Investigation of suitable precursors for manganese oxide catalysts in ethyl acetate oxidation

Abstract

The control of ethyl acetate emissions from fermentation and extraction processes in the pharmaceutical industry is of great importance to the environment. We have developed three Mn₂O₃ catalysts by using different Mn precursors (MnCl₂, Mn(CH₃COO)₂, MnSO₄), named as Mn₂O₃-Cl, -Ac, -SO₄. The tested catalytic activity results showed a sequence with Mn precursors as: Mn₂O₃-Cl > Mn₂O₃-Ac > Mn₂O₃-SO₄. The Mn₂O₃-Cl catalyst reached a complete ethyl acetate conversion at 212℃ (75℃ lower than that of Mn₂O₃-SO₄), and this high activity 100% could be maintained high at 212℃ for at least 100 hr. The characterization data about the physical properties of catalysts did not show an obvious correlation between the structure and morphology of Mn₂O₃ catalysts and catalytic performance, neither was the surface area the determining factor for catalytic activity in the ethyl acetate oxidation. Here we firstly found there is a close linear relationship between the catalytic activity and the amount of lattice oxygen species in the ethyl acetate oxidation, indicating that lattice oxygen species were essential for excellent catalytic activity. Through H₂ temperature-programmed reduction (H₂-TPR) results, we found that the lowest initial reduction temperature over the Mn₂O₃-Cl had stronger oxygen mobility, thus more oxygen species participated in the oxidation reaction, resulting in the highest catalytic performance. With convenient preparation, high efficiency, and stability, Mn₂O₃ prepared with MnCl₂ will be a promising catalyst for removing ethyl acetate in practical application.

Keywords: Catalytic oxidation; Ethyl acetate; Lattice oxygen species; Manganese; Precursor.