Hydrogen sulfide chemistry has recently undergone a renewed interest due to the current energ y transition, requiring a proper treatment of such impurities in the sources like shale gas or biogas. Moreover, the lower-temperature, diluted conditions considered nowadays for reducing pollutant emissions require a wider-range development and validation of the pyrolysis and oxidation mechanisms. In this work, this was addressed through an experimental campaign carried out in three reactor facilities, namely a jet-stirred reactor and two flow reactors. A wide range of operating conditions could thus be covered, in terms of equivalence ratios under lean conditions (0.018 & LE; phi & LE; 0.5), temperatures (400 K & LE; T & LE; 2000 K) and residence times (0.1 s & LE; tau & LE; 2 s). The mole fractions of reactants (H2S, O2), products (SO2, H2O) and intermediates (H2) were measured. In parallel , a kinetic mechanism of H2S pyrolysis and oxidation was developed by including the latest available kinetic rates on su l f u r pyrolysis and oxidation chemistry, which were added to a core H2/O2 module, previously validated. Such a mechanism included a re-evaluation of selected key reaction steps, identified via sensitivity analysis. Results showed a general agreement of the experimental measurements with predictions: in the case of pyrolysis, the thermal decomposition reaction (H2S + M = H2 + S + M) was identified as the sole controllin g step: a critical choice of the kinetic rate had to be made, due to the significant disagreement among the literatu r e rates. Con-cerning oxidation, the H-abstraction from H2S by O2 was found to be the major bottleneck at the lowest tem-peratures, with HO2 becoming a key abstractor, too, under ve r y lean conditions. At higher temperatures, a key role was played instead by the H-abstraction of H2S with S (H2S + S = SH + SH), acting in the reverse direction and providing S radicals, boosting the oxidation process.

An experimental, theoretical and kinetic-modeling study of hydrogen sulfide pyrolysis and oxidation

Alessandro Stagni;Luna Pratali Maffei;Tiziano Faravelli
2022-01-01

Abstract

Hydrogen sulfide chemistry has recently undergone a renewed interest due to the current energ y transition, requiring a proper treatment of such impurities in the sources like shale gas or biogas. Moreover, the lower-temperature, diluted conditions considered nowadays for reducing pollutant emissions require a wider-range development and validation of the pyrolysis and oxidation mechanisms. In this work, this was addressed through an experimental campaign carried out in three reactor facilities, namely a jet-stirred reactor and two flow reactors. A wide range of operating conditions could thus be covered, in terms of equivalence ratios under lean conditions (0.018 & LE; phi & LE; 0.5), temperatures (400 K & LE; T & LE; 2000 K) and residence times (0.1 s & LE; tau & LE; 2 s). The mole fractions of reactants (H2S, O2), products (SO2, H2O) and intermediates (H2) were measured. In parallel , a kinetic mechanism of H2S pyrolysis and oxidation was developed by including the latest available kinetic rates on su l f u r pyrolysis and oxidation chemistry, which were added to a core H2/O2 module, previously validated. Such a mechanism included a re-evaluation of selected key reaction steps, identified via sensitivity analysis. Results showed a general agreement of the experimental measurements with predictions: in the case of pyrolysis, the thermal decomposition reaction (H2S + M = H2 + S + M) was identified as the sole controllin g step: a critical choice of the kinetic rate had to be made, due to the significant disagreement among the literatu r e rates. Con-cerning oxidation, the H-abstraction from H2S by O2 was found to be the major bottleneck at the lowest tem-peratures, with HO2 becoming a key abstractor, too, under ve r y lean conditions. At higher temperatures, a key role was played instead by the H-abstraction of H2S with S (H2S + S = SH + SH), acting in the reverse direction and providing S radicals, boosting the oxidation process.
2022
Hydrogen sulfide
Sulphur oxides
Jet-stirred reactor
Flow reactor
Ab initio
Detailed kinetics
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11311/1221422
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