Journal
FUEL PROCESSING TECHNOLOGY
Volume 253, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.fuproc.2023.107989
Keywords
Hemicellulose; Xylan; Branched monosaccharides; Pyrolysis; Density functional theory
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This study explored the pyrolysis behaviors and mechanisms of different monosaccharides, including arabinose, galactose, galacturonic acid, and glucuronic acid. The roles of structural differences in these monosaccharides were analyzed, and it was found that glucuronic acid undergoes a special C-C bond breaking reaction during pyrolysis. The findings provide a deep understanding of the pyrolysis chemistry of hemicellulose and the role of different branches.
The high percentage of branched units with different structures leads to the complex pyrolysis chemistry and product distribution of hemicellulose. In this study, four main branched monosaccharides, i.e., arabinose (Ara), galactose (Gal), galacturonic acid (GacA), and glucuronic acid (GlcA) were employed as typical xylan-based hemicellulose model compounds. The pyrolysis behaviors and mechanisms of these monosaccharides were deeply explored by the combination of pyrolysis experiments and density functional theory (DFT) calculations. Particularly, the roles of structural differences of these monosaccharides were carefully analyzed. Due to the uronic acid group, GacA and GlcA were easier to decompose, having two weightloss peaks with close intensity, and the release of CO2 had greater intensity than Ara and Gal pyrolysis at low temperatures. GlcA with the equatorial hydroxyl group can undergo a special C-C bond breaking reaction to depart the C6 uronic acid group to release HCOOH. The fast pyrolysis of these monosaccharides obtained similar product species but distinct relative contents. The structure of an uncertain hydromethyl-furnaose product was identified as 5-(hydroxymethyl)furan-3(2H)-one (5-HMFO) by combined DFT calculations and experimental results. The findings of this work are beneficial to gain a deep understanding of the pyrolysis chemistry of hemicellulose, especially the role of different branches.
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