Kinetic models of reaction systems for the in situ epoxidation of unsaturated fatty acid esters and triglycerides

Janković, Milovan; Sinadinović‐Fišer, Snežana

doi:10.2298/hemind0412569j

Cited by 20 publications

(30 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[13] In the presence of a heterogeneous solid catalyst, the peroxyacid formation step includes different substeps, such as diffusion of reactants into catalyst pores, adsorption of reactants on the catalyst surface, reaction at the catalyst surface, and diffusion of products from the catalyst to the bulk reaction mixture. The in situ epoxidation of cottonseed oil with PAA in the presence of a heterogeneous acid catalyst can be depicted as follows: All the experiments were carried out isothermally, under a stirring speed of 2400 rev/min, to ensure that there is no diffusional mass transfer resistance at the solid-liquid and liquid-liquid interfaces, and also it has been proved that the intraparticle diffusional effect is negligible.…”

Section: Epoxidation Kineticsmentioning

confidence: 99%

“…The model was developed based on the assumptions made by Janković and Sinadinović-Fišer, [13] and the model that fits the experimental data was based on a chemisorption mechanism as shown below. Besides the reaction of PAA formation (Reaction 5), the derived model includes the epoxidation reaction (Reaction 6) and the reactions involving oxirane cleavage (Reactions 7a and 7b).…”

Section: Epoxidation Kineticsmentioning

confidence: 99%

See 1 more Smart Citation

Selective epoxidation of natural triglycerides using acidic ion exchange resin as catalyst

Dinda

Goud

Patwardhan

et al. 2011

Asia-Pacific J Chem Eng

View full text Add to dashboard Cite

Epoxidation is a very useful reaction in organic synthesis. Due to the high reactivity of the epoxide group it can be used as an active intermediate for the synthesis of many high-value products. Epoxides are commercial products and they have many industrial uses. Understanding the kinetics of epoxidation reactions can lead to production of value-added products from locally available renewable natural resources. This research investigated the kinetics of epoxidation of cottonseed oil by peroxyacetic acid (PAA) generated in situ from hydrogen peroxide and glacial acetic acid (AA) in the presence of acidic ion exchange resin (AIER) catalysts, namely Amberlite IR-120. The effect of several variables including temperature, stirring speed, catalyst loading, and particle size, concentration of hydrogen peroxide and AA on oxirane conversion was studied. A satisfactory level of oxirane conversion (greater than 65%) with high selectivity (greater than 90%) could be obtained if the epoxidation was carried out at optimum conditions, using in situ generated PAA. The Langmuir-Hinshelwood-Hougen-Watson (L-H-H-W) kinetic model approach has been adopted for the development of overall reaction rate equations, and the proposed kinetic model includes the major side reactions for the estimation of kinetic parameters. Kinetic parameters were estimated by fitting experimental data using a nonlinear regression method. From the estimated kinetic constants, the activation energy for the AIER catalysed epoxidation of cottonseed oil was found to be 10.1 kcal mol −1 . 

show abstract

Section: Epoxidation Kineticsmentioning

confidence: 99%

Section: Epoxidation Kineticsmentioning

confidence: 99%

Selective epoxidation of natural triglycerides using acidic ion exchange resin as catalyst

Dinda

Goud

Patwardhan

et al. 2011

Asia-Pacific J Chem Eng

View full text Add to dashboard Cite

show abstract

“…The mechanism for the in situ epoxidation in the presence of homogeneous catalyst is generally described as follows: (i) formation of peroxyacetic acid in the aqueous phase in the presence of catalyst; (ii) transfer of peroxyacetic acid from the aqueous phase to the oil phase; (iii) reaction of peroxyacetic acid in the oil phase to produce epoxides and to release acetic acid; (iv) degradation of the epoxide ring in the oil phase, as well as at the oilaqueous interface; (v) transfer of acetic acid from the oil phase back to the aqueous phase [20].…”

Section: Kinetic Modelmentioning

confidence: 99%

Epoxidation of karanja (Pongamia glabra) oil catalysed by acidic ion exchange resin

