacetone , chemistry , glycolaldehyde , glyceraldehyde , glyoxal , pyrolysis , glycerol , decomposition , organic chemistry , photochemistry , catalysis , aerosol , biomass burning , dehydrogenase , enzyme
Levoglucosan, the major intermediate in wood gasification, is decomposed selectively to C 1 /C 2 fragments at 550–600 °C. Kinetic analyses suggest that radical chain mechanisms with the involvement of short‐lived carbonyl intermediates explain the lower production of larger fragments. To address this hypothesis, the gas‐phase reactivities of glyceraldehyde (Gald), 1,3‐dihydroxyacetone (DHA), and glycerol, as simple C 3 model compounds, were compared at 400–800 °C under N 2 flow at residence times of 0.9–1.4 s. Retro‐aldol fragmentation and dehydration proceeded for the pyrolysis of Gald/DHA at 400 °C, far below the 600 °C decomposition point of glycerol. Pyrolysis of Gald/DHA generated exclusively syngas (CO and H 2 ). On the basis of the results of theoretical calculations, the effects of carbonyl intermediates on reactivity were explained by postulating uni‐ and bimolecular reactions, although the bimolecular reactions became less effective at elevated temperatures.