Matematičko modelovanje višefaznih reakcionih procesa u proizvodnji obnovljivih i mineralnih dizel goriva
Mathematical modelling of myltiphase reaction of renewable and mineral diesel fuels
dc.contributor.advisor | Orlović, Aleksandar | |
dc.contributor.other | Glišić, Sandra | |
dc.contributor.other | Jovović, Aleksandar M. | |
dc.creator | Almagrbi, Abdualnaser Muftah | |
dc.date.accessioned | 2016-01-05T12:43:04Z | |
dc.date.available | 2016-01-05T12:43:04Z | |
dc.date.available | 2020-07-03T09:22:27Z | |
dc.date.issued | 2013-10-14 | |
dc.identifier.uri | http://eteze.bg.ac.rs/application/showtheses?thesesId=1211 | |
dc.identifier.uri | https://nardus.mpn.gov.rs/handle/123456789/2948 | |
dc.identifier.uri | https://fedorabg.bg.ac.rs/fedora/get/o:8125/bdef:Content/download | |
dc.identifier.uri | http://vbs.rs/scripts/cobiss?command=DISPLAY&base=70036&RID=45042959 | |
dc.description.abstract | Višefazni reakcioni procesi predstavljaju ključne stupnjeve u proizvodnji dizel goriva, obnovljivih i mineralnih. U savremenim rafinerijama proces hidrotritinga zauzima značajno mesto pri čemu se odvija u prisustvu čvrstog katalizatora. Glavni ciljevi procesa hidrotritinga u preradi nafte su uklanjanje sumpora, stabilizacija proizvoda i uklanjanje drugih neželjenih primesa. Hidrodesulfurizacija gasnog ulja se odvija u reaktoru sa nepokretnim slojem katalizatora uz prisustvo vodonika na povišenom pritisku (uobičajeno do 60 bar-a) i temperaturi (633 K). U ovoj disertaciji razvijen je deterministički matematički model reaktora za simulaciju procesa. Model čine diferencijalni bilansi toplote i hemijskih vrsta, kao i odgovarajuće kinetičke jednačine za reakcije desulfurizacije. Sistem diferencijalnih jednačina koje čine model je rešavan primenom programa napisanog u MATLAB-u. Višefazni reakcioni proces sinteze biodizela je modelovan i simuliran za nekatalitičku etanolizu i metanolizu triglicerida na povišenom pritisku i temperaturi. Raspodela faza i ravnoteža za sistem para – tečnost i para – tečnost – tečnost metanola i etanola sa trioleinom je ispitivana sa ciljem određivanja parametara koji omogućavaju visoku konverziju ulja. Simlacija ravnoteže faza korišćenjem RK-Aspen jednačine stanja u UniSim softveru pokazala je veoma dobro slaganje sa eksperimentalnim podacima. Rezultati simulacija ukazuju na važan uticaj na reakcioni mehanizam i na ukupnu kinetiku procesa u sub-kritičnoj oblasti (T < 270 ◦C na 200 bar-a) s obzirom da u početnoj fazi reakcije egzistiraju dve faze, što uzrokuje lošiji kontakt između reaktanata. U slučaju postojanja jedne reakcione faze (T > 270 ◦C na 200 bar-a) inicijalno visoka brzina reakcije je limitirana na visokim konverzijama zbog porasta stepena odigravanja povratne reakcije. Matematički model nekatalitičke sinteze biodizela je tretiran kao kompleksna uzastopno – paralelna povratna reakcija. Kinetički parametri su određeni primenom standardnih optimizacionih metoda i najbolji rezultati su dobijeni primenom metode genetičkog algoritma. Primena ove metode za određivanje kinetičkih parametara rezultovala je povešanom preciznošću predviđanja koncentracija važnih intermedijera, monoglicerida i diglicerida. Energije aktivacije u izrazima za kinetičke konstante dobijene primenom metode genetičkog algoritma su u veoma dobrom slaganju sa teoretskim vrednostima određenim metodom proračuna molekulskih orbitala. | sr |
