Stable Deacon Process for HCl Oxidation over RuO<sub>2</sub>

Crihan, Daniela; Knapp, Marcus; Zweidinger, Stefan; Lundgren, Edvin; Weststrate, C.J.; Andersen, Jesper N; Seitsonen, Ari P.; Over, Herbert

doi:10.1002/anie.200705124

Cited by 125 publications

(142 citation statements)

References 16 publications

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“…Crihan et al reported that the RuO 2-x Cl x in which bridging O atoms are replaced by Cl atoms is active and stable [7]. López et al have reported a mechanism of the HCl oxidation to Cl 2 over RuO 2 by using DFT calculations in combination with experiments.…”

Section: Introductionmentioning

confidence: 97%

Development of RuO2/Rutile-TiO2 Catalyst for Industrial HCl Oxidation Process

2010

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Sumitomo Chemical has developed a low energy consuming and green process for the catalytic oxidation of HCl to Cl 2 , especially when compared with the electrolysis process. The RuO 2 /rutile-TiO 2 catalyst has high catalytic activity and thermal stability due to ultra-fine RuO 2 crystallites that cover the surface of the TiO 2 primary particles with strong interaction. In addition, the silica modified RuO 2 /rutile-TiO 2 catalyst shows higher thermal stability by preventing the RuO 2 sintering due to using dispersed SiO 2 particles. With these catalysts, high reaction rates required for industrial applications are achieved, even at low temperatures.

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Section: Introductionmentioning

confidence: 97%

Development of RuO2/Rutile-TiO2 Catalyst for Industrial HCl Oxidation Process

2010

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“…There is strong evidence that the surface chlorination may play a major role in the stabilization of the RuO 2 catalyst. 4 Still the actual chlorination mechanism of RuO 2 is only poorly understood. In the present paper we report on high resolution core level spectroscopy (HRCLS) and temperature programmed reaction (TPR) experiments in combination with density functional theory (DFT)…”

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confidence: 99%

Hydrogen-Promoted Chlorination of RuO₂(110)

et al. 2010

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High resolution core level photoemission spectroscopy and temperature programmed reaction experiments together with density functional theory calculations were used to elucidate the chlorination mechanism of ruthenium dioxide RuO 2 (110) by hydrogen chloride exposure on the atomic scale. The surface selective chlorination accounts for the extraordinary stability of the RuO 2 catalyst in the Sumitomo process -the heterogeneously catalyzed oxidation of hydrogen chloride by oxygen. The selective replacement of bridging oxygen atoms by chlorine atoms depends on the formation of water molecules serving as leaving groups. Water is produced by the chlorine assisted recombination of two neighboring surface hydroxyl groups at around 450 K -a temperature where water instantaneously leaves the surface. Finally, the bridging vacancy is filled in by chlorine atoms, thereby forming bridging chlorine atoms. Pre-adsorbed hydrogen has shown to facilitate the chlorination process for stoichiometry reasons. The general strategy of transforming bridging O atoms into a good leaving group has been corroborated by the chlorination of RuO 2 (110) via CO pretreatment and subsequent Cl 2 exposure with CO 2 as leaving group.2

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“…For many years, this way of the olefins production was thermodynamically complicated by the necessity to perform the Deacon reaction, for which no effective catalysts were available. Nowadays, a RuO 2 /TiO 2 catalyst is proposed for the Deacon reaction that allows performing this process at temperatures below 300 • C [19][20][21]. Catalysts based on ruthenium also show good performance in other reactions involving chlorine or its derivatives, such as the oxychlorination of methane and ethane [22].…”

Section: Introductionmentioning

confidence: 98%

“…Hevia et al [23] suggested that the active site of the RuO 2 /TiO 2 catalyst in the Deacon reaction was RuO 2−x Cl x ruthenium oxychloride. Crihan et al [20] indicated that RuO 2 surface was chlorinated during the catalyzed oxidation of HCl with oxygen by selective replacement of bridging oxygen atoms by bridging chlorine atoms. This view was confirmed by Teschner et al [24] showed that the surface of RuO 2 was extensively chlorinated at typical Deacon reaction conditions.…”

Section: Introductionmentioning

confidence: 99%