Fatty Acid Epoxidation on Enzymes: Experimental Study and Modeling of Batch and Semibatch Operation

Abstract

Biolubricants, plasticizers, bio-based rigid foams, and non-isocyanate polyurethanes can be made in a green way from epoxidized fatty acids. The classical technology for fatty acid epoxidation requires a reaction carrier, which acts as the real epoxidation agent. The process is complicated and involves a safety risk because of the appearance of percarboxylic acids. Therefore, the direct epoxidation of fatty acids in the presence of an immobilized enzyme is an attractive pathway to epoxidized fatty acids. Oleic acid was used as the model compound is this work, and commercial immobilized lipase Novozym 435 was used as the catalyst and hydrogen peroxide as the epoxidation agent. Batch and semibatch operation modes were tested in a laboratory-scale stirred tank reactor. The experimental results showed that almost complete conversions of the double bonds in oleic acid were achievable under isothermal batch and semibatch operation, with low concentrations of ring-opening byproducts. Semibatch operation gave an improvement of the product yield. Mathematical modeling of the experimental data was based on the reaction stoichiometry OA + HP → POA + W and OA + POA → EOA + OA, where OA = oleic acid, HP = hydrogen peroxide, POA = peroleic acid, W = water, and EOA = epoxized OA. Rate equations for the formation of peroleic acid and epoxide were derived, and the numerical values of the kinetic and adsorption parameters were estimated with nonlinear regression analysis. The reactor models consisted of ordinary differential equations, which were solved numerically during the parameter estimation until the optimal parameter values were reached. The model gave a very good description of the experimental data.