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Gotovo sve zemlje Europske unije, a i većina zemalja u tranziciji u posljednjem su desetljeću, a neke i ranije, pokrenule proizvodnju biogoriva i to biodizelskoga goriva i etanola. Na temelju pregleda brojnih rezultata istraživanja u svijetu, u ovom se radu analiziraju najvažnija svojstva biodizelskoga goriva, njegova dosadašnja primjena kao alternativnog goriva za dizel motore, te utjecaj njegova sagorijevanja na okoliš u odnosu na mineralno dizel gorivo. Kako je osnovna sirovina za proizvodnju biodizela iz obnovljivih resursa ulje uljane repice, detaljno se analizira postojeća struktura sjetve i udio uljane repice na obradivim površinama u Hrvatskoj, te realne mogućnosti proizvodnje ove kulture za neprehrambeni lanac, odnosno mogućnosti proizvodnje biodizela u Hrvatskoj., Practically all the countries in the European Union and most of the transition countries have in the last decade, and some even earlier than that, started off the production of biofuels, that is, of biodiesel fuel and ethanol. On the basis of a survey of numerous results of investigations in the world, in this work the most important properties of biodiesel fuel are reviewed, its employment to date as alternative fuel for diesel engines, and the environmental impact of its combustion as compared with that of mineral diesel fuel. Since the basic raw material for the production of biodiesel from renewable resources is the oil of oilseed rape, a detailed analysis is given of the existing structure of the crop and the percentage of the cultivable land in Croatia given over to oilseed rape, as well as the realistic opportunities for the production of this crop for the non-food chain, in other words, the opportunity for the production of biodiesel in Croatia.

In addition to being used in food, fuel and lubricants, vegetable oils are promising in many other applications such as food additives, nutritional supplements, cosmetics and biomedicine; however, their low oxidative stability can limit their use. Microencapsulation is a well-established method for the preservation of oil against degradation, controlled release of active ingredients, protection against external factors during storage, and enhanced durability. In this article, microencapsulation methods for vegetable oil are reviewed, including physical methods (spray-drying and freeze-drying), physicochemical methods (complex coacervation, ionic gelation and electrostatic layer-by-layer deposition), and chemical methods (interfacial/in situ polymerization). This article also provides information on the principles, parameters, advantages, disadvantages and applications of these methods., Biljna ulja se osim u prehrani te kao goriva i maziva, mogu koristiti kao dodaci hrani, nutraceutici, u proizvodnji kozmetike i biomedicini, no primjena im je ograničena zbog slabe oksidacijske stabilnosti. Mikroinkapsulacija je uobičajena metoda zaštite ulja od razgradnje i vanjskih čimbenika tijekom skladištenja, kojom se kontrolira otpuštanje aktivnih sastojaka i produljuje trajnost ulja. U ovom je radu dan kratki pregled metoda mikroinkapsulacije biljnih ulja, uključujući fizikalne (sušenje raspršivanjem i zamrzavanjem), fizikalno-kemijske (kompleksna koacervacija, ionsko geliranje i slojeviti elektrostatski premazi) i kemijske (međufazna i in situ polimerizacija) postupke. Osim toga, ovaj rad donosi informacije o principima, parametrima, prednostima i nedostacima, te mogućim primjenama ovih metoda.

U ovom istraživanju određivana je oksidacijska stabilnost mješavine hladno prešanog lješnjakovog ulja i lanenog ulja u omjeru 50 : 50 sa i bez dodataka prirodnih i sintetskih antioksidanasa te sinergista. Primjenom standardnih metoda, određeni su parametri kvalitete ulja (peroksidni broj, slobodne masne kiseline). Antioksidansi koji su korišteni u ovom radu su ekstrakti nara, ružmarina i kadulje, eterično ulje konopljike, lavande, slatkog pelina, divlje mrkve, smilja, propil galat i mješavina tokoferola te sinergist limunska kiselina. Oksidacijska stabilnost ulja ispitivana je primjenom Oven testa. Rezultati ispitivanja prikazani su vrijednostima peroksidog broja tijekom 4 dana trajanja testa. Primjena ekstrakta ružmarina pokazala je bolju zaštitu mješavine ulja od oksidacije u odnosu na ekstrakt kadulje i nara. Dodatkom eteričnog ulja smilja i lavande postignuta je veća zaštita mješavine hladno prešanog lješnjakovog ulja i lanenog ulja prema oksidacijskom kvarenju. Dodatkom sinergista limunske kiseline, prirodnom antioksidansu ekstraktu ružmarina ostvarena je najveća zaštita mješavine ulja od oksidacijskog kvarenja. In this research was determined oxidation stability of mixture consisted of cold-pressed oil of hazelnut and linseed oil in ratio 50 : 50, with and without natural and synthetic antioxidants and synergists. Using standard methods it was defined oil quality parameter (peroxide number, free fatty acids). Antioxidants that were used in this research are: pomegranate extract, rosmary and sage extract, essential oils of hemp, lavander, sweet wormwood, wild carrot, immortelle, propyl galate, tocopherol mix and syinergistic citric acid. Oil oxidation stability was tested using Oven test. The results of testing are shown in peroxide number value during the 4 days of testing. Use of rosmary extract showed better protection of oil mixture from oxidation in comparison with pomegranate and sage extract. By adding essential oil of immortelle and lavander it was achieved greater protection of mixture consisted of cold-pressed oil of hazelnut and linseed to oxidation degradation. With the addition of synergistic citric acid to natural antioxidant rosemary extract, has been proven the highest protection against oil oxidation.

