Highly oxygenates molecules formed by oxidation of terpenes in a jet-stirred reactor

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Submitted on 23 May 2019

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Highly oxygenates molecules formed by oxidation of terpenes in a jet-stirred reactor

N. Belhadj, R. Benoit, P. Dagaut, G. Dayma, M Lailliau, Z. Serinyel

To cite this version:

N. Belhadj, R. Benoit, P. Dagaut, G. Dayma, M Lailliau, et al.. Highly oxygenates molecules formed by oxidation of terpenes in a jet-stirred reactor. 11th International Conference on Chemical Kinetics, Jun 2019, Orléans, France. �hal-02137425�

HIGHLY OXYGENATES MOLECULES FORMED BY OXIDATION OF TERPENES

IN A JET-STIRRED REACTOR

N. BELHADJ, R. BENOIT, P. DAGAUT, G. DAYMA, M. LAILLIAU, Z. SERINYEL

CNRS–INSIS, ICARE, 1C avenue de la Recherche Scientifique, Orléans, France

Université d’Orléans, Collegium Sciences et Techniques, 1 rue de Chartres, Orléans, France

Introduction

With the growing interest for biomass-derived fuels the understanding of the combustion chemistry of terpenes becomes of major scientific importance.

We studied the low-temperature oxidation of a series of terpenes (α- and β-pinene and limonene) in a jet-stirred reactor at atmospheric pressure. The formation of ketohydroperoxides and highly oxygenated molecules (HOMs) was observed.

Acknowledgements

Experimental setup

Terpenes oxidation

Reaction pathways to ketohydroperoxides

Experimental conditions

Analyses were performed on solubilized products of terpenes oxidation in cooled acetonitrile. The samples were analyzed using HESI electrospray ionization (+/-)

and an Orbitrap mass spectrometer (resolution: 140,000, mass accuracy <0.5 ppm RMS).

Experimental conditions selected based on the kinetic of oxidation of cyclic paraffins in a JSR to favor the production of ketohydroperoxides: and HOMs 1 bar, T = 590 K, ϕ = 0.5, τ = 1 s

Positive HESI ionization

M + H+ _{=> MH}+

Negative HESI ionization

MH => H+ _{+ M}

-Funding from Région Centre Val de Loire, FEDER, CPER PROMESTOCK, and the Labex Caprysses (ANR-11-LABX-0006-01) is gratefully acknowledged

Results

Ketohydroperoxides

HOMs

HOMs formation mechanism

OOQOOH  HOOPOOH (alternative H-transfer, i.e., not from

H

2 addition:

HOOPOOH + O₂  (HOO)₂POO  (HOO)₂P’OOH (HOO)₂P’OOH → OH + (HOO)₂P’=O (C₁₀H₁₄O₅)

4th _O

2 addition:

(HOO)₂P’OOH + O₂  (HOO)₃P’OO  (HOO)₃P”OOH (HOO)₃P”OOH → OH + (HOO)₃P”=O (C₁₀H₁₄O₇)

5th _O

2 addition:

(HOO)₃P”OOH + O₂  (HOO)₄P”’OO  (HOO)₄P”’OOH (HOO)₄P”’OOH → OH + (HOO)₄P”’=O (C₁₀H₁₄O₉)

HESI C-trap octopole orbitrap HCD cell C₁₀H₁₄O₃ : M MH+ _{m/z= 183.10167} M(-H)- _{m/z= 181.08715}

H/D exchange using D₂O: -OH -OD to confirm the presence of -OOH

MD+ _{m/z= 184.10785} C₁₀H₁₄O₅ : M M(-H)- _{m/z= 213.07688} C₁₀H₁₄O₇ : M M(-H)- _{m/z= 245.06694} C₁₀H₁₄O₉ : M M(-H)- _{m/z= 277.05661} R + O₂  RO₂  _QOOH 2nd O₂ addition: QOOH + O₂  OOQOOH OOQOOH  HOOQ’OOH HOOQ’OOH → OH + HOOQ’O (KHP) 0.00E+00 5.00E+06 1.00E+07 1.50E+07 2.00E+07 2.50E+07 3.00E+07 183.0970183.0980183.0990183.1000183.1010183.1020183.1030183.1040 C10H14O3 H+ 0.00E+00 1.00E+07 2.00E+07 3.00E+07 4.00E+07 5.00E+07 6.00E+07 181.0840181.0850181.0860181.0870181.0880181.0890181.0900 C10H14O3 H- 0 1000000 2000000 3000000 4000000 5000000 6000000 7000000 8000000 9000000 10000000 184.1060 184.1070 184.1080 184.1090 C10H14O3 D+ 0.00E+00 1.00E+06 2.00E+06 3.00E+06 4.00E+06 5.00E+06 6.00E+06 213.0750 213.0760 213.0770 213.0780 213.0790 C10H14O5 H- 0.00E+00 5.00E+04 1.00E+05 1.50E+05 2.00E+05 2.50E+05 3.00E+05 3.50E+05 245.0642 245.0652 245.0662 245.0672 245.0682 245.0692 C10H14O7 H- 0.00E+00 1.00E+03 2.00E+03 3.00E+03 4.00E+03 5.00E+03 6.00E+03 7.00E+03 8.00E+03 277.0545 277.0555 277.0565 277.0575 277.0585 C10H14O9 H-