Dehydration Leads to Hydrocarbon Gas Formation in Thermal Degradation of Gas-Phase Polyalcohols

To understand the molecular mechanisms of hydrocarbon gas formation in biomass gasification, gasification of simple polyalcohols (glycerol, propylene glycol, and ethylene glycol) were studied at 400, 600, and 800 °C (residence times: 0.9–1.4 s) from the viewpoint of dehydration reactions that form aldehydes with various substituents as intermediates to produce hydrocarbon gases. The results were also compared with those of glyceraldehyde and dihydroxyacetone, which are reported to produce syngas (H 2 and CO) selectively. All polyalcohols became reactive at 600 °C to form condensable products in 15.7–24.7% yields (C-based), corresponding to 33.9–38.4% based on the amounts of reacted polyalcohols. These condensable products, mostly aldehydes, act as gas-forming intermediates, because the polyalcohols were completely gasified at 800 °C (hydrocarbon gas contents: 20.3–35.3%, C-based). Yields of the intermediates bearing alkyl groups at 600 °C were proportionally correlated to the yields of hydrocarbon gases at 800 °C, suggesting that the alkyl groups are further converted into hydrocarbon gases via the fragmentation of acyl radicals. Dehydration reactions were suggested to occur in both heterolytic and radical mechanisms by theoretical calculations. Glyceraldehyde tended to fragment directly into CO and H 2 , instead of forming a dehydration intermediate. These results are informative for controlling the product gas composition in biomass gasification.