Goud

Patwardhan

Dinda

et al. 2007

Euro J Lipid Sci & Tech

View full text Add to dashboard Cite

Epoxidation of karanja (Pongamia glabra) oil catalysed by acidic ion exchange resinKaranja oil with an iodine value of 89 g/100 g was epoxidised in situ with aqueous hydrogen peroxide and acetic acid in the presence of Amberlite IR-120 acidic ion exchange resin as catalyst. The effect of the operating variables on the oxirane oxygen content, as well as on the oxirane ring stability and the iodine value of the epoxidised karanja oil, were determined. The variables studied were stirring speed, hydrogen peroxide-to-ethylenic unsaturation molar ratio, acetic acid-to-ethylenic unsaturation molar ratio, temperature, and catalyst loading. The effects of these parameters on the conversion to the epoxidised oil were studied and the optimum conditions for the maximum oxirane content were established. The proposed kinetic model takes into consideration the two side reactions, namely, epoxy ring opening involving the formation of hydroxy acetate and hydroxyl groups, and the reaction between the peroxyacid and the epoxy group. The kinetic and adsorption constants of the rate equations were estimated by the best fit using Marquardt's algorithm. Good agreement between experimental and predicted data validates the proposed kinetic model. From the estimated kinetic constants, the apparent activation energy for the epoxidation reaction was found to be 11 kcal/mol. Keywords: Epoxidation, peroxyacetic acid, karanja oil (Pongamia glabra), acidic ion exchange resin, kinetics.Eur. J. Lipid Sci. Technol. 109 (2007) 575-584 DOI 10.1002/ejlt.200600298 575 IntroductionEpoxidation of plant oils (triacylglycerols), commonly referred to as "vegetable oils", is a commercially important reaction as the epoxides obtained from these renewable resources, and from their transesterification products, have wide applications in materials such as plasticisers and polymer stabilisers [1][2][3].Fats and oils are renewable resources that can be treated chemically or enzymatically to produce materials that can often act as replacement for materials derived from petroleum. Fatty epoxides can be used directly as plasticisers that are compatible with polyvinyl chloride (PVC) and stabilisers for PVC resins to improve flexibility, elasticity, and toughness and to impart stability to the polymer towards heat and UV radiation. Due to the high reactivity of the oxirane ring, epoxides also act as a raw material for a variety of chemicals, such as alcohols, glycols, alkanolamines, carbonyl compounds, olefinic compounds, and polymers like polyesters, polyurethanes, and epoxy resins. Epoxidised oil with a higher oxirane oxygen value and a lower iodine value is considered to be of better quality [4][5][6]. Today, one of the most important epoxidised vegetable oils is epoxidised soybean oil (ESO), and its worldwide production is about 200,000 t/year [7].On an industrial scale, the epoxidation of plant oils is currently carried out with the "Prileschajew reaction", in which the unsaturated oils react with a percarboxylic acid, such as peroxyacetic acid or peroxyf...

show abstract

“…Janković and Sinadinović-Fišer [76] have already postulated a kinetic model for the in situ formation of peracetic acid from acetic acid and hydrogen peroxide in the presence of a homogeneous acid catalyst. The mechanism can be summarized in the following steps: (i) formation of peracetic acid in the presence of the catalyst and (ii) reaction between peracetic acid and the double bonds to produce oxirane rings, releasing acetic acid.…”

Section: Kinetic Model For the In Situ Epoxidation Of Grape Seed Oilmentioning

confidence: 99%

“…There is a small diference among these values and our determined one (7.3 kcal/mol). Janković and Sinadinović-Fišer [76] concluded that the number and the position of the double bonds, their position with respect to the carboxylic group, and the presence of cis-or trans-isomers have …”

Section: Kinetic Model For the In Situ Epoxidation Of Grape Seed Oilmentioning

confidence: 99%

Revalorization of Grape Seed Oil for Innovative Non-Food Applications

Haro¹,

Rodrı́guez²,

Carmona³

et al. 2018

Grapes and Wines - Advances in Production, Processing, Analysis and Valorization

View full text Add to dashboard Cite

Grape processing produces a substantial amount of residues that are highly polluting and expensive to treat, being grape seed one of the main by-products with high commercial interest. During the extraction process of grape seed oil, most of the nutraceutical compounds remain on the solid cake. This book chapter resumes the potential utilization of grape seed oil for producing biobased materials through environmentally friendly processes that could substitute petroleum-derived products. Special atention is given to transesteriication and epoxidation processes. The transesteriication of grape seed oil in presence of methanol drives to the production of a biodiesel with excellent low-temperature properties. According to EN 14214, grape seed oil-based biodiesel presents a slightly lower cetane number than the speciied limit. In addition, this biodiesel presents a low oxidation stability which can be improved by the incorporation of oxidation stabilizer. Atending to the epoxidation of grape seed oil, short reaction times and high temperatures are advised. Epoxidized grape seed oil can be used for the synthesis of biobased polyols and its further application on the synthesis of polyurethane compounds.

show abstract

Kinetic models of reaction systems for the in situ epoxidation of unsaturated fatty acid esters and triglycerides

Cited by 20 publications

References 11 publications

Selective epoxidation of natural triglycerides using acidic ion exchange resin as catalyst

Selective epoxidation of natural triglycerides using acidic ion exchange resin as catalyst

Epoxidation of karanja (Pongamia glabra) oil catalysed by acidic ion exchange resin

Revalorization of Grape Seed Oil for Innovative Non-Food Applications

Contact Info

Product

Resources

About