Chinese Journal of Catalysis

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Ethyl and butyl acetate oxidation over manganese oxides

Olívia Salomé G. P. Soares, Raquel P. Rocha, José J. M. Órfão, Manuel F. R. Pereira, José L. Figueiredo   

  1. Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials(LSRE-LCM), Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal
  • Received:2017-11-07 Revised:2017-11-21 Online:2018-01-18 Published:2018-01-19
  • Contact: 10.1016/S1872-2067(17)62986-3

Abstract:

Mangenese oxides were synthesized using two new methods, a novel solvent-free reaction and a reflux technique, that produced cryptomelane-type products (K-OMS-2). Oxides were also synthesized using conventional methods and all specimens were applied to the oxidation of ethyl acetate and butyl acetate, acting as models for the volatile organic compounds found in industrial emissions. The catalysts were also characterized using N2 adsorption, X-ray diffraction, scanning electron microscopy, temperature programmed reduction and X-ray photoelectron spectroscopy. Each of the manganese oxides was found to be very active during the oxidation of both esters to CO2, and the synthesis methodology evidently had a significant impact on catalytic performance. The K-OMS-2 nanorods synthesized by the solvent-free method showed higher activity than K-OMS-2 materials prepared by the reflux technique, and samples with cryptomelane were more active than those prepared by the conventional methods. The catalyst with the highest performance also exhibited good stability and allowed 90% conversion of ethyl and butyl acetate to CO2 at 213 and 202℃, respectively. Significant differences in the catalyst performance were observed, clearly indicating that K-OMS-2 nanorods prepared by the solvent-free reaction were better catalysts for the selected VOC oxidations than the mixtures of manganese oxides traditionally obtained with conventional synthesis methods. The superior performance of the K-OMS-2 catalysts might be related to the increased average oxidation state of the manganese in these structures. Significant correlations between the catalytic performance and the surface chemical properties were also identified, highlighting the K-OMS-2 properties associated with the enhanced catalytic performance of the materials.

Key words: Volatile organic compound, Ethyl acetate, Butyl acetate, Manganese oxide, Catalytic oxidation