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Troter, Dragan Z. 1987-
Primena eutektičkih rastvarača sa holin hloridom u heterogeno katalizovanoj etanolizi suncokretovog ulja
Autorstvo-Nekomercijalno-Bez prerade 3.0 Srbija (CC BY-NC-ND 3.0)
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Academic metadata
Doktorska disertacija
Tehničko-tehnološke nauke
Univerzitet u Nišu
Tehnološki fakultet
Katedra za hemijsko-inženjerske nauke
Other Theses Metadata
Application of choline chloride-based deep eutectic solvents in the heterogeneously catalyzed ethanolysis of sunflower oil
[D. Z. Troter]
[13], 131 list
Biografija autora: list 127;
Bibliografija: listovi 89-109.
Datum odbrane: 14.02.2019.
Chemistry and Chemical Technologies
Todorović, Zoran B. 1958- (mentor)
Veljković, Vlada B. 1953- (član komisije)
Miladinović, Marija R. (član komisije)
Zdujić, Miodrag V. (član komisije)
In this doctoral dissertation the synthesis of fatty acid ethyl esters (FAEEs) from triacylglycerols’ derived from the expired sunflower oil was analyzed via chemically-catalyzed ethanolysis reaction. The ethanolysis was performed as a heterogeneous alkaline catalyzed reaction in which the catalyst was CaO (calcined and non-calcined) in the presence of different choline chloride (ChCl)-based deep eutectic solvents, namely ChCl:urea (ChCl:U), ChCl:1,3-dimethylurea (ChCl:DMU), ChCl:thiourea (ChCl:TU), ChCl:propylene glycol (ChCl:PG), ChCl:ethylene glycol (ChCl:EG) and ChCl:glycerol (ChCl:G) in ChCl:hydrogen bond donor molar ratio 1:2. The physical (density, dynamic viscosity, electrical conductivity and refractive index) and the thermodynamic (thermal expansion coefficient, molecular volume, lattice energy and heat capacity) properties of the prepared deep eutectic solvents were determined at atmospheric pressure over the temperature range of 293.15–363.15 K. These prepared deep eutectic solvents and their constituents were individually tested as cosolvents in the ethanolysis of expired sunflower oil catalyzed by either calcined or non-calcined CaO at temperature of 70 °C and ethanol-to-oil molar ratio of 12:1. All tested deep eutectic solvents promoted the ethanolysis by a successful activation of non-calcined CaO, which was attributed to the CaCO3 and Ca(OH)2 dissolution from the surface of the solid catalyst particles. Either with calcined or non-calcined CaO, the polyol-based deep eutectic solvents gave higher FAEEs’ content than the amide-based deep eutectic solvents. ChCl:EG and ChCl:PG were more efficient than ChCl:G even with non-calcined CaO. However, ChCl:G is more suitable since glycerol, as a by-product of the ethanolysis, can be used for preparation of this deep eutectic solvent, so the overall FAEE production costs could be reduced. The phase separation of the reaction mixture was faster in the presence of the deep eutectic solvents. After five reuses, non-calcined CaO activated by ChCl:U, ChCl:EG, ChCl:PG or ChCl:G yielded the FAEE content of 85.5±1.5%, 86.2±0.9%, 85.2±0.7% and 83.4±1.1%, respectively after 2 h.
Deep eutectic solvents, choline chloride, amides, polyols, physical properties, thermodynamic properties, cosolvents, calcium oxide, ethanolysis, batch process
66.061.18:66.097]:665.347.8(043.3)
T350
Serbian
534066326
Tekst
In this doctoral dissertation the synthesis of fatty acid ethyl esters (FAEEs) from triacylglycerols’ derived from the expired sunflower oil was analyzed via chemically-catalyzed ethanolysis reaction. The ethanolysis was performed as a heterogeneous alkaline catalyzed reaction in which the catalyst was CaO (calcined and non-calcined) in the presence of different choline chloride (ChCl)-based deep eutectic solvents, namely ChCl:urea (ChCl:U), ChCl:1,3-dimethylurea (ChCl:DMU), ChCl:thiourea (ChCl:TU), ChCl:propylene glycol (ChCl:PG), ChCl:ethylene glycol (ChCl:EG) and ChCl:glycerol (ChCl:G) in ChCl:hydrogen bond donor molar ratio 1:2. The physical (density, dynamic viscosity, electrical conductivity and refractive index) and the thermodynamic (thermal expansion coefficient, molecular volume, lattice energy and heat capacity) properties of the prepared deep eutectic solvents were determined at atmospheric pressure over the temperature range of 293.15–363.15 K. These prepared deep eutectic solvents and their constituents were individually tested as cosolvents in the ethanolysis of expired sunflower oil catalyzed by either calcined or non-calcined CaO at temperature of 70 °C and ethanol-to-oil molar ratio of 12:1. All tested deep eutectic solvents promoted the ethanolysis by a successful activation of non-calcined CaO, which was attributed to the CaCO3 and Ca(OH)2 dissolution from the surface of the solid catalyst particles. Either with calcined or non-calcined CaO, the polyol-based deep eutectic solvents gave higher FAEEs’ content than the amide-based deep eutectic solvents. ChCl:EG and ChCl:PG were more efficient than ChCl:G even with non-calcined CaO. However, ChCl:G is more suitable since glycerol, as a by-product of the ethanolysis, can be used for preparation of this deep eutectic solvent, so the overall FAEE production costs could be reduced. The phase separation of the reaction mixture was faster in the presence of the deep eutectic solvents. After five reuses, non-calcined CaO activated by ChCl:U, ChCl:EG, ChCl:PG or ChCl:G yielded the FAEE content of 85.5±1.5%, 86.2±0.9%, 85.2±0.7% and 83.4±1.1%, respectively after 2 h.