Call: +34 876 555042
Email: hcarsten@unizar.es
Address: Oficina CB1-0-2 Edificio Torres Quevedo C/ María de Luna 2 50018 Zaragoza Spain
ABOUT ME
Research Interests
Kinetic analysis of complex gas phase reactions related to environmental chemistry, pyrolysis and combustion. I have a background as experimentalist (laser photolysis / LIF detection; low pressure flame studies using MBMS techniques or flow reactors combined with GC analysis) but work recently mainly on ab initio calculated thermochemistry. The objective of my current research is to develop software that automatically generated concise but complete reaction networks for predetermined conditions using a rate-based criterion for reaction selection.
PUBLICATIONS
2019
Vermeire, Florence H; Carstensen, Hans-Heinrich; Herbinet, Olivier; Battin-Leclerc, Frédérique; Marin, Guy B; Geem, Kevin M Van
The thermal decomposition of furfural: Molecular chemistry unraveled Journal Article
In: Proceedings of the Combustion Institute, vol. 37, no. 1, pp. 445–452, 2019, ISSN: 15407489.
@article{Vermeire2019,
title = {The thermal decomposition of furfural: Molecular chemistry unraveled},
author = {Florence H Vermeire and Hans-Heinrich Carstensen and Olivier Herbinet and Frédérique Battin-Leclerc and Guy B Marin and Kevin M Van Geem},
doi = {10.1016/j.proci.2018.05.119},
issn = {15407489},
year = {2019},
date = {2019-01-01},
journal = {Proceedings of the Combustion Institute},
volume = {37},
number = {1},
pages = {445--452},
publisher = {Elsevier Ltd},
abstract = {The thermal decomposition of furfural is investigated experimentally and through theoretical calculations at the CBS-QB3 level of theory. Furfural is a major product observed during biomass pyrolysis, but despite its importance there are many speculations about the thermal decomposition channels of this compound. To address these open questions new experiments are performed in a jet-stirred reactor at atmospheric pressure and temperatures ranging from 900 to 1100 K with a furfural inlet mole fraction of 0.005 and He as diluent. The residence time is set to 2 s. The main products observed by GC analysis are CO, CO2, $alpha$-pyrone, furan, 3-furaldehyde, propyne, propadiene, acetylene, methane and benzene. Small amounts of other aromatics, e.g. toluene, styrene, benzaldehyde and phenol are observed as well. Theoretical calculations at the CBS-QB3 level are used to extend the furfural potential energy surface and to identify possible reaction pathways to the observed products. The unimolecular non-radical decomposition channel through $alpha$-pyrone as proposed in literature is confirmed as the main channel, but carbene pathways are found to make small contributions as well. Furthermore, pericyclic reactions are suggested to contribute to the molecular elimination of CO in open-chain molecules and Diels Alder reactions are found to be important for the formation of CO2 and aromatics. Finally, even radical chemistry initiated by homolytic scission of the approximately 380 kJ/mol strong C-H bond in the furfural carbonyl group has a non-negligible influence.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The thermal decomposition of furfural is investigated experimentally and through theoretical calculations at the CBS-QB3 level of theory. Furfural is a major product observed during biomass pyrolysis, but despite its importance there are many speculations about the thermal decomposition channels of this compound. To address these open questions new experiments are performed in a jet-stirred reactor at atmospheric pressure and temperatures ranging from 900 to 1100 K with a furfural inlet mole fraction of 0.005 and He as diluent. The residence time is set to 2 s. The main products observed by GC analysis are CO, CO2, $alpha$-pyrone, furan, 3-furaldehyde, propyne, propadiene, acetylene, methane and benzene. Small amounts of other aromatics, e.g. toluene, styrene, benzaldehyde and phenol are observed as well. Theoretical calculations at the CBS-QB3 level are used to extend the furfural potential energy surface and to identify possible reaction pathways to the observed products. The unimolecular non-radical decomposition channel through $alpha$-pyrone as proposed in literature is confirmed as the main channel, but carbene pathways are found to make small contributions as well. Furthermore, pericyclic reactions are suggested to contribute to the molecular elimination of CO in open-chain molecules and Diels Alder reactions are found to be important for the formation of CO2 and aromatics. Finally, even radical chemistry initiated by homolytic scission of the approximately 380 kJ/mol strong C-H bond in the furfural carbonyl group has a non-negligible influence.
2018
Ince, Alper; Carstensen, Hans-Heinrich; Sabbe, Maarten; Reyniers, Marie-Françoise; Marin, Guy B
Modeling of thermodynamics of substituted toluene derivatives and benzylic radicals textitvia group additivity Journal Article
In: AIChE Journal, vol. 64, no. 10, pp. 3649–3661, 2018, ISSN: 00011541.
