Kinetic and modeling studies of the reaction S+H2S

Gao, Yide; Zhou, Chenlai; Sendt, Karina; Haynes, Brian S.; Marshall, Paul

doi:10.1016/j.proci.2010.05.020

Cited by 13 publications

(5 citation statements)

References 21 publications

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“…Most of the reactions of H 2 S with the radical pool have been characterized experimentally and theoretically over a wider temperature range. For H 2 S + H (R2), H 2 S + O (R3, R4), and H 2 S + S (R12), we rely on rate constants determined by Marshall and coworkers . The rate constant for H 2 S + OH (R5) was taken from the theoretical study by Ellingson and Truhlar ; it provides an explanation for the unusual temperature dependence of the reaction, and the calculated value is in good agreement with experiment .…”

Section: Detailed Kinetic Modelmentioning

confidence: 94%

“…Owing to the low reactivity of the SH radical, the SH + SH reaction becomes important, even at oxidizing conditions. This reaction has two major product channels:

\begin{matrix} true \\ right SH + SH ⇄ H_{2} normalS + normalS \end{matrix}

\begin{matrix} true \\ right SH + SH (+ normalM) ⇄ HSSH (+ normalM) \end{matrix}

The rate constant for the H 2 S + S reaction (R12), which is believed to be largely independent of pressure, was taken from the combined experimental and theoretical study of Gao et al . The high‐ and low‐pressure limits, as well as the falloff behavior, for the SH + SH recombination step (R43) were initially drawn from the RRKM study of Zhou et al .…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

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An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

Song

Hashemi

Christensen

et al. 2016

Int J of Chemical Kinetics

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Hydrogen sulfide oxidation experiments were conducted in O2/N2 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 H2S 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 SO2 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 + O2 ⇄ SO2 + 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 H2S + S (promoting reaction) and HSSH (terminating). Further work is desirable on the SH + SH recombination and on subsequent reactions in the S2 subset of the mechanism. Under oxidizing conditions, a high O2 concentration (augmented by the high pressure) causes the termolecular reaction SH + O2 + O2 → HSO + O3 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 H2S + O3 reaction, which are currently not well established.

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Section: Detailed Kinetic Modelmentioning

confidence: 94%

“…Owing to the low reactivity of the SH radical, the SH + SH reaction becomes important, even at oxidizing conditions. This reaction has two major product channels:

\begin{matrix} true \\ right SH + SH ⇄ H_{2} normalS + normalS \end{matrix}

\begin{matrix} true \\ right SH + SH (+ normalM) ⇄ HSSH (+ normalM) \end{matrix}

Section: Detailed Kinetic Modelmentioning

confidence: 99%

An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

Song

Hashemi

Christensen

et al. 2016

Int J of Chemical Kinetics

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“…The two major product channels for this reaction are H 2 S + S, which initiates a chain-branching sequence (S + O 2 → SO + O, and SO + O 2 → SO 2 + O), and HSSH, which is terminating. We adopted the rate constant for H 2 S + S ⇌ SH + SH from Gao et al, while for the SH + SH recombination reaction, the high-pressure limit from Zhou et al was lowered by a factor of 4, following Song et al…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

“…Mathieu et al 11 38 while for the SH + SH recombination reaction, the high-pressure limit from Zhou et al 25 was lowered by a factor of 4, following Song et al 15 In the recent modeling study of CH 4 /H 2 S oxidation by Bongartz and Ghoniem, 13 it was assumed that reactions of species containing both carbon and sulfur could be omitted from the reaction mechanism without a significant loss of accuracy. However, the present study indicates that direct interactions between hydrocarbon and sulfur species are important.…”

Section: ■ Detailed Kinetic Modelmentioning

confidence: 99%

Experimental and Modeling Investigation of the Effect of H₂S Addition to Methane on the Ignition and Oxidation at High Pressures

et al. 2016

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The autoignition and oxidation behavior of CH4/H2S mixtures has been studied experimentally in a rapid compression machine (RCM) and a high-pressure flow reactor. The RCM measurements show that the addition of 1% H2S to methane reduces the autoignition delay time by a factor of 2 at pressures ranging from 30 to 80 bar and temperatures from 930 to 1050 K. The flow reactor experiments performed at 50 bar show that, for stoichiometric conditions, a large fraction of H2S is already consumed at 600 K, while temperatures above 750 K are needed to oxidize 10% methane. A detailed chemical kinetic model has been established, describing the oxidation of CH4 and H2S as well as the formation and consumption of organosulfuric species. Computations with the model show good agreement with the ignition measurements, provided that reactions of H2S and SH with peroxides (HO2 and CH3OO) are constrained. A comparison of the flow reactor data to modeling predictions shows satisfactory agreement under stoichiometric conditions, while at very reducing conditions, the model underestimates the consumption of both H2S and CH4. Similar to the RCM experiments, the presence of H2S is predicted to promote oxidation of methane. Analysis of the calculations indicates a significant interaction between the oxidation chemistry of H2S and CH4, but this chemistry is not well understood at present. More work is desirable on the reactions of H2S and SH with peroxides (HO2 and CH3OO) and the formation and consumption of organosulfuric compounds.

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“…For the reaction H 2 S + S = SH + SH, two duplicate reactions corresponding to different reaction channels were defined in the original sulfur mechanism [35]. We determined the uncertainties in the pre-exponential factors of each of these by varying them and comparing the resulting fit to the original data of Gao et al [49] and Shiina et al [50]. The limits on the variation of the pre-exponential factor that were chosen are +20%/-40% for the first of the two duplicate reactions and ±25% for the second reaction.…”

Section: Mechanism Selection and Optimizationmentioning

confidence: 99%

Chemical kinetics mechanism for oxy-fuel combustion of mixtures of hydrogen sulfide and methane

Bongartz

Ghoniem

2015

Combustion and Flame

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Oxy-fuel combustion of sour gas, a mixture of natural gas (essentially methane (CH 4 )), carbon dioxide (CO 2 ), and hydrogen sulfide (H 2 S), could enable the utilization of large natural gas resources, especially when combined with enhanced oil recovery. In this work, a detailed chemical reaction mechanism for oxy-fuel combustion of sour gas is presented. To construct the mechanism, a CH 4 sub-mechanism was chosen based on a comparative validation study for oxy-fuel combustion. This mechanism was combined with a mechanism for H 2 S oxidation, and the sulfur sub-mechanism was then optimized to give better agreement with relevant experiments. The optimization targets included predictions for the laminar burning velocity, ignition delay time, and pyrolysis of H 2 S, and H 2 S oxidation in a flow reactor. The rate parameters of 15 sulfur reactions were varied in the optimization within their respective uncertainties. The optimized combined mechanism was validated against a larger set of experimental data over a wide range of conditions for oxidation of H 2 S and interactions between carbon and sulfur species. Improved overall agreement was achieved through the optimization and all important trends were captured in the modeling results. The optimized mechanism can be used to make qualitative and some quantitative predictions on the combustion behavior of sour gas. The remaining discrepancies highlight the current uncertainties in sulfur chemistry and underline the need for more accurate direct determination of several important rate constants as well as more validation data.

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Kinetic and modeling studies of the reaction S+H2S

Cited by 13 publications

References 21 publications

An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

Experimental and Modeling Investigation of the Effect of H₂S Addition to Methane on the Ignition and Oxidation at High Pressures

Chemical kinetics mechanism for oxy-fuel combustion of mixtures of hydrogen sulfide and methane

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Kinetic and modeling studies of the reaction S+H2S

Cited by 13 publications

References 21 publications

An Exploratory Flow Reactor Study of H2S Oxidation at 30–100 Bar

An Exploratory Flow Reactor Study of H2S Oxidation at 30–100 Bar

Experimental and Modeling Investigation of the Effect of H2S Addition to Methane on the Ignition and Oxidation at High Pressures

Chemical kinetics mechanism for oxy-fuel combustion of mixtures of hydrogen sulfide and methane

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An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

An Exploratory Flow Reactor Study of H₂S Oxidation at 30–100 Bar

Experimental and Modeling Investigation of the Effect of H₂S Addition to Methane on the Ignition and Oxidation at High Pressures