Oxidation of hydrogen sulfide and CO2 mixtures: Laser-based multi-speciation and kinetic modeling

dc.contributor.authorElkhazraji, Ali
dc.contributor.authorWang, Qi
dc.contributor.authorMonge Palacios, Manuel
dc.contributor.authorZou, Jiabiao
dc.contributor.authorAlshaarawi, Amjad
dc.contributor.authorSepulveda, Adrian Cavazos
dc.contributor.authorSarathy, Mani
dc.contributor.authorFarooq, Aamir
dc.contributor.departmentMechanical Engineering
dc.contributor.departmentMechanical Engineering Program
dc.contributor.departmentPhysical Sciences and Engineering
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentClean Combustion Research Center
dc.contributor.departmentChemical Engineering
dc.contributor.departmentChemical Engineering Program
dc.contributor.institutionExploration and Petroleum Engineering Center-Advanced Research Center (EXPEC ARC), Saudi Aramco, Dhahran 34465, Saudi Arabia
dc.date.accessioned2024-04-01T06:21:38Z
dc.date.available2024-04-01T06:21:38Z
dc.date.issued2024-04
dc.description.abstractHydrogen sulfide (H2S), encountered in sour natural gas and in fossil fuel refineries, has adverse health and environmental impacts, but also the potential to be a source of clean hydrogen. This work addresses knowledge gaps and inconsistencies in H2S oxidation measurements and model predictions, emphasizing the scarcity of detailed kinetic modeling of H2S oxidation in the presence of carbon dioxide (CO2), a significant component of acid gas. This study leverages a shock tube coupled with laser absorption techniques to investigate the oxidation of mixtures of acid gas (H2S and CO2) with high H2S concentrations, equivalence ratios between 1.5 and 3.0, over the temperature range of 1300 – 1900 K and pressure near 1.3 bar. A detailed kinetic mechanism is proposed and validated through the measurement of time-histories of SO2, H2O, and CO, during fuel-rich acid gas oxidation. For the species measurements, we first conducted a comprehensive wavelength analysis for interference-free detection of the target species, providing new temperature-dependent absorption cross-section measurements of SO2 at its strongest IR band; moreover, we proposed a new laser-based thermometry technique for temperature time-history measurements behind reflected shock waves. The proposed kinetic mechanism is updated based on our recently calculated rate constants for reactions involving sulfurous species using high-level quantum chemistry and master equation calculations. The model outperforms former models at predicting measured time histories across the range of experimental conditions and elucidates different stages of the formation of target species. Important reactions in the new kinetic model are identified and discussed with reference to literature models, highlighting the reasons for the differences in model predictions.
dc.description.sponsorshipResearch reported in this publication was funded by King Abdullah University of Science and Technology (KAUST).
dc.eprint.versionPost-print
dc.identifier.doi10.1016/j.cej.2024.150421
dc.identifier.eid2-s2.0-85188157220
dc.identifier.issn1385-8947
dc.identifier.journalChemical Engineering Journal
dc.identifier.pages150421
dc.identifier.urihttps://repository.kaust.edu.sa/handle/10754/697826
dc.identifier.volume486
dc.publisherElsevier BV
dc.relation.urlhttps://linkinghub.elsevier.com/retrieve/pii/S1385894724019089
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Chemical Engineering Journal. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Chemical Engineering Journal, [486, , (2024-04)] DOI: 10.1016/j.cej.2024.150421 . © 2024. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.embargodate2026-04-01
dc.titleOxidation of hydrogen sulfide and CO2 mixtures: Laser-based multi-speciation and kinetic modeling
dc.typeArticle
display.details.left<span><h5>Embargo End Date</h5>2026-04-01<br><br><h5>Type</h5>Article<br><br><h5>Authors</h5><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-7737-2211&spc.sf=dc.date.issued&spc.sd=DESC">Elkhazraji, Ali</a> <a href="https://orcid.org/0000-0002-7737-2211" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-9636-9659&spc.sf=dc.date.issued&spc.sd=DESC">Wang, Qi</a> <a href="https://orcid.org/0000-0002-9636-9659" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0003-1199-5026&spc.sf=dc.date.issued&spc.sd=DESC">Monge Palacios, Manuel</a> <a href="https://orcid.org/0000-0003-1199-5026" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-9551-9221&spc.sf=dc.date.issued&spc.sd=DESC">Zou, Jiabiao</a> <a