@article{Ince2018,
title = {Modeling of thermodynamics of substituted toluene derivatives and benzylic radicals textitvia group additivity},
author = {Alper Ince and Hans-Heinrich Carstensen and Maarten Sabbe and Marie-Françoise Reyniers and Guy B Marin},
url = {http://doi.wiley.com/10.1002/aic.16350},
doi = {10.1002/aic.16350},
issn = {00011541},
year = {2018},
date = {2018-10-01},
journal = {AIChE Journal},
volume = {64},
number = {10},
pages = {3649--3661},
publisher = {John Wiley and Sons Inc.},
abstract = {The thermodynamic properties of unsubstituted, mono-, and di-substituted toluene derivatives and benzylic radicals with hydroxy, methoxy, formyl, vinyl, methyl, and ethyl substituents are calculated with the bond additivity corrected (BAC) post-Hartree-Fock CBS-QB3 method. Benson's group additivity (GA) scheme is extended to toluene derivatives by determining six group additive value (GAV) and five non-nearest neighbor interaction (NNI) parameters through least-squares regression to a database of thermodynamic properties of 168 compounds and to benzylic radicals by defining 6 GAV and 14 NNI parameters based on a set of 168 radicals. Comparison between CBS-QB3/BAC and GA-calculated thermodynamic values shows that the standard enthalpies of formation generally agree within 4 kJ mol−1, whereas the entropies and the heat capacities generally deviate <4 J mol−1 K−1. textcopyright 2018 American Institute of Chemical Engineers AIChE J, 64: 3649–3661, 2018.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The thermodynamic properties of unsubstituted, mono-, and di-substituted toluene derivatives and benzylic radicals with hydroxy, methoxy, formyl, vinyl, methyl, and ethyl substituents are calculated with the bond additivity corrected (BAC) post-Hartree-Fock CBS-QB3 method. Benson’s group additivity (GA) scheme is extended to toluene derivatives by determining six group additive value (GAV) and five non-nearest neighbor interaction (NNI) parameters through least-squares regression to a database of thermodynamic properties of 168 compounds and to benzylic radicals by defining 6 GAV and 14 NNI parameters based on a set of 168 radicals. Comparison between CBS-QB3/BAC and GA-calculated thermodynamic values shows that the standard enthalpies of formation generally agree within 4 kJ mol−1, whereas the entropies and the heat capacities generally deviate <4 J mol−1 K−1. textcopyright 2018 American Institute of Chemical Engineers AIChE J, 64: 3649–3661, 2018.
Fenard, Yann; Gil, Adrià; Vanhove, Guillaume; Carstensen, Hans-Heinrich; Geem, Kevin M Van; Westmoreland, Phillip R; Herbinet, Olivier; Battin-Leclerc, Frédérique
A model of tetrahydrofuran low-temperature oxidation based on theoretically calculated rate constants Journal Article
In: Combustion and Flame, vol. 191, pp. 252–269, 2018, ISSN: 15562921.
@article{Fenard2018,
title = {A model of tetrahydrofuran low-temperature oxidation based on theoretically calculated rate constants},
author = {Yann Fenard and Adrià Gil and Guillaume Vanhove and Hans-Heinrich Carstensen and Kevin M Van Geem and Phillip R Westmoreland and Olivier Herbinet and Frédérique Battin-Leclerc},
doi = {10.1016/j.combustflame.2018.01.006},
issn = {15562921},
year = {2018},
date = {2018-05-01},
journal = {Combustion and Flame},
volume = {191},
pages = {252--269},
publisher = {Elsevier Inc.},
abstract = {The first detailed kinetic model of the low-temperature oxidation of tetrahydrofuran has been developed. Thermochemical and kinetic data related to the most important elementary reactions have been derived from ab initio calculations at the CBS-QB3 level of theory. A comparison of the rate constants at 600 K, obtained from these calculations with values estimated using recently published rate rules for alkanes, sometimes show differences of several orders of magnitude for alkylperoxy radical isomerizations, HO2-eliminations, and oxirane formations. The new model satisfactorily reproduces previously published ignition delay times obtained in a rapid-compression machine and in a shock tube, as well as numerous product mole fractions measured in a jet-stirred reactor at low to intermediate temperatures and in a low-pressure laminar premixed flame. To highlight the most significant reaction pathways, flow-rate and sensitivity analyses have been performed with this new model.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The first detailed kinetic model of the low-temperature oxidation of tetrahydrofuran has been developed. Thermochemical and kinetic data related to the most important elementary reactions have been derived from ab initio calculations at the CBS-QB3 level of theory. A comparison of the rate constants at 600 K, obtained from these calculations with values estimated using recently published rate rules for alkanes, sometimes show differences of several orders of magnitude for alkylperoxy radical isomerizations, HO2-eliminations, and oxirane formations. The new model satisfactorily reproduces previously published ignition delay times obtained in a rapid-compression machine and in a shock tube, as well as numerous product mole fractions measured in a jet-stirred reactor at low to intermediate temperatures and in a low-pressure laminar premixed flame. To highlight the most significant reaction pathways, flow-rate and sensitivity analyses have been performed with this new model.
Vermeire, Florence H; Carstensen, Hans-Heinrich; Herbinet, Olivier; Battin-Leclerc, Frédérique; Marin, Guy B; Geem, Kevin M Van
Experimental and modeling study of the pyrolysis and combustion of dimethoxymethane Journal Article
In: Combustion and Flame, vol. 190, pp. 270–283, 2018, ISSN: 15562921.
