Extractive catalytic oxidative desulfurization (ECODS) is the one of the recent methods used in fuel desulfurization which involved the use of catalyst in the oxidative desulfurization of diesel fuel. This study is aimed to test the effectiveness of synthesized choline chloride (ChCl) based deep eutectic solvent (DES) in fuel desulfurization via ECODS method, with the presence of graphene oxide (GO) as catalyst and hydrogen peroxide (H2O2) as oxidant. In this study, 16 DESs based on choline chloride were synthesized using glycerol (GLY), ethylene glycol (EG), tetraethylene glycol (TEG) and polyethylene glycol (PEG). The characterization of the synthesized DES was carried out via Fourier transform infrared spectroscopy (FTIR) analysis, density, and viscosity determination. According to the screening result, ChCl-PEG (1:4) was found to be the most effective DES for desulfurization using ECODS method, with a removal of up to 47.4% of sulfur containing compounds in model oil in just 10 min per cycle after the optimization of the reaction parameters, and up to 95% desulfurization efficiency could be achieved by six cycles of desulfurization. It is found that the addition of GO as catalyst does not increase the desulfurization performance drastically; hence, future studies for the desulfurization performance of DESs made up from ChCl and PEG and its derivatives can be done simply by using extraction desulfurization (EDS) method instead of ECODS method, for cost reduction purpose and easier regulation of DES waste into environment.
The biggest challenge faced in oil refineries is the removal of sulfur compounds in fuel oil. The sulfur compounds which are found in fuel oil such as gasoline and diesel, react with oxygen in the atmosphere to produce sulfur oxide (SOx) gases when combusted. These sulfur compounds produced from the reaction with oxygen in the atmosphere may result in various health problems and environmental effects. Hydrodesulfurization (HDS) is the conventional process used to remove sulfur compounds from fuel oil. However, the high operating conditions required for this process and its inefficiency in removing the organosulfur compounds turn to be the major drawbacks of this system. Researchers have also studied several alternatives to remove sulfur from fuel oil. The use of ionic liquids (ILs) has also drawn the interest of researchers to incorporate them in the desulfurization process. The environmental effects resulting from the use of these ILs can be eliminated using eutectic-based ionic liquids (EILs), which are known as greener solvents. In this research, a combination of extractive desulfurization (EDS) and oxidative desulfurization (ODS) using a photocatalyst and EIL was studied. The photocatalyst used is a pre-reported catalyst, Cu-Fe/TiO2 and the EIL were synthesized by mixing choline chloride (ChCl) with organic acids. The acids used for the EILs were propionic acid (PA) and p-toluenesulfonic acid (TSA). The EILs synthesized were characterized using thermogravimetry analyser (TGA) differential scanning calorimetry (DSC) analysis to determine the physical properties of the EILs. Based on the TGA analysis, ChCl (1): PA (3) obtained the highest thermal stability whereas, as for the DSC analysis, all synthesized EILs have a lower melting point than its pure component. Further evaluation on the best EIL for the desulfurization process was carried out in a photo-reactor under UV light in the presence of Cu-Fe/TiO2 photocatalyst and hydrogen peroxide (H2O2). Once the oxidation and extraction process were completed, the oil phase of the mixture was analyzed using high performance liquid chromatography (HPLC) to measure the sulfur removal efficiency. In terms of the desulfurization efficiency, the EIL of ChCl (1): TSA (2) showed a removal efficiency of about 99.07%.
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