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Kinetic study of ethyl ester transesterification using a hybrid silica catalyst

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Abstract

CTA-MCM-41 hybrid silica was prepared using a 40 °C non hydrothermal method for 2 h and was characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. Using these techniques was possible to confirm the structural organization with a highly organized hexagonal matrix of the MCM-41 type, quantify the presence of hexadecyltrimethylammonium cations present in the pores of silica and, consequently, to measure the concentration of the catalytic sites present in the material, 1.83 mmol g−1. This catalyst was used in the transesterification of the esters with the aim of determining the influence of the length of the ester side-chain on the reaction kinetics. The ethyl esters tested had the length of the ester side-chain in the range 1–4 carbons. The catalytic tests were performed at temperatures ranging from 20 to 50 °C, employing a methanol/ester molar ratio of 6:1 and 4% of catalyst relative to the total reactants mass. Conversion close to 80% was observed for the ethyl acetate at 40 °C and decreased as the length of the ester side-chain increased. Fitting using a pseudo-homogeneous reversible first order model enabled determination of the kinetic parameters for each reaction with activation energies between 41.3 and 48.3 kJ mol−1. Inductive and diffusional effects explain the slower reaction rate and higher activation energy as the size of the molecule increase.

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Acknowledgements

The authors are grateful for the financial support provided by the following Brazilian agencies: Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Grant #132824/2018-3 and Grant #141307/2018-8) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES, #001). The authors thank the Structural Characterization Laboratory of UFSCar (LCE/DEMa/UFSCar) for the microscopy analyses.

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  1. Catalysis Laboratory, Department of Chemical Engineering, Federal University of São Carlos, Rod. Washington Luiz, km 235, São Carlos, SP, 13665-905, Brazil

    Luana do Nascimento Rocha de Paula, Gustavo Medeiros de Paula & Dilson Cardoso

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  1. Luana do Nascimento Rocha de Paula
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  2. Gustavo Medeiros de Paula
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de Paula, L.N.R., de Paula, G.M. & Cardoso, D. Kinetic study of ethyl ester transesterification using a hybrid silica catalyst. Reac Kinet Mech Cat 135, 2427–2439 (2022). https://doi.org/10.1007/s11144-022-02258-y

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