A novel continuous countercurrent epoxidation process

Latourette, H. K.; Castrantas, H. M.; Gall, Ralph J.; Dierdorff, L. H.

doi:10.1007/bf02631598

Cited by 7 publications

(7 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In situ epoxidation of soybean oil with peracetic acid in the presence of an ion exchange resin is a heterogeneous catalytic process in which peracetic acid formation is an acid-catalyzed reaction: [1] whereas the main reaction involving the epoxy group formation is an uncatalyzed reaction: [2] The following side reactions of the epoxy ring cleavage that may take place are acid-catalyzed: [3] To reduce the number of model parameters, i.e., to simplify the mathematical model, which represents the system of differential equations for rates of the reactions shown above, heat and mass diffusion resistances in the system liquid-solid are usually ignored (15,18). Since the stirring was good and the epoxidation was conducted isothermally, those diffusion resistances were assumed to be negligible and the steps concerning the transport phenomena in our studies of kinetics were also ignored.…”

Section: Table 1 Values Of Reaction Variables and Product Properties mentioning

confidence: 99%

Kinetics of in situ epoxidation of soybean oil in bulk catalyzed by ion exchange resin

Sinadinović‐Fišer

Janković

Petrovìć

2001

J Americ Oil Chem Soc

130

View full text Add to dashboard Cite

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...

show abstract

Section: Table 1 Values Of Reaction Variables and Product Properties mentioning

confidence: 99%

Kinetics of in situ epoxidation of soybean oil in bulk catalyzed by ion exchange resin

Sinadinović‐Fišer

Janković

Petrovìć

2001

J Americ Oil Chem Soc

130

View full text Add to dashboard Cite

show abstract

“…The general process for the synthesis of the epoxide groups is known as an epoxidation reaction wherein an alkene is reacted with an organic peroxy acid . In-situ epoxidation using hydrogen peroxide as oxygen donar and acetic or formic acid as the peroxygen carrier has achieved commercial importance (Latourette et al, 2006). With hydrogen peroxide and acetic acid, however, acid catalysts, such as sulfuric acid or strong cation exchange resins, are needed to speed up peracid formation, whereas performic acid formation requires no strong acid.…”

mentioning

confidence: 99%

Synthesis And Characterization Of Epoxidized Thevetia Peruviana Seed Oil

Kwao

2023

IJPBMS

View full text Add to dashboard Cite

The seed oil of Thevetia peruviana was extracted using soxhlet extraction method with n-hexane. The physicochemical parameters of the extracted oil were determined using standard analytical methods. The extracted oil was epoxidized using peracid generated in situ from aqueous hydrogen peroxide (H2O2) and glacial acetic acid. The epoxidized oil was analysed for the functional groups present using Fourier Transform Infrared (FTIR) Spectrometer. The physiochemical parameters of Thevetia peruviana seed oil showed the following results; acid value (3.86 mg KOH/g), iodine value (92.5 Wij’s), peroxide value (30.0 meq/kg), kinetic viscosity (1.7cp) and saponification value (121.76 mgKOH/g) while the epoxidized oil has acid value (0.49 mg KOH/g), iodine value (68.10 Wij’s), peroxide value (7.99 meq/kg), kinetic viscosity (5.57cp) and saponification value (156.1 mgKOH/g). The FTIR results showed that both unepoxidised and epoxidized oils showed the following functional groups OH at wavelengths 3469.50 cm-1, 3468.72 cm-1 and 3467.75 cm-1; CH at 2917.75 cm-1, 2922.47 cm-1 and 2924.61 cm-1; CH2 at 2852.39 cm-1, 2852.81 cm-1 and 2853.68 cm-1; C=O at 2679.32 cm-1, 2679.41 cm-1 and 2673.30 cm-1; C=C at 1656.14 cm-1, 1654.55 cm-1 and 1655.5 cm-1 while the C≡C at wavelength 2030.69 cm-1 that was identified in the unepoxidised oil was found to be absent in the epoxidised oil and a peak indicating epoxyl group was identified in the epoxidized oil. The percentage conversion of oxirane was determined to be 83.5%. This shows that epoxides were effectively formed. The high oil yield and percentage conversion of oxirane makes Thevetia peruviana a good feedstock for production of industrial intermediates

show abstract

“…The most widely used process is the epoxidation of unsaturated compounds with either pre-or in-situ-formed organic peracids. In-situ epoxidation using hydrogen peroxide with either acetic or formic acid as the peroxygen carrier has achieved commercial importance (4)(5)(6)(7). With hydrogen peroxide and acetic acid, however, acid catalysts, such as sulfuric acid or strong cation exchange resins, are needed to speed up peracid formation, whereas performic acid formation requires no strong acid.…”

mentioning

confidence: 99%

Model for a cascade continuous epoxidation process

Hang

Yang

1999

J Americ Oil Chem Soc

View full text Add to dashboard Cite

A steady-state mathematical model was developed to analyze the performance of a cascade continuous epoxidation process that was applied to the epoxidation of unsaturated compounds with in-situ-formed performic acid. The model equations were nonlinear, and the model prediction was calculated by solving the model equations using a numerical solution procedure. The experimental results supported the model prediction in that good agreement between the model predictions and experimental results was achieved. The model is necessary for precise operation control, process estimation, and operating parameter optimization and regulation, and will provide a theoretical foundation and research method for automatic control and engineering scale-up.Paper no. J8853 in JAOCS 76, 89-92 (January 1999).The epoxidation of unsaturated fatty acid derivatives, primarily soybean oil and other vegetable oils, is carried out on an industrial scale, producing plasticizers that are compatible with polyvinyl chloride (PVC) and which also act as PVC stabilizers, primarily against heat degradation. In general, the degree of compatibility and stability of an epoxidized oil increases with increasing purity and oxirane number. The iodine value (IV) is a measure of the number of double bonds, while the oxirane value (EPO) is an indication of the percentage content (%, by wt) of epoxide oxygen. The quality of the epoxidized oil is better the higher the oxirane value and the lower the iodine number (1-3). Several processes are available for the preparation of epoxidized oils. The most widely used process is the epoxidation of unsaturated compounds with either pre-or in-situ-formed organic peracids. In-situ epoxidation using hydrogen peroxide with either acetic or formic acid as the peroxygen carrier has achieved commercial importance (4-7). With hydrogen peroxide and acetic acid, however, acid catalysts, such as sulfuric acid or strong cation exchange resins, are needed to speed up peracid formation, whereas performic acid formation requires no strong acid. In our laboratory, the previous study of the kinetics and mechanism of the epoxidation of oils with in-situformed performic acid, as well as the kinetics of oxirane cleavage of epoxidized silkworm pupae oil, showed that formation as well as cleavage of the oxirane ring occurred simultaneously during the epoxidation process. The results indicate that the net yield of epoxides is determined by rates of both reactions, which depend on several factors, such as organic acid concentration and reaction temperature (8,9).Compared with a batch process, a continuous process has three advantages: (i) stable product quality; (ii) convenience, because of use of automatic control; and (iii) lower production costs. Additionally, the continuous process is useful for controlling by-product formation and improving reaction selectivity and yield by changing material contacting time and reaction temperature.Although the epoxidation of unsaturated oils has been extensively investigated, mathematical modeling of a con...

show abstract

A novel continuous countercurrent epoxidation process

Cited by 7 publications

References 7 publications

Kinetics of in situ epoxidation of soybean oil in bulk catalyzed by ion exchange resin

Kinetics of in situ epoxidation of soybean oil in bulk catalyzed by ion exchange resin

Synthesis And Characterization Of Epoxidized Thevetia Peruviana Seed Oil

Model for a cascade continuous epoxidation process

Contact Info

Product

Resources

About