Oxidation of pinane to 2-pinane hydroperoxide over encaged metal phthalocyanines in Y zeolites. Mechanism and kinetic modelling

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Abstract

The influence of the oxygen donor (t-butyl hydroperoxide [t-BHP], O(2), H(2)O(2)) and the central metal (Cu, Co, Fe, Mn), on the activity and selectivity of metallophthalocyanines when free or encaged in NaY, for the oxidation of cis-pinane, is reported. The effect of encapsulation enhances catalyst stability and influences its activity and selectivity. Encaged complexes yield mainly 2-pinane hydroperoxide and insignificant amounts of 2-pinanol, while with their homogeneous counterparts, selectivities to 2-pinanol are higher. The ratio of 2-pinane hydroperoxide/2-pinanol depends on the amount of the complex, indicating that 2-pinane hydroperoxide is also in this last case, the primary oxidation product. With the purpose of checking the effect of the concentration of the oxidant agent on selectivity, oxidation experiments were carried out with slow addition of t-BHP, under semibatch conditions. A chain reaction mechanism initiated by t-BHP decomposition is proposed and a kinetic model was built for the semibatch reactor assuming internal mass transfer limitations concerning pinane. (C) 2000 Elsevier Science B.V. All rights reserved.
Original languageEnglish
Pages (from-to)163-172
Number of pages10
JournalJournal Of Molecular Catalysis A-Chemical
Volume156
Issue number1-2
DOIs
Publication statusPublished - 20 May 2000

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Keywords

  • Pinane hydroperoxide
  • Zeolite Y
  • Oxidation
  • Phthalocyanine complexes
  • Pinane

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