Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran

Ruben de Bruycker (1) , Luc-Sy Tran (1, 2) , Hans-Heinrich Carstensen (1) , Pierre-Alexandre Glaude (2) , Fabiola Monge (3) , Maria Alzueta (3) , Frédérique Battin-Leclerc (2) , Kevin M van Geem (1)

1 Laboratory for Chemical Technology
2 LRGP - Laboratoire Réactions et Génie des Procédés
3 I3A - Aragón Institute of Engineering Research [Zaragoza]

Saturated cyclic ethers are being proposed as next-generation bio-derived fuels. However, their pyrolysis and combustion chemistry has not been well established. In this work, the pyrolysis and combustion chemistry of 2-methyl-tetrahydrofuran (MTHF) was investigated through experiments and detailed kinetic modeling. Pyrolysis experiments were performed in a dedicated plug flow reactor at 170 kPa, temperatures between 900 and 1100 K and a N2 (diluent) to MTHF molar ratio of 10. The combustion chemistry of MTHF was investigated by measuring mole fraction profiles of stable species in premixed flat flames at 6.7 kPa and equivalence ratios 0.7, 1.0 and 1.3 and by determining laminar burning velocities of MTHF/air flat flames with unburned gas temperatures of 298, 358 and 398 K and equivalence ratios between 0.6 and 1.6. Furthermore, a kinetic model for pyrolysis and combustion of MTHF was developed, which contains a detailed description of the reactions of MTHF and its derived radicals with the aid of new high-level theoretical calculations. Model calculated mole fraction profiles and laminar burning velocities are in relatively good agreement with the obtained experimental data. At the applied pyrolysis conditions, unimolecular decomposition of MTHF by scission of the methyl group and concerted ring opening to 4-penten-1-ol dominates over scission of the ring bonds; the latter reactions were significant in tetrahydrofuran pyrolysis. MTHF is mainly consumed by hydrogen abstraction reactions. Subsequent decomposition of the resulting radicals by β-scission results in the observed product spectrum including small alkenes, formaldehyde, acetaldehyde and ketene. In the studied flames, unimolecular ring opening of MTHF is insignificant and consumption of MTHF through radical chemistry dominates. Recombination of 2-oxo-ethyl and 2-oxo-propyl, primary radicals in MTHF decomposition, with hydrogen atoms and carbon-centered radicals results in a wide range of oxygenated molecules.

Mots clés: Bio-fuel; 2-methyl-tetrahydrofuran; pyrolysis; laminar premixed flame; detailed kinetic model.

Domaines: Chimie organique; Chimie théorique et/ou physique

Ruben de Bruycker, Luc-Sy Tran, Hans-Heinrich Carstensen, Pierre-Alexandre Glaude, Fabiola Monge, et al.. Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran. Combustion and Flame, 2017, 176, pp.409-428. ⟨10.1016/j.combustflame.2016.11.017⟩. ⟨hal-02928433⟩