The excessive CO2 in the environment resulting from the combustion of fossil fuels has posed a significant challenge in terms of its conversion and utilization. In this work, the thermochemical conversion of guaiacol under supercritical CO2 (scCO2) was proposed, which not only enabled the consumption of CO2 but also facilitated the conversion of biomass into valuable products. It was concluded that the carbon gasification efficiency (CE) and hydrogen gasification efficiency (HE) were 37.10 % and 51.77 %, respectively, when the CO reached the maximum of 8.72 ± 0.28 mol/kg at 700 °C for 20 min. The addition of catalyst promoted the production of H2 and increased CE, the H2 yield of guaiacol gasification under different catalysts was ordered as Al2O3 > KOH > without catalyst > KCl. As the reaction temperature increased, the unreacted guaiacol and phenol decreased and were gradually converted to liquid products such as pyrene and benzo[c]phenanthrene. With the increase in reaction temperature, the more fully guaiacol was reacted, the easier it was to carbonize and form more carbon microspheres. In addition, reaction pathways for free radicals were proposed, including cleavage of free radicals, isomerization of free radicals, secondary cleavage of free radicals and recombination of free radicals. In short, degrading guaiacol using scCO2 is a feasible approach, which provides a new direction for the disposal and energy recovery of biomass in the future.
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