Modeling of the kinetic for the acidolysis of different triacylglycerols and caprylic acid catalyzed by Lipozyme IM immobilized in packed bed reactor

This work proposes a lumped kinetic model for the acidolysis of a triacylglycerol (TAG) and an odd free fatty acid (FFA) in a non-aqueous medium, catalyzed by a 1,3 specific lipase immobilized on a solid support. This model is based on the mechanism of the acidolysis reaction by considering the following hypothesis: (1) only the fatty acids in positions 1 and 3 of TAG are exchanged and these two positions in the glycerol backbone are equivalent and (2) the only intermediate of appreciable lifespan in which the enzyme participates is the acyl-enzyme complex. The kinetic equation obtained for the rate of incorporation of an odd fatty acid to TAG has been applied to the results obtained in the acidolysis of three oils (commercial triolein, cod liver oil (CLO) and a commercial oil enriched in eicosapentaenoic acid (EPA), EPAX 4510TG) with caprylic acid (CA), catalyzed by the immobilized lipase Lipozyme IM contained in a packed bed reactor (PBR). The acidolysis has been carried out by recirculating the reaction mixture through the PBR until the reaction equilibrium was reached. In these conditions it has been proved that the PBR behaves as a perfect mixed dispersion reactor and the experimental results obtained at low TAG concentrations (<100mol/m3) have been acceptably fitted to the kinetic expression obtained from the proposed model, with only two fitting parameters.However, for TAG concentrations higher than 100mol/m3, an appreciable reduction of the reaction rate was observed. This result was due to the decrease of the effective diffusivity of reactants within the pores of the support where the lipase is immobilized, since the viscosity of the reaction mixture increases appreciably when the reactant concentration also does. When this phenomenon is included in the developed kinetic model, the experimental results obtained at high TAG concentrations could also be explained, even in absence of the organic solvent (nn-hexane). It is observed that the influence of diffusion into the pores increases with the degree of CA incorporation to TAG, which was due to the increase of TAG and native fatty acid concentrations in the particle pores, which determines a continuous decrease in the effective diffusivity of CA.