Hydrothermal carbonization of sawdust with the bio-oil of same origin impacts evolution of structures of hydrochar

The high tendency towards polymerization is a bottle-neck issue in upgrading of bio-oil, which, however, is highly desirable in co-hydrothermal carbonization (HTC) of biomass with bio-oil for enhancing production of hydrochar . In this study, co-HTC of bio-oil of the same origin with poplar sawdust was conducted at 180 to 260 °C. The results showed that the HTC in a water medium containing 10% bio-oil could enhanced the yield of hydrochar by ca. 36% at 220 or 260 °C through the cross-polymerization of the sugar-derived furans and ketones/aldehydes as well as the phenolics in bio-oil with the sawdust-derived organics. Furans/sugars in bio-oil showed much more contribution to the increase of hydrochar yield than the phenolics like guaiacol . The highly reactive organics in bio-oil even could react with the crystal region of cellulose at 180 °C, and affected property of hydrochar at especially the higher temperatures by promoting deoxygenation , enhancing carbonization, eliminating polar functionalities like -OH, retaining C=O for continued polymerization, etc. The co-existence of aliphatic organics and phenolics in bio-oil renders the simultaneous formation of highly volatile fraction and aromatic structures in the hydrochar. These created the carbon-rich hydrochar with higher crystallinity , lower hydrophilicity and improved comprehensive combustion index.