@article{Vermeire2018,
title = {Experimental and modeling study of the pyrolysis and combustion of dimethoxymethane},
author = {Florence H Vermeire and Hans-Heinrich Carstensen and Olivier Herbinet and Frédérique Battin-Leclerc and Guy B Marin and Kevin M Van Geem},
doi = {10.1016/j.combustflame.2017.12.001},
issn = {15562921},
year = {2018},
date = {2018-04-01},
journal = {Combustion and Flame},
volume = {190},
pages = {270--283},
publisher = {Elsevier Inc.},
abstract = {The pyrolysis and low- to intermediate temperature oxidation chemistry of dimethoxymethane (DMM), the simplest oxymethylene ether, is studied theoretically and experimentally in a JSR setup. The potential energy surfaces for peroxy species relevant during the low-temperature oxidation of dimethoxymethane are studied at the CBS-QB3 level of theory and the results are used to calculate thermodynamic properties of the main species as well as rate expressions for important reactions. An elementary step model for DMM pyrolysis and oxidation is built with the automatic kinetic model generation software Genesys. To describe the chemistry of small species not directly related to DMM, the AramcoMech 1.3 mechanism developed by Metcalfe et al. is used. If the more recently extended version of this mechanism, i.e. the propene oxidation mechanism published by Burke et al., was used as alternative base mechanism, large discrepancies for the mole fractions of CO2, methyl formate and methanol during the pyrolysis of DMM were observed. The validation of the new DMM model is carried out with new experimental data that is acquired in an isothermal quartz jet-stirred reactor at low and intermediate temperatures. Different equivalence ratios, ϕ= 0.25, ϕ= 1.0, ϕ= 2.0 and ϕ= ∞, are studied in a temperature range from 500 K to 1100 K, at a pressure of 1.07 bar and with an inlet DMM mole fraction of 0.01. The experimental trends are well predicted by the model without any tuning of the model parameters although some improvements are possible to increase quantitative agreement. The largest discrepancies are observed at fuel lean conditions for the hydrocarbon mole fractions, and at low-temperatures as can be noticed by the over prediction of formaldehyde and methyl formate. The kinetic model is also validated against plug flow reactor, jet-stirred reactor and lean and rich premixed flames data from the literature. Rate of production analyses are performed to identify important pathways for low- and intermediate-temperature oxidation and pyrolysis.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The pyrolysis and low- to intermediate temperature oxidation chemistry of dimethoxymethane (DMM), the simplest oxymethylene ether, is studied theoretically and experimentally in a JSR setup. The potential energy surfaces for peroxy species relevant during the low-temperature oxidation of dimethoxymethane are studied at the CBS-QB3 level of theory and the results are used to calculate thermodynamic properties of the main species as well as rate expressions for important reactions. An elementary step model for DMM pyrolysis and oxidation is built with the automatic kinetic model generation software Genesys. To describe the chemistry of small species not directly related to DMM, the AramcoMech 1.3 mechanism developed by Metcalfe et al. is used. If the more recently extended version of this mechanism, i.e. the propene oxidation mechanism published by Burke et al., was used as alternative base mechanism, large discrepancies for the mole fractions of CO2, methyl formate and methanol during the pyrolysis of DMM were observed. The validation of the new DMM model is carried out with new experimental data that is acquired in an isothermal quartz jet-stirred reactor at low and intermediate temperatures. Different equivalence ratios, ϕ= 0.25, ϕ= 1.0, ϕ= 2.0 and ϕ= ∞, are studied in a temperature range from 500 K to 1100 K, at a pressure of 1.07 bar and with an inlet DMM mole fraction of 0.01. The experimental trends are well predicted by the model without any tuning of the model parameters although some improvements are possible to increase quantitative agreement. The largest discrepancies are observed at fuel lean conditions for the hydrocarbon mole fractions, and at low-temperatures as can be noticed by the over prediction of formaldehyde and methyl formate. The kinetic model is also validated against plug flow reactor, jet-stirred reactor and lean and rich premixed flames data from the literature. Rate of production analyses are performed to identify important pathways for low- and intermediate-temperature oxidation and pyrolysis.
2017
Bruycker, Ruben De; Tran, Luc Sy; Carstensen, Hans-Heinrich; Glaude, Pierre-Alexandre; Monge, Fabiola; Alzueta, María U; Battin-Leclerc, Frédérique; Geem, Kevin M Van
Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran Journal Article
In: Combustion and Flame, vol. 176, pp. 409–428, 2017, ISSN: 15562921.
@article{DeBruycker2017,
title = {Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran},
author = {Ruben De Bruycker and Luc Sy Tran and Hans-Heinrich Carstensen and Pierre-Alexandre Glaude and Fabiola Monge and María U Alzueta and Frédérique Battin-Leclerc and Kevin M Van Geem},
doi = {10.1016/j.combustflame.2016.11.017},
issn = {15562921},
year = {2017},
date = {2017-02-01},
journal = {Combustion and Flame},
volume = {176},
pages = {409--428},
publisher = {Elsevier Inc.},
abstract = {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 $beta$-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.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
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 $beta$-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.