Effect of Nanoparticles on the Thermal Characterization and Kinetics of Crude Oils

Date

2024-7-11

Author

Diken, Bahar Pınar

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In this thesis, the thermal characteristics, model-free kinetics of various crude oil samples, and nanoparticle effects were experimentally studied under laboratory conditions. The oil samples, each massing 10 mg, were added with copper nanoparticles at concentrations of 10%, 20%, and 30% by mass. Also, some oil samples were mixed with crushed limestone by mass to simulate the reservoir media. In these experiments, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were utilized at five different heating rates (5, 10, 15, 20, and 25°C/min) under atmospheric conditions to determine the reaction regions, corresponding peak temperatures, mass loss, and residue of the crude oil samples both with and without copper nanoparticles. The same gas flow rate (80 ml/min for the balance purge gas and 120 ml/min for the sample purge gas) was used during all the experiments. The TGA and DSC experiments continued up to 850 °C and 600 °C, respectively. In all samples, two distinct reaction regions were observed in the curves due to the oxidative degradation of crude oil components. Initially, the evaporation of free moisture and volatile hydrocarbons, combustion of light hydrocarbons, and fuel formation occurred in the first reaction region. Subsequently, the primary combustion took place in the second region, where the fuel was burned. The mass loss in the reaction regions was determined from the TGA curves, while the heat flow to the samples in these regions was analyzed from the DSC curves. As the heating rate increased, the peak temperatures shifted to right, and reaction regions became broader. Furthermore, an increase in the percentage of copper nanoparticles led to narrower reaction intervals and reduced peak temperature values. The results obtained from the TGA were consistent with those from the DSC. In the thesis, model-free kinetics, particularly the KAS (Kissinger-Akahira-Sunose) and OFW (Ozawa-Flynn-Wall) methods, were utilized to determine the activation energy of the studied samples. The introduction of copper nanoparticles into crude oil samples leads to a reduction in activation energy. For example, the mean activation energy of Crude Oil 1