Methyl Oleate Synthesis by TiO<sub>2</sub> Photocatalytic Esterification of Oleic Acid: Optimisation by Response Surface Quadratic Methodology, Reaction Kinetics and Thermodynamics
R. A. Welter, Harrson Silva Santana, Lucimara Gaziola de la Torre, Mark J. Robertson, Osvaldir Pereira Taranto, Michael Oelgemöller
Abstract
Abstract Methyl oleate, an example of a FAME (fatty acid methyl ester), was produced by oleic acid (OA) photoesterification with TiO 2 and UVA light. Different parameters were evaluated and optimised: catalyst pretreatment, temperature (25–65 °C), catalyst loading (1–30 % w/w OA ) and oleic acid : alcohol molar ratio (1 : 3–1 : 55). Response surface quadratic methodology obtained by central composite rotational design (RSM‐CCRD) was used to evaluate the main operational conditions of the photoesterification process. A high conversion of 98 % (±0.8) at 55 °C, 20 % TiO 2 (w/w OA ), and 1(OA) : 55(methanol) molar ratio was achieved. The photoesterification mechanism is furthermore proposed. The Langmuir‐Hinshelwood kinetic model considered the forward and backward reaction as first‐order fits with the best accuracy (R 2 of 0.997). The thermodynamic results (ΔG 338.15K =−20.75 kJ/mol, ΔH=13.75 kJ/mol, and ΔS=0.47 kJ/mol.K) indicate that the operating conditions are important, both to supply the energy requirement of the reaction, but also to increase the miscibility of the reactants.