href="https://orcid.org/0000-0002-9551-9221" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Alshaarawi, Amjad,equals">Alshaarawi, Amjad</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Sepulveda, Adrian Cavazos,equals">Sepulveda, Adrian Cavazos</a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-3975-6206&spc.sf=dc.date.issued&spc.sd=DESC">Sarathy, Mani</a> <a href="https://orcid.org/0000-0002-3975-6206" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0001-5296-2197&spc.sf=dc.date.issued&spc.sd=DESC">Farooq, Aamir</a> <a href="https://orcid.org/0000-0001-5296-2197" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><br><h5>KAUST Department</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Mechanical Engineering,equals">Mechanical Engineering</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Mechanical Engineering Program,equals">Mechanical Engineering Program</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Physical Sciences and Engineering,equals">Physical Sciences and Engineering</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Physical Science and Engineering (PSE) Division,equals">Physical Science and Engineering (PSE) Division</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Clean Combustion Research Center,equals">Clean Combustion Research Center</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Chemical Engineering,equals">Chemical Engineering</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Chemical Engineering Program,equals">Chemical Engineering Program</a><br><br><h5>Date</h5>2024-04</span>
display.details.right<span><h5>Abstract</h5>Hydrogen sulfide (H2S), encountered in sour natural gas and in fossil fuel refineries, has adverse health and environmental impacts, but also the potential to be a source of clean hydrogen. This work addresses knowledge gaps and inconsistencies in H2S oxidation measurements and model predictions, emphasizing the scarcity of detailed kinetic modeling of H2S oxidation in the presence of carbon dioxide (CO2), a significant component of acid gas. This study leverages a shock tube coupled with laser absorption techniques to investigate the oxidation of mixtures of acid gas (H2S and CO2) with high H2S concentrations, equivalence ratios between 1.5 and 3.0, over the temperature range of 1300 – 1900 K and pressure near 1.3 bar. A detailed kinetic mechanism is proposed and validated through the measurement of time-histories of SO2, H2O, and CO, during fuel-rich acid gas oxidation. For the species measurements, we first conducted a comprehensive wavelength analysis for interference-free detection of the target species, providing new temperature-dependent absorption cross-section measurements of SO2 at its strongest IR band; moreover, we proposed a new laser-based thermometry technique for temperature time-history measurements behind reflected shock waves. The proposed kinetic mechanism is updated based on our recently calculated rate constants for reactions involving sulfurous species using high-level quantum chemistry and master equation calculations. The model outperforms former models at predicting measured time histories across the range of experimental conditions and elucidates different stages of the formation of target species. Important reactions in the new kinetic model are identified and discussed with reference to literature models, highlighting the reasons for the differences in model predictions.<br><br><h5>Acknowledgements</h5>Research reported in this publication was funded by King Abdullah University of Science and Technology (KAUST).<br><br><h5>Publisher</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.publisher=Elsevier BV,equals">Elsevier BV</a><br><br><h5>Journal</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.journal=Chemical Engineering Journal,equals">Chemical Engineering Journal</a><br><br><h5>DOI</h5><a href="https://doi.org/10.1016/j.cej.2024.150421">10.1016/j.cej.2024.150421</a><br><br><h5>Additional Links</h5>https://linkinghub.elsevier.com/retrieve/pii/S1385894724019089</span>
kaust.personElkhazraji, Ali
kaust.personWang, Qi
kaust.personMonge Palacios, Manuel
kaust.personZou, Jiabiao
kaust.personSarathy, Mani
kaust.personFarooq, Aamir
orcid.authorElkhazraji, Ali::0000-0002-7737-2211
orcid.authorWang, Qi::0000-0002-9636-9659
orcid.authorMonge Palacios, Manuel::0000-0003-1199-5026
orcid.authorZou, Jiabiao::0000-0002-9551-9221
orcid.authorAlshaarawi, Amjad
orcid.authorSepulveda, Adrian Cavazos
orcid.authorSarathy, Mani::0000-0002-3975-6206
orcid.authorFarooq, Aamir::0000-0001-5296-2197
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