Cilj: Utvrditi razliku u antioksidativnoj aktivnosti maslinovog, suncokretovog, bučinog i crnog ulja i njihovih tokoferolnih ekstrakata te proučiti kinetiku i mehanizam reakcije između slobodnih radikala i antioksidansa. Materijali i metode: Antioksidativna aktivnost ulja i tokoferolnih ekstrakata mjerena je spektrofotometrijski uz uporabu DPPH˙ (2,2-difenil-1-pikril-hidrazil), dok je Trolox ekvivalent poslužio kao referentni standard za kvantifikaciju rezultata dobivenih DPPH˙ testom. Pomoću kinetičkih monofaznih i bifaznih matematičkih modela procijenjena je i analizirana inhibicija signala DPPH˙. Rezultati: Vrijednost TEAC-a ukazuje da maslinovo i suncokretovo ulje (2,16 mmol/L) posjeduju jaču antioksidativnu aktivnost u odnosu na crno (1,85 mmol/L) i bučino ulje (1,68 mmol/L), a ujedno i intenzivniju inhibiciju DPPH˙ radikala. Tokoferolni ekstrakti imaju puno slabiji antioksidativni učinak od analiziranih biljnih ulja, pri čemu je najdjelotvorniji ekstrakt suncokretova ulja koji čini 22,1 % antioksidativne aktivnosti ulja, a najslabiji ekstrakt bučina ulja sa samo 13,9 %. Nestanak DPPH˙ radikala u uzorcima ulja odvija se u dva susljedna koraka, početnog eksponencijalnog koji se odvija unutar 7 min reakcije, ovisno o vrsti ulja, i drugog sporog, gdje su promjene proporcionalne s vremenom. Kod tokoferolnih ekstrakata brzi korak reakcije nije uočen, ukazujući time da se reakcija odvija mehanizmom kinetike prvog reda. Zaključak: Rezultati ukazuju da biljna ulja imaju jači učinak u inhibiciji radikala u odnosu na tokoferolne ekstrakte, pa se njihovom pravilnom konzumacijom potpomaže organizmu u „borbi“ protiv slobodnih radikala. Zapravo, najvažniji dio antioksidacijskog sustava obrane organizma od slobodnih radikala čini sinergističko djelovanje antioksidansa, odnosno antioksidansi u sinergiji imaju jači učinak nego sumarni učinak svih pojedinačnih antioksidansa., Aim: To determine the difference in the antioxidant activity of the olive, sunflower, pumpkin and black oil and their tocopherol extracts as well as to examine the kinetics and mechanism of reactions between free radicals and antioxidants. Materials and Methods: Antioxidant activity of the oils and tocopherol extracts was measured spectrophotometrically using DPPH˙ (2,2-diphenyl-1-picrylhydrazil) while Trolox equivalent was used as a reference standard for the quantification of the results obtained by the DPPH˙ test. DPPH˙ signal inhibition was evaluated and analyzed by monophasic and biphasic kinetics mathematical models. Results: The TEAC values suggest that olive and sunflower oil (2.16 mmol/L) have a stronger antioxidant activity than black (1.85 mmol/L) and pumpkin oil (1.68 mmol/L) and they possess stronger inhibition of the DPPH˙ radical. Tocopherol extracts have a much weaker antioxidant effect than the analyzed vegetable oils, where the sunflower extract is most effective, making 22.1 % of the antioxidant oil activity, while the weakest extract is the pumpkin oil extract oil with only 13.9 %. DPPH˙ radical disappearance in oil samples takes place in two successive phases, the initial exponential which takes place within 7 min of the reaction, depending on the oil type, and the second slow phase where the changes are proportional to the time. The rapid reaction phase by tocopherol extracts was not noticed, indicating that the reaction takes places by the mechanism of the first order kinetics. Conclusion: The results indicate that vegetable oils have a stronger effect on the radical inhibition than the tocopherol extracts, and by their proper consumption they will support the organism in the “fight” against free radicals. In addition, the most important role of the antioxidant defense system against free radicals makes the synergic interactions among the different molecules present in the food, indicating that antioxidants in synergy have a stronger potential than the sum of all individual antioxidants.

