The low-grade energy properties and high O content of biomass limit its efficient energy utilization. Torrefaction is known to be one of the most promising thermochemical conversion methods for upgrading biomass. 250 °C Gas-pressurized (GP) torrefaction realizes deep decomposition of hemicellulose in biomass to as high as 99.7% by deoxygenation and aromatization. However, the above thermochemical conversion mechanism at molecular-level is currently scant. Here, a novel molecular structural parameter method and pure hemicellulose torrefaction were employed to investigate the thermochemical conversion mechanism. Results demonstrate that O content of 250 °C GP torrefied hemicellulose was as low as 28.8 wt%, which was considerably lower than 44.6 wt% of traditional torrefied hemicellulose. There are five deoxygenation mechanisms of hemicellulose during the GP torrefaction: deacetylation, decarbonylation, dehydroxylation, ring opening and cyclization reactions to produce CO2/CH3COOH, CO, H2O, ketones/aldehydes and furans. The deoxygenation and aromatization reactions cause the chemical structure of hemicellulose evolution significantly, these mechanisms are: active hemicellulose undergo aromatization reaction through cyclization and deoxidation to generate preliminary 2-ring furans polymer, followed by stepwise polymerization reactions to form 4-ring and 6-ring furans polymers. These polymerization reactions further greatly enhance deoxygenation reaction. A thermochemical conversion mechanism model is developed based on the above investigation. This work provides a novel method for determining the molecular structure and reaction mechanism of thermochemical converted biomass.
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