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Mathematical model of reaction sistem for in situepoxidation of soybean oil with peracetic acid

dc.contributor.advisorSinadinović-Fišer, Snežana
dc.contributor.otherOmorjan, Radovan
dc.contributor.otherSinadinović-Fišer, Snežana
dc.contributor.otherSkala, Dejan
dc.creatorJanković, Milovan
dc.date.accessioned2018-12-19T17:10:42Z
dc.date.available2018-12-19T17:10:42Z
dc.date.available2020-07-03T13:53:07Z
dc.date.issued2013-09-16
dc.identifier.urihttp://nardus.mpn.gov.rs/handle/123456789/10374
dc.identifier.urihttps://www.cris.uns.ac.rs/DownloadFileServlet/DisertacijaJankovic_Doktorat.pdf?controlNumber=(BISIS)83242&fileName=Jankovic_Doktorat.pdf&id=567&source=NaRDuS&language=srsr
dc.identifier.urihttps://www.cris.uns.ac.rs/record.jsf?recordId=83242&source=NaRDuS&language=srsr
dc.identifier.urihttps://www.cris.uns.ac.rs/DownloadFileServlet/IzvestajKomisije147072982718615.pdf?controlNumber=(BISIS)83242&fileName=147072982718615.pdf&id=6686&source=NaRDuS&language=srsr
dc.description.abstractCilj ove doktorske disertacije je postavljanje matematičkog modela složenog trofaznog reakcionog sistem za epoksidovanje sojinog ulja in situ formiranom persirćetnom kiselinom iz sirćetne kiseline i vodonik peroksida u prisustvu jonoizmenjivačke smole kao katalizatora. Model uzima u obzir koncentracije reaktanata i produkata u vodenoj i uljnoj fazi. Pored osnovnih reakcija stvaranja persirćetne kiseline i epoksida, model obuhvata i sporednu reakciju otvaranja epoksi prstena sa sirćetnom kiselinom. Za modelovanje reakcije formiranja persirćetne kiseline na površini katalizatora primenjeni su Langmuir-Hinshelwood- Hougen-Watson i Rideal-Eley postulati. Postavljeni trofazni model predstavlja sistem običnih diferencijalnih jednačina prvog reda koji opisuje promenu broja molova komponenata i funkcionalnih grupa sa vremenom izvođenja procesa epoksidovanja, i sadrži više parametara razvrstanih na kinetičke, termodinamičke i parametre koji se odnose na prenos mase. Parametri modela zavise od uslova izvođenja epoksidovanja i to svi od temperature, a neki i od sastava i inteziteta mešanja. Za konstantu hemijske ravnoteže reakcije nastajanja persirćetne kiseline je izvedena semiteorijska zavisnost od temperature koja daje vrednosti istog reda veličine i istog smera promene sa temperaturom kao i većina podataka objavljenih u literaturi. Za izračunavanje koeficijenta raspodele sirćetne kiseline između uljne i vodene faze potrebno je odrediti zavisnost konstante fazne ravnoteže tečno-tečno sirćetne kiseline od sastava i temperature. Utvrđeno je da je UNIFAC model grupnih doprinosa za koeficijente aktivnosti nepogodan za predskazivanje ravnoteže tečno-tečno. Eksperimentalni podaci za ovu konstantu ravnoteže su uspešno korelisani UNIQUAC modelom za koeficijente aktivnosti. Parametri reparametrizovane Arrheniusove zavisnosti konstanti brzina reakcija i konstanti sorpcije učesnika reakcije stvaranja persirćetne kiseline od temperature određeni su simultano sa parametrima koji se odnose na prenos mase i sa odnosom koeficijenata raspodele persirćetne i sirćetne kiseline između uljne i vodene faze, fitovanjem eksperimentalnih podataka epoksidovanja sojinog ulja, tj. minimizacijom sume kvadrata odstupanja računskih od eksperimentalno određenih vrednosti jodnog broja i sadržaja epoksi kiseonika tokom epoksidovanja. Fitovanje je uspešno izvedeno primenom metode Marquardta, dok su pomenute računske vrednosti dobijene numeričkom integracijom sistema diferencijalnih jednačina modela primenom Runge-Kutta metode IV reda.sr
dc.description.abstractThe objective of this doctoral thesis was development of mathematical model for complex three-phase reaction system for soybean oil epoxidation with peracetic acid formed in situ from acetic acid and hydrogen peroxide in a presence of an ion exchange resin as catalyst. The local concentrations of components in water and oil phases were introduced into the model. In addition to reactions of the peracetic acid and epoxy compound formation, model considers the side reaction of epoxy ring cleavage with acetic acid. Approximate modeling of peracetic acid formation was based on Langmuir-Hinshelwood-Hougen- Watson and Rideal-Eley postulates. Established threephase model is a system of ordinary first order differential equations which describes change of components and functional groups amounts with reaction time. Besides kinetic parameters, model comprises the thermodynamic ones as well as parameters of mass transfer between the oil and water phase. All model parameters are dependent on temperature and some additionally on composition and intensity of stirring. A semitheoretical temperature dependency of chemical equilibrium constant for peracetic acid formation was established. The order of magnitude and temperature trend of the calculated chemical equilibrium constant are in agreement with the most data given in a literature. For calculation of partition coefficient for acetic acid between oil and water phase, temperature and composition dependency of liquid-liquid equilibrium constant for acetic acid is necessary. It was found that UNIFAC model of group contribution was non-applicable for the prediction of the equilibrium constant. The experimental data for the equilibrium constant were, however, successfully fitted by UNIQUAC model. Temperature dependencies of the reaction rate constants and sorption constants of reactants and products in peracetic acid formation reaction are expressed by reparameterized Arrhenius equation. The parameters of such equation were determined simultaneously with mass transfer parameters and ratio of peracetic acid and acetic acid partition coefficients between oil and water phase by fitting the experimental data i.e. by minimization of least sum of squares of deviation between the calculated and experimentally determined iodine value and epoxy oxygen content . Marquardt method was successfully used to fit the experimental data. A fourth-ordered Runge-Kutta method was applied for integrating the system of differential equations of the model.en
dc.formatapplication/pdf
dc.languagesr (latin script)
dc.publisherУниверзитет у Новом Саду, Технолошки факултетsr
dc.rightsopenAccessen
dc.sourceУниверзитет у Новом Садуsr
dc.subjectMatematički modelsr
dc.subjectMathematical modelen
dc.subjectepoxidationen
dc.subjectsoybean oilen
dc.subjectperaceticaciden
dc.subjectliquid-liquid equilibriaen
dc.subjectepoksidovanjesr
dc.subjectsojino uljesr
dc.subjectpersirćetna kiselinasr
dc.subjectravnoteža tečno-tečnosr
dc.titleMatematički model reakcionog sistema za in situ epoksidovanje sojinog ulja persirćetnom kiselinomsr
dc.title.alternativeMathematical model of reaction sistem for in situepoxidation of soybean oil with peracetic aciden
dc.typedoctoralThesissr
dc.rights.licenseBY-NC-ND
dc.identifier.fulltexthttp://nardus.mpn.gov.rs/bitstream/id/39954/IzvestajKomisije.pdf
dc.identifier.fulltexthttp://nardus.mpn.gov.rs/bitstream/id/39953/Disertacija.pdf


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