Hemijskim transformacijama se iz biljnih ulja dobijaju vredni derivati, poput epoksidovanih biljnih ulja, koji sekoriste u hemijskoj i polimernoj industriji. Kvalitet, patime i primena epoksidovanih biljnih ulja, zavise odsadržaja epoksidnih grupa u derivatizovanom ulju, koji bitrebalo da je što veći. Kako epoksidne grupe nastajuoksidacijom dvostrukih veza u trigliceridima kaodominantnoj grupi jedinjenja u biljnim uljima, pogodnasirovina za epoksidovanje su visoko nezasićena ulja,kakvo je laneno.Proizvodnja epoksidovanih biljnih ulja zahteva izbortakvih procesnih uslova pri kojima bi se postigli štopotpunija konverzija dvostrukih veza i što većaselektivnost procesa u odnosu na epoksidnu grupu. Zato jekao cilj ove doktorske disertacije postavljeno određivanjeoptimalnih vrednosti procesnih uslova epoksidovanjalanenog ulja persirćetnom kiselinom formiranom in situ izsirćetne kiseline i 30% vodenog rastvora vodonikperoksida u prisustvu jonoizmenjivačke smole kaokatalizatora. Određivanje je izvedeno primenommetodologije odzivne površine, kao i korišćenjem u ovojdisertaciji predloženih kinetičkih modela ispitivanogreakcionog sistema, u oba slučaja sa maksimumomrelativnog prinosa epoksida kao funkcijom cilja.Ispitivanje uticaja procesnih uslova, i to temperature,molskog odnosa reaktanata, količine katalizatora i brzinemešanja, na tok procesa epoksidovanja je bilo osnov zadefinisanje graničnih vrednosti procesnih uslova unutarkojih je tražen maksimum prinosa epoksida. Oblast dugihvremena reagovanja, koja nije od interesa za industriju, jeizbegnuta adekvatnim izborom temperature.Pri optimalnim vrednostima procesnih uslovaepoksidovanja lanenog ulja, određenim primenommetodologije odzivne površine, postignuto je dobroslaganje očekivane i eksperimentalno određene vrednostimaksimalnog relativnog prinosa epoksida, sa odstupanjemod 3,28%.Za potrebe određivanja optimalnih uslova izvođenjaprocesa epoksidovanja biljnih ulja korišćenjem kinetičkihmodela, razvijena su tri pseudohomogena modelaispitivanog trofaznog multireakcionog sistema. Poredkinetike osnovnih reakcija formiranja persirćetne kiseline i reakcije epoksidovanja dvostrukih veza triglicerida biljnog ulja, kao i kinetike sporedne reakcije otvaranja epoksidnegrupe sa sirćetnom kiselinom, u predloženim modelima jeuzeta u obzir i raspodela sirćetne i persirćetne kiselineizmeđu uljne i vodene faze sistema. Opisan je i uticajmasno-kiselinskog sastava ulja, odnosno broja dvostrukihveza u masno-kiselinskim lancima triglicerida, na kinetikureakcija. Za koeficijent raspodele sirćetne kiseline izmeđutečnih faza reakcionog sistema predložena je empirijskakorelacija koja je dala dobro slaganje izračunatihvrednosti sa eksperimentalnim podacima. Kinetičkiparametri modela su određeni fitovanjemeksperimentalnih podataka o promenama količinadvostruke veze i epoksidne grupe sa vremenom izvođenjaprocesa epoksidovanja. Na osnovu statističkih pokazateljauspešnosti fitovanja eksperimentalnih podataka, potvrđenaje prepostavka da je pseudohomogeni model publikovan uliteraturi unapređen uzimanjem u obzir pomenutihfenomena raspodele komponenata reakcione smeše imasno-kiselinskog sastava sirovine pri modelovanjureakcionog sistema epoksidovanja biljnih uljapersirćetnom kiselinom.Korišćenjem predloženih pseudohomogenih modelareakcionog sistema za određivanje optimalnih uslovaizvođenja procesa epoksidovanja lanenog ulja in situformiranom persirćetnom kiselinom u prisustvujonoizmenjivačke smole, dobijeno je odstupanje od 5,51%očekivane od eksperimentalno određene vrednostirelativnog prinosa epoksida.Bolje slaganje predviđene sa eksperimentalno određenomvrednošću relativnog prinosa epoksida u kontrolnomeksperimentu je dobijeno primenom metodologije odzivnepovršine u poređenju sa korišćenjem kinetičkih modela priodređivanju optimalnih vrednosti procesnih uslova. To je iočekivano, s obzirom da regresiona jednačina korišćena uokviru metodologije odzivne površine bolje fituje relativniprinos epoksida. Standardna devijacija relativnog prinosepoksida za regresionu jednačinu je 8,9 puta niža od oneizračunate za kinetički model koji najbolje predviđaoptimalne procesne uslove epoksidovanja lanenog uljapersirćetnom kiselinom., Vegetable oils can be transformed into added valueproducts by various chemical modifications, such asepoxidation. The epoxidized vegetable oils have awide range of applications in the chemical andpolymer industry. The quality, and consequently theapplication, of epoxidized vegetable oil is influencedby the epoxy group content. Since the epoxy groupsare formed by the oxidation of double bonds intriglycerides, the main constituent of vegetable oils,highly unsaturated vegetable oils, such as linseedoil, are desirable raw materials.The manufacturing of epoxidized vegetable oilsrequires the optimization of the process conditionsin order to achieve complete conversion of doublebonds and high selectivity of the process in respectto the epoxy groups. Therefore, the aim of thisdoctoral thesis is to determine the optimal processconditions for the epoxidation of linseed oil withperacetic acid, formed in situ from acetic acid and30% hydrogen peroxide in the presence of an ionexchange resin as the catalyst. The optimal processconditions were determined by response surfacemethodology, as well as by using developed pseudohomogeneouskinetic models that describe theinvestigated reaction system. For both optimizationmethods, the relative epoxy yield was selected as anobjective function to be maximized.The effects of process conditions, such astemperature, molar ratio of reactants, catalystamount and steering speed, on the kinetics of theepoxidation were studied in order to defineconstraints for the optimization. To avoid longreaction times, which are not of interest inmanufacturing, an adequate temperature range wasselected. Under the optimized process conditions for theepoxidation of linseed oil, which were determinedby response surface methodology, good agreementbetween the calculated and experimentallydetermined relative epoxy yields was achievedwithin 3.28%.Three models describing the three-phase multireactionsystem of vegetable oil epoxidation withperacetic acid were developed and further used forthe optimization. The models are pseudohomogeneouswith respect to the catalyst. Besidesthe kinetics of the main reactions of peracetic acidand epoxy group formation, the models take intoaccount the side reaction of the epoxy group openingwith acetic acid. The partitioning of the acetic acidand peracetic acid between the oil and aqueousphases is considered. In two proposed models, theeffect of fatty acid composition on the kinetics of theprocess is also described by considering the numberof double bonds in the fatty acid chains. Thedeveloped empirical correlation for the partitioncoefficient for acetic acid between the liquid phasesshows good agreement between the calculated andexperimental data. The kinetic parameters of theproposed pseudo-homogeneous models weredetermined by fitting the experimentally determinedchanges of the double bond and epoxy groupamounts with reaction time of the epoxidation.Statistical values of the models` parametersdetermination confirmed the hypothesis that thepseudo-homogeneous model proposed in theliterature can be improved by considering thepartitioning phenomena and the effect of the oil fattyacid composition on the kinetics of the vegetableoils epoxidation with peracetic acid.Under the optimized process conditions for theepoxidation of linseed oil with peracetic acid formedin situ in the presence of the ion exchange resin,which were determined by using proposed pseudohomogeneousmodels, the experimentallydetermined relative epoxy yield was 5.51% lowerthan the calculated.Better agreement between the calculated andexperimentally determined values for the relativeepoxy yield, achieved under the optimal processconditions, is obtained when the response surfacemethodology (RSM) was applied as opposed towhen the kinetic models were used for thedetermination of the optimal process conditions.This is in accordance with better fitting of therelative epoxy yield by RSM regression equationthan by kinetics models. Standard deviation of therelative epoxy yield for RSM regression equation is 8.9 times lower than the standard deviation for themost successful kinetic model used for prediction ofthe optimal process conditions for the epoxidation ofthe linseed oil by peracetic acid.