dc.description.abstract | Multiphase reaction processes constitute key steps in manufacturing of diesel fuels, both renewable and mineral. In modern refineries there is a major role for the hydrotreating processes that operate under high pressure in the presence of a solid catalyst. The main role of hydrotreating within the petroleum refining is the removal of sulphur compounds, the stabilization of the product and the removal of other undesirable impurities. Hydrodesulphurization of gas oil takes place in a reactor with a fixed bed catalyst in the presence of hydrogen at elevated pressure (normally up to 60 bar) and temperature (633 K). In this thesis, a mathematical model of a deterministic type was developed and used to simulate the hydrotreating reactor operation. The model consists of differential balance equations of heat and chemical species, and the corresponding kinetic equations for the reactions of hydrodesulphurization of sulphur compounds. The system of differential equations that constitute the mathematical model was solved using the MATLAB software package. Multiphase reactions for biodiesel synthesis were modeled and simulated for non-catalytic methanolysis and ethanolysis of triglycerides under high pressure and at elevated temperature. The vapour–liquid or vapour–liquid–liquid equilibrium and phase distribution of methanol and ethanol with triolein were investigated in order to determine the range of pressure and temperature required for high oil conversion. Simulation of phase equilibrium using RK-Aspen EOS and UniSim software were found to correlate well with the experimental data. Simulation results show the important influence of the phase equilibrium on the reaction mechanism and overall kinetics under subcritical conditions (T < 270 ◦C at 200 bar) since the two liquid phases exist at the beginning of reaction, thereby limiting the contact between the reactants. In case of single reaction phase (T > 270 ◦C at 200 bar) the initially high reaction rate is limited at high conversion levels due to increasing extent of reversible reaction. Mathematical model of non-catalytic biodiesel synthesis was treated as complex parallel and consequtive reversible reaction. Kinetic parameters were estimated using standard optimization methods and the best results were obtained with Genetic Algorithm procedure. The application of this method resulted in kinetic parameters with improved accuracy in predicting concentrations of important reaction intermediates, i.e. diglycerides and monoglycerides. Activation energies of kinetic parameters obtained by the Genetic Algorithm method are in very agreement with theoretical values determined by molecular orbital calculations. | en |
dc.format | application/pdf | |
dc.language | en | |
dc.publisher | Универзитет у Београду, Технолошко-металуршки факултет | sr |
dc.rights | openAccess | en |
dc.rights.uri | https://creativecommons.org/licenses/by-nc-nd/4.0/ | |
dc.source | Универзитет у Београду | sr |
dc.subject | matematičko modelovanje | sr |
dc.subject | mathematical modeling | en |
dc.subject | multiphase reaction processes | en |
dc.subject | biodiesel | en |
dc.subject | renewable diesel | en |
dc.subject | diesel fuel | en |
dc.subject | hydrotreating | en |
dc.subject | višefazni reakcioni procesi | sr |
dc.subject | biodizel | sr |
dc.subject | obnovljivi dizel | sr |
dc.subject | dizel gorivo | sr |
dc.subject | hidrotriting | sr |
dc.title | Matematičko modelovanje višefaznih reakcionih procesa u proizvodnji obnovljivih i mineralnih dizel goriva | sr |
dc.title | Mathematical modelling of myltiphase reaction of renewable and mineral diesel fuels | en |
dc.type | doctoralThesis | en |
dc.rights.license | BY-NC-ND | |
dcterms.abstract | Орловић, Aлександар; Јововић, Aлександар М.; Глишић, Сандра; Aлмагрби, Aбдуалнасер Муфтах; Математичко моделовање вишефазних реакционих процеса у производњи обновљивих и минералних дизел горива; Математичко моделовање вишефазних реакционих процеса у производњи обновљивих и минералних дизел горива; | |
dc.identifier.fulltext | https://nardus.mpn.gov.rs/bitstream/id/17947/Disertacija.pdf | |
dc.identifier.fulltext | http://nardus.mpn.gov.rs/bitstream/id/17947/Disertacija.pdf | |
dc.identifier.rcub | https://hdl.handle.net/21.15107/rcub_nardus_2948 |