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Influence of the reactant concentration in selective hydrogenation of 1,3-butadiene over supported gold catalysts under alkene rich conditions: A consideration of reaction mechanism

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Abstract

This article is about the reaction of selective hydrogenation of 1,3-butadiene performed in an excess of alkenes (propene/butadiene ratio = 100) over supported gold catalysts, so as to mimic the conditions of purification of light alkenes (C4 cuts) from the presence of impurities (highly unsaturated compounds, 1–3%). Gold was found highly selective (close to 100%, no propane or butane formation) for the hydrogenation of butadiene to butenes at 100% conversion of butadiene. The influence of the concentrations of the various reactants, i.e. hydrogen, butadiene and propene, on the rates of butadiene and propene hydrogenation was investigated, and the apparent reaction orders were deduced from the dependence of rate on partial pressure in the gas phase. The reason for the high selectivity of gold catalysts is that the reaction of hydrogenation of alkenes occurs at much higher temperature (0.1% conversion at 300°C) than that of selective hydrogenation of butadiene (100% at T <170°C). Moreover, the presence of propene has only a limited influence on the reaction of butadiene hydrogenation, while butadiene has no influence on propene hydrogenation; the two reactions of hydrogenation hardly influence each other. Hydrogen dissociation is the rate limiting step of the reaction (partial order of 0.7 and 1 with respect to H2 for butadiene and propene hydrogenation, respectively), responsible for the low activity of gold. The catalytic properties of gold were compared to those of palladium-based catalysts, and reasons for their different behaviour were discussed.

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Author information

Correspondence to Catherine Louis.

Additional information

Catherine Louis is currently researcher at the French National Center for Scientific Research (CNRS) at the Laboratoire de Réactivité de Surface (LRS) of the Université Pierre et Marie Curie in Paris. Her research focuses on the preparation of supported metal catalysts and on the understanding of the chemical phenomena occurring during catalyst preparation. She has been working on gold catalysts since 2000. At LRS, she is the leader of a team entitled “Reactivity of Catalytic materials based on noble Metal and pseudo-Metals” comprising six permanent researchers. She is also the leader of the French network on Gold Nanoparticles “gold-nano”.

Laurent Delannoy is presently an Associate Professor in Inorganic Chemistry at the Pierre and Marie Curie University (UPMC — Paris 6). He received his PhD in Chemistry (Heterogeneous Catalysis) at the University of Science and Technology of Lille (France) in 2000. He joined the research group of Dr. Catherine Louis in 2002. His research interest involves the preparation and characterization of gold catalysts and the study of the performances of the gold catalysts in several hydrogenation and oxidation reactions.

Antoine Hugon is currently Research Engineer at IFP, working on hydrotreatment catalysts. He did his PhD at the LRS on selective hydrogenation of dienes over goldbased catalysts. His thesis was financially supported both by the CNRS and the WGC. He is graduated as a chemical engineer from ESCOM, in 2003, where he studied organic chemistry and chemical engineering.

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Hugon, A., Delannoy, L. & Louis, C. Influence of the reactant concentration in selective hydrogenation of 1,3-butadiene over supported gold catalysts under alkene rich conditions: A consideration of reaction mechanism. Gold Bull 42, 310–320 (2009). https://doi.org/10.1007/BF03214953

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Keywords

  • gold
  • catalyst
  • selective hydrogenation
  • butadiene
  • propene
  • kinetics

Running title

  • kinetics of selective hydrogenation of butadiene over gold catalysts