Using vanadium catalysts for the oxidation of hydrogen chloride with molecular oxygen

Tarabanko, Valery E.; Tarabanko, Nikolay; Koropachinskaya, N. V.

doi:10.1134/s2070050410030098

Cited by 13 publications

(13 citation statements)

References 4 publications

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“…These conditions can even affect the catalyst itself: chlorination of the catalyst (possibly with subsequent chloride evaporation) is known to be the cause of the loss of activity in some Deacon catalysts [17,45]. On the one hand, cerium trichloride that forms under certain conditions during the operation of cerium dioxide HCl oxidation catalysts [25,42] is not volatile at the temperature used in the experiments (703 K).…”

Section: On the Chlorination Of Ceria-based Deacon Catalystsmentioning

confidence: 97%

Electrospun ceria-based nanofibers for the facile assessment of catalyst morphological stability under harsh HCl oxidation reaction conditions

et al. 2015

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Section: On the Chlorination Of Ceria-based Deacon Catalystsmentioning

confidence: 97%

Electrospun ceria-based nanofibers for the facile assessment of catalyst morphological stability under harsh HCl oxidation reaction conditions

et al. 2015

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“…Copper compounds, such as anhydrous CuCl 2 (tolbachite), CuCl (nantokite), CuO (tenorite) and Cu 2 OCl 2 (melanothallite), together with variable amounts of NaCl, occur within the scoria subsurface layer (Vergasova et al, 2000;Pekov, 2007 and our observations). The contributions of some highly active catalysts, such as vanadium-based substances (Tarabanko et al, 2009 and references therein), cannot be excluded. Seven copper vanadates were observed at the Tolbachik cones (Zelenski et al, 2011).…”

Section: Basalt As a Catalystmentioning

confidence: 99%

Volcanic emissions of molecular chlorine

Zelenski

Taran

2012

Geochimica et Cosmochimica Acta

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“…Current Deacon-related research concentrates on searching for efficient and stable catalyst materials replacing expensive and less abundant ruthenium dioxide. ,− The limited amount of Ru resources leads to concerns about Ru shortage in the case of increasing demand in heterogeneous catalysis. One promising alternative to RuO 2 is CeO 2 , which was shown to be stable and active at 700 K .…”

Section: Summary and Concluding Remarksmentioning

confidence: 99%

Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

Over

2012

J. Phys. Chem. C

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Heterogeneous catalysis of the HCl oxidation by oxygen (Deacon process) over RuO2 is a green chemistry route to recover high purity Cl2 from HCl waste in an almost energy neutral way on a large industrial scale. The outstanding properties of RuO2-based catalysts are long-term stability under such harsh reaction conditions and high catalytic activity, allowing for lower reaction temperatures and hence for higher Cl2 conversions at equilibrium. In this Feature Article, I will be reviewing the atomic-scale insights into this Deacon process gained on single-crystalline RuO2(110) model catalysts. The extraordinary stability of RuO2(110) is traced to the selective and self-limited replacement of bridging surface oxygen by chlorine, thereby transforming active surface sites with basic Brønsted character into inactive sites and thereby suppressing the bulk chlorination of RuO2. The reaction mechanism has been clarified by utilizing experimental surface science techniques together with density functional theory (DFT) calculations. Oxygen adsorption proceeds dissociatively across two neighboring undercoordinated Ru sites, thereby forming two undercoordinated surface on-top O (Oot) atoms (homolytic cleavage). These Oot species are able to accept H from dissociative adsorption of HCl to form on-top Cl (Clot) and on-top hydroxyl groups (OotH). The heterolytic cleavage of HCl requires both acidic (undercoordinated Ru) and basic surface centers (undercoordinated O). Another H-transfer to the hydroxyl groups produces the byproduct water which desorbs at 420 K. The recombination of adjacent adsorbed Clot produces finally the desired product Cl2, an elementary reaction step with the highest activation barrier of 228 kJ/mol. Yet, oxygen adsorption constitutes the rate-determining step in the Deacon process over RuO2(110) under typical reaction conditions since strongly adsorbed Clot blocks dissociative oxygen adsorption. The overall reaction mechanism is governed by a delicate interplay of surface kinetics and thermodynamics, i.e., the adsorption energies of reactants, reaction intermediates and products.

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Using vanadium catalysts for the oxidation of hydrogen chloride with molecular oxygen

Cited by 13 publications

References 4 publications

Electrospun ceria-based nanofibers for the facile assessment of catalyst morphological stability under harsh HCl oxidation reaction conditions

Electrospun ceria-based nanofibers for the facile assessment of catalyst morphological stability under harsh HCl oxidation reaction conditions

Volcanic emissions of molecular chlorine

Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process

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Using vanadium catalysts for the oxidation of hydrogen chloride with molecular oxygen

Cited by 13 publications

References 4 publications

Electrospun ceria-based nanofibers for the facile assessment of catalyst morphological stability under harsh HCl oxidation reaction conditions

Electrospun ceria-based nanofibers for the facile assessment of catalyst morphological stability under harsh HCl oxidation reaction conditions

Volcanic emissions of molecular chlorine

Atomic-Scale Understanding of the HCl Oxidation Over RuO2, A Novel Deacon Process

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Product

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Atomic-Scale Understanding of the HCl Oxidation Over RuO₂, A Novel Deacon Process