274. The thermal decomposition of carbonyl sulphide

Partington, J. R.; Neville, H. H.

doi:10.1039/jr9510001230

Cited by 16 publications

(15 citation statements)

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“…The available experimental data for thermal conversion of OCS are derived under pyrolysis or oxidation conditions. Data for thermal conversion of OCS in an inert atmosphere (pyrolysis), reported from batch reactors , flow reactors , and shock tubes , were not considered for model validation in the present work. The results are consistent with the reaction sequence,

OCS + M ⇌ CO + S + M

OCS + S ⇌ CO + {normalS}_{2}

and the rate constant for (R1), derived from the batch reactor (823–873 K) and shock tube work (1500–3230 K), is mostly in agreement within a factor of two (see Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Arrhenius plot for the reaction OCS + M

⇌

CO + S + M. Experimental results (symbols) from Partington and Neville , Hay and Belford , Schecker and Wagner , Woiki and Roth , Oya et al , and Murakami et al . The solid line denotes the recommendation of Oya et al, which is the preferred value in the present model.…”

Section: Detailed Kinetic Modelmentioning

confidence: 89%

“…We have adopted the rate constant for (R1) from the work of Oya et al . Remarkably, a linear extrapolation of the rate constant of Oya et al (1900–3230 K) to the conditions of the batch reactor work of Partington and Neville (823–873 K) shows agreement within a factor of two.…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

“…In the recovery of sulfur from acid gases, OCS can be formed from oxidation of CS 2 or from reaction of H 2 S with carbon oxides . Thermal decomposition and oxidation of OCS have been studied in batch reactors , flow reactors , shock tubes , and laminar premixed flames . Detailed chemical kinetic modeling of OCS oxidation has mostly been limited to shock tube conditions, simulating ignition delays , or atomic S or O profiles in OCS/O 2 /Ar mixtures.…”

Section: Introductionmentioning

confidence: 99%

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Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

Glarborg

Marshall

2013

Int J of Chemical Kinetics

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A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfactorily oxidation of OCS over a wide range of stoichiometric air-fuel ratios (0.5 ≤ λ ≤ 7.3), temperatures (450-1700 K), and pressures (0.02-3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled by the competition between chain-branching and -propagating steps; modeling predictions are particularly sensitive to the branching fraction for the OCS + O reaction to form CO + SO or CO 2

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OCS + M ⇌ CO + S + M

OCS + S ⇌ CO + {normalS}_{2}

and the rate constant for (R1), derived from the batch reactor (823–873 K) and shock tube work (1500–3230 K), is mostly in agreement within a factor of two (see Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Arrhenius plot for the reaction OCS + M

⇌

Section: Detailed Kinetic Modelmentioning

confidence: 89%

Section: Detailed Kinetic Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

Glarborg

Marshall

2013

Int J of Chemical Kinetics

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“…Later it was shown by Stock et al (1924) that the CO, reaction is much faster than the CO reaction; reaction 4 was appreciable even at room temperature, whereas reaction 2 began to be measurable only at 400°C. The equilibrium conditions of the two decomposition reactions of COS (reactions 2 and 4) have been investigated by Partington and Neville (1951). It was found that at 450"C, 25% of added CO suppressed the CO reaction and made it possible to study the CO, reaction separately.…”

Section: Cosmentioning

confidence: 99%

The CO‐catalyzed conversion of H₂S to H₂ + sulfur part 2. The thermal decomposition of COS

et al. 1999

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Research and Technology Branch, Alberta Energy, Edmonton, AB T5K 2G6, CanadaThe pyrolysis of COS has been studied over the temperature range 300 to 750°C using a variety of catalysts. The observed product distribution confirmed that two parallel reaction paths: 2 COS -+ 2 CO + S, (2) and 2 COS -+ CO, + CS, (4) are involved in the decomposition. The decomposition yield increased with rising temperature, accompanied with a shift in selectivity. At temperatures lower than -700°C the disproportionation reaction 4 was predominant, whereas at temperatures higher than 70O0C, reaction 2 was favoured. In the high-temperature region (700 to 750°C) it was possible to achieve full suppression of reaction 4 with added CS,. The pyrolysis of COS was also studied in a reactor packed with quartz chips without catalysts at high temperatures. Between 800 and 9OO"C, up to 99% conversion (with respect to the thermodynamic limit) could be achieved, with the almost complete absence of the disproportionation reaction 4. The results point to the commercial potential in the two-step reaction sequence: 2 H,S + 2 CO t) 2 COS + 2 H, 2 H,S t) 2 H, + S, 2 cos tf 2 co + s, for the economic conversion of hydrogen sulfide to hydrogen and sulfur.On a etudie la pyrolyse du COS dans une gamme de temperatures de 200 a 750°C a I'aide de divers catalyseurs. La distribution de produits observee confirme que deux chemins de reaction parallbles interviennent dans la decomposition, soit 2 COS + 2 CO + S, (2) et 2 COS + CO, + CS, (4). Le rendement de decomposition augmente avec la hausse de la temperature et est accompagne d'un changement de selectivite. A des temperatures inferieures a -700"C, la reaction de dismutation 4 I'emporte, tandis qu'a des temperatures superieures a 700"C, la reaction 2 est favorisee. Dans la region des temperatures superieures a 700"C, la reaction 2 est favorisee. Dans la region des temperatures elevees (700 a 750"C), il a ete possible d'eliminer totalement la reaction 4 par ajout de CS,. La pyrolyse de COS a egalement ete etudiee dans un reacteur garni d'eclats de quartz sans catalyseur a des temperatures elevees. Entre 800 et 900"C, jusqu'a 99% de la conversion (en tenant compte de la limite thennodynamique) a pu itre realisee, avec I'absence presque complete de la reaction de dismutation 4. Les resultats montrent le potentiel economique de la sequence de reaction a deux etapes : 2 H,S + 2 CO c+ 2 COS + 2 H, 2 cos t) 2 co + s, 2 H,S t) 2 H, + s, he hydrogen content of hydrogen sulfide is close to 6% T and if hydrogen sulfide could be converted directly to its elements, sulfur and hydrogen, the hydrogen thereby produced would be industrially significant. In the current, universallyapplied Claus process, only the sulfur is recovered while the hydrogen in the hydrogen sulfide is burnt to water, and essentially wasted. Extensive research has been directed in the recent past to develop alternative technologies for the economic conversion hydrogen sulfide to sulfur and hydrogen. One of such alternative technologies, would be the two-...

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