Experimental and modeling study of the high-temperature combustion chemistry of tetrahydrofurfuryl alcohol
Luc-Sy Tran, Hans-Heinrich Carstensen, Kae Ken Foo, Nathalie Lamoureux, Sylvie Gosselin, Laurent Gasnot Abderrahman El-Bakali, Pascale Desgroux
"Experimental and modeling study of the high-temperature combustion chemistry of tetrahydrofurfuryl alcohol"
Proceedings of the Combustion Institute 38 (2021) 631–640
Lignocellulosic tetrahydrofuranic (THF) biofuels have been identified as promising fuel candidates for
spark-ignition (SI) engines. To support the potential use as transportation biofuels, fundamental studies of
their combustion and emission behavior are highly important. In the present study, the high-temperature
(HT) combustion chemistry of tetrahydrofurfuryl alcohol (THFA), a THF based biofuel, was investigated
using a comprehensive experimental and numerical approach.
Representative chemical species profiles in a stoichiometric premixed methane flame doped with ∼20%
(molar) THFA at 5.3 kPa were measured using online gas chromatography. The flame temperature was obtained
by NO laser-induced fluorescence (LIF) thermometry. More than 40 chemical products were identified
and quantified. Many of them such as ethylene, formaldehyde, acrolein, allyl alcohol, 2,3-dihydrofuran,
3,4-dihydropyran, 4-pentenal, and tetrahydrofuran-2-carbaldehyde are fuel-specific decomposition products
formed in rather high concentrations. In the numerical part, as a complement to kinetic modeling, high-level
theoretical calculations were performed to identify plausible reaction pathways that lead to the observed
products. Furthermore, the rate coefficients of important reactions and the thermochemical properties of
the related species were calculated. A detailed kinetic model for high-temperature combustion of THFA was
developed, which reasonably predicts the experimental data. Subsequent rate analysis showed that THFA
is mainly consumed by H-abstraction reactions yielding several fuel radicals that in turn undergo either β-scission reactions or intramolecular radical addition that effectively leads to ring enlargement. The impor-
tance of specific reaction channels generally correlates with bond dissociation energies. Along THFA reaction
routes, the derived species with cis configuration were found to be thermodynamically more stable than their
corresponding trans configuration, which differs from usual observations for hydrocarbons.
Lignocellulosic tetrahydrofuranic (THF) biofuels have been identified as promising fuel candidates for
spark-ignition (SI) engines. To support the potential use as transportation biofuels, fundamental studies of
their combustion and emission behavior are highly important. In the present study, the high-temperature
(HT) combustion chemistry of tetrahydrofurfuryl alcohol (THFA), a THF based biofuel, was investigated
using a comprehensive experimental and numerical approach.
Representative chemical species profiles in a stoichiometric premixed methane flame doped with ∼20%
(molar) THFA at 5.3 kPa were measured using online gas chromatography. The flame temperature was obtained
by NO laser-induced fluorescence (LIF) thermometry. More than 40 chemical products were identified
and quantified. Many of them such as ethylene, formaldehyde, acrolein, allyl alcohol, 2,3-dihydrofuran,
3,4-dihydropyran, 4-pentenal, and tetrahydrofuran-2-carbaldehyde are fuel-specific decomposition products
formed in rather high concentrations. In the numerical part, as a complement to kinetic modeling, high-level
theoretical calculations were performed to identify plausible reaction pathways that lead to the observed
products. Furthermore, the rate coefficients of important reactions and the thermochemical properties of
the related species were calculated. A detailed kinetic model for high-temperature combustion of THFA was
developed, which reasonably predicts the experimental data. Subsequent rate analysis showed that THFA
is mainly consumed by H-abstraction reactions yielding several fuel radicals that in turn undergo either β-scission reactions or intramolecular radical addition that effectively leads to ring enlargement. The impor-
tance of specific reaction channels generally correlates with bond dissociation energies. Along THFA reaction
routes, the derived species with cis configuration were found to be thermodynamically more stable than their
corresponding trans configuration, which differs from usual observations for hydrocarbons.