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Graphical abstractHighlights► Thermal analysis provides real-time data on hydrothermal reactions under realistic conditions. ► From DSC, hemicellulose hydrolysis has low enthalpy change but xylose degradation is exothermic. ► Hydrothermal exothermic degradation reactions may be similar to early stage biomass pyrolysis. ► DMTA shows that the polymeric structure of lignin in biomass is degraded at high temperatures. ► Hydrothermal reactions are effective at greater than 50% solids content.

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