De Araujo Gonacalves J.,Laboratorio Of Tecnologias Verdes |
Ramos A.L.D.,Federal University of Sergipe |
Rocha L.L.L.,Laboratorio Of Tecnologias Verdes |
Domingos A.K.,Laboratorio Of Tecnologias Verdes |
And 4 more authors.
Journal of Physical Organic Chemistry | Year: 2011
Biodiesel can be obtained from fatty acid raw materials through esterification. The reactivity of lauric, palmitic, stearic, oleic, and linoleic fatty acids with methanol using powdered niobic acid as a heterogeneous catalyst was investigated in this work, both experimentally (in a batch reactor) and theoretically. A 23 experimental design was used, with methanol/fatty acid molar ratio, catalyst concentration, and temperature as main factors. An empirical model demonstrated that temperature is the most important variable. Fourteen heterogeneous and 56 homogeneous-like kinetic models were tested. A homogeneous-like model considering zero order for all species and inhibition by water was the most adequate for experiments without catalyst. A homogeneous-like model considering a second-order reaction in relation to the fatty acid and no water inhibition was the most adequate for niobic acid catalyzed reaction. Molecular modeling confirmed the experimental results showing that the reactivity is directly related to the increase of unsaturated bonds and the reduction of carbon chain length. The polarity of the fatty acid is determinant in the reactivity. At the molecular level, reaction occurs between the HOMO orbital of methanol and LUMO orbitals of fatty acids and reactivity is higher when the energy difference between these orbitals is lower. © 2010 John Wiley & Sons, Ltd.