Experimental and kinetic modeling studies of furfural pyrolysis at low and atmospheric pressures

Furfural (2-furaldehyde) is a promising platform chemical for lignocellulosic biofuels, but its thermal decomposition channels are not well understood. To better understand furfural thermal decomposition kinetics, flow tube reactor pyrolysis combined with synchrotron vacuum ultraviolet photoionization mass spectrometry at low and atmospheric pressures and temperatures from 929 to 1365 K was investigated. Carbon monoxide, methane, acetylene, propyne, allene, furan, and vinylketene as the main products were detected and measured. A detailed kinetic model for furfural pyrolysis consisting of 585 species and 3018 reactions was built based on the potential energy surface, and validated against the experimental data from the current and previous studies. Rate of production analysis shows that furfural mainly underwent unimolecular non-radical decomposition channel to form vinylketene and carbon monoxide. Sequential decomposition of vinylketene led to the production of allene, propyne and carbon monoxide, etc. H-atom addition reactions on the furan ring was the main source of furan. HCO, CH3 and COOCH3 groups influence the decomposition pathways of furanic fuels, and accelerate their decomposition with decomposition temperatures in the sequence of methyl 2-furoate < furfural < 2,5-dimethylfuran < 2-methylfuran < furan.

Automated summary

Investigation of furfural thermal decomposition kinetics using flow tube reactor pyrolysis and synchrotron vacuum ultraviolet photoionization mass spectrometry revealed that the main products included carbon monoxide, methane, acetylene, propyne, allene, furan, and vinylketene. A detailed kinetic model consisting of 585 species and 3018 reactions was built and validated against experimental data, showing that furfural mainly underwent unimolecular non-radical decomposition to form vinylketene and carbon monoxide. Hydrogen addition reactions on the furan ring were identified as the main source of furan. The decomposition pathways of furanic fuels were influenced by specific functional groups, accelerating their decomposition process.