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Unveiling pyrolysis mechanism of furfural: a theoretical and kinetic study
Yuqiang Li1, Jiaxin Sun1, Shoulong Lin1
1School of Energy Science and Engineering, Central South University, Changsha 410083, China.
Abstract:
As a core platform molecule in biomass conversion, furfural requires accurate prediction of its pyrolysis behavior for the practical application of furan-based alternative fuels. However, existing pyrolysis models are inadequate for describing its thermal decomposition, as many kinetic parameters estimated via the analogical method introduce significant uncertainty. This study employs quantum chemical calculations based on Transition State Theory (TST) and Rice Ramsperger Kassel Marcus (RRKM) theory to systematically investigate hydrogen-abstraction, hydrogen-addition, and unimolecular reactions in furfural pyrolysis, with reaction rates calculated over 500-2500 K. Results show that the analogical method overestimates the rates of hydrogen-abstraction and hydrogen-addition reactions at low temperatures. Simulation validation was conducted using a Perfectly Stirred Reactor (PSR). Mole fraction comparison analysis confirms the improved model more accurately reproduces the variation trends and magnitudes of experimental data. Sensitivity analysis indicates that the modified model corrects the potential overestimation of the contribution of addition pathways in the original model.
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