The kinetics of the epoxidation of soybean oil in bulk by peracetic acid formed in situ, in the presence of an ion exchange resin as the catalyst, was studied. The proposed kinetic model takes into consideration two side reactions of the epoxy ring opening involving the formation of hydroxy acetate and hydroxyl groups as well as the reactions of the formation of the peracid and epoxy groups. The catalytic reaction of the peracetic acid formation was characterized by adsorption of only acetic acid and peracetic acid on the active catalyst sites, and irreversible surface reaction was the overall rate-determining step. Kinetic parameters were estimated by fitting experimental data using the Marquardt method. Good agreement between the calculated and experimental data indicated that the proposed kinetic model was correct. The effect of different reaction variables on epoxidation was also discussed. The conditions for obtaining optimal epoxide yield (91% conversion, 5.99% epoxide content in product) were found to be: 0.5 mole of glacial acetic acid and 1.1 mole of hydrogen peroxide (30% aqueous solution) per mole of ethylenic unsaturation, in the presence of 5 wt% of the ion exchange resin at 75°C, over the reaction period of 8 h.Paper no. J9753 in JAOCS 78, 725-731 (July 2001).Although numerous references exist in the literature concerning the methods of epoxidation of different olefinic substrates, many fewer are concerned with the kinetics of epoxidation. The kinetics of the process depend on the reaction conditions. Epoxidation of vegetable oils can be carried out in solution or in bulk, with in situ (1-3) formed or preformed peracids (4-9), with homogeneous or heterogeneous catalysts. A kinetic model for in situ epoxidation of anchovy oil with partially preformed peracetic acid in the presence of a resin catalyst was reported (10). In the range of the operating variables, epoxidation and ring opening were described by a pseudo first-order reaction, applying the principle of the stationary state. Two studies of the kinetics of the in situ epoxidation of oleic acid with hydrogen peroxide and acetic acid and of methyl esters of palm olein by performic and peracetic acid, both carried out in the presence of sulfuric acid as a catalyst, concluded that the rate-determining step of the epoxidation process was the formation of peracetic (or performic) acid (11,12). Rangarajan et al. (13) reported kinetic parameters for the in situ epoxidation of soybean oil by peracetic acid, again in the presence of sulfuric acid as the catalyst, but treated it as a two-phase system. Significantly higher rates were obtained when heat and mass transfer limitations were removed. The proposed model also predicted the effect of the addition of an inert solvent on epoxidation.With an acidic ion exchange resin as the catalyst for the epoxidation of vegetable oils, the porous structure of the solid catalyst and the size of the natural unsaturated triglycerides were found to minimize side reactions and thus improve selectivity (SE) (14). The p...
Mathematical models that describe the kinetics of reaction systems for the in situ epoxidation of unsaturated fatty acid esters or triglycérides with organic peracids are reviewed in this paper. The advantages and inadequacies of each model are discussed. A mono-phase pseudo-first order kinetic model was compared with a two phase model based on the Langmuir-Hinshelwood-Hougen-Watson (LHHW) postulates proposed by the authors of this paper. The comparison was performed on the experimentally determined values for the in situ epoxidation of soybean oil by peracetic acid in the presence of different quantities of ion exchange resin used as the catalyst. It was concluded that a complete model for in situ epoxidation in the presence of ion exchange resin as the catalyst was still not given for perorganic acid formation. In particular, we report here the possibilities of the creation of an "ideal" model for in situ epoxidation
The
kinetics of the epoxidation of castor oil in benzene with peracetic
acid formed in situ from acetic acid and hydrogen
peroxide in the presence of an ion-exchange resin as a catalyst was
studied. Eighteen pseudo-two-phase models are established that, besides
the main reactions of peracid and epoxy ring formation, also consider
the side reaction of epoxy ring cleavage with acetic acid. Kinetic
expressions for the heterogeneously catalyzed peracetic acid formation
are developed on the basis of Eley–Rideal and Langmuir–Hinshelwood–Hougen–Watson
postulates. An equation derived for the temperature dependency of
the chemical equilibrium constant for peracetic acid formation is
applied. Kinetic and adsorption parameters were estimated by fitting
experimental data using the Marquardt method. The best-fit model correctly
interprets data of double bond and epoxy group contents as a function
of reactant ratios, catalyst concentrations, and temperatures applied
during epoxidation. The proposed model better fits experimental data
than the pseudohomogeneous model reported in the literature.
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