Condensation of α‑Carbonyl Aldehydes Leads to the Formation of Solid Humins during the Hydrothermal Degradation of Carbohydrates

Catalytic hydrothermal conversion of carbohydrates could provide a series of versatile valuable platform chemicals, but the formation of solid humins greatly decreased the efficiency of the process. Herein, by studying the hydrothermal degradation behavior and analyzing the degradation paths of kinds of model compounds including carbohydrates, furan compounds, cyclic ketone derivatives, and some simple short carbon-chain oxy-organics, we demonstrate that α-carbonyl aldehydes and α-carbonyl acids are the key primary precursors for humin formation during the hydrothermal conversion process. Then, we analyzed the hydrothermal degradation paths of two simple α-carbonyl aldehydes including glyoxal and pyruvaldehyde and found that the α-carbonyl aldehydes could undergo aldol condensation followed by acetal cyclization and dehydration to form solid humins rich of furan ring structure or undergo Cannizaro route (hydration followed by 1,2-hydride shift) to form corresponding α-hydroxy acids. On the basis of the hydrothermal behavior of the α-carbonyl aldehydes, we mapped the hydrothermal degradation routes of carbohydrates (glucose, fructose, and xylose) and illuminated the formation details of α-carbonyl aldehydes, α-hydroxy acids, γ-lactones, furfural derivatives, and humins. Finally, we deduced the typical structure fragments of humins from three α-carbonyl aldehydes of pyruvaldehyde, 2,5-dioxo-6-hydroxy-hexanal, and 3-deoxyglucosone, all of which could be formed during the hydrothermal degradation of hexose.