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An Exploratory Flow Reactor Study of H 2 S Oxidation at 30–100 Bar
Author(s) -
Song Yu,
Hashemi Hamid,
Christensen Jakob Munkholt,
Zou Chun,
Haynes Brian S.,
Marshall Paul,
Glarborg Peter
Publication year - 2017
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21055
Subject(s) - chemistry , stoichiometry , oxidizing agent , reaction rate constant , bar (unit) , reaction rate , reaction mechanism , redox , hydrogen , branching (polymer chemistry) , analytical chemistry (journal) , inorganic chemistry , kinetics , catalysis , organic chemistry , physics , quantum mechanics , meteorology
Hydrogen sulfide oxidation experiments were conducted in O 2 /N 2 at high pressure (30 and 100 bar) under oxidizing and stoichiometric conditions. Temperatures ranged from 450 to 925 K, with residence times of 3–20 s. Under stoichiometric conditions, the oxidation of H 2 S was initiated at 600 K and almost completed at 900 K. Under oxidizing conditions, the onset temperature for reaction was 500–550 K, depending on pressure and residence time, with full oxidization to SO 2 at 550–600 K. Similar results were obtained in quartz and alumina tubes, indicating little influence of surface chemistry. The data were interpreted in terms of a detailed chemical kinetic model. The rate constants for selected reactions, including SH + O 2 ⇄ SO 2 + H, were determined from ab initio calculations. Modeling predictions generally overpredicted the temperature for onset of reaction. Calculations were sensitive to reactions of the comparatively unreactive SH radical. Under stoichiometric conditions, the oxidation rate was mostly controlled by the SH + SH branching ratio to form H 2 S + S (promoting reaction) and HSSH (terminating). Further work is desirable on the SH + SH recombination and on subsequent reactions in the S 2 subset of the mechanism. Under oxidizing conditions, a high O 2 concentration (augmented by the high pressure) causes the termolecular reaction SH + O 2 + O 2 → HSO + O 3 to become the major consumption step for SH, according to the model. Consequently, calculations become very sensitive to the rate constant and product channels for the H 2 S + O 3 reaction, which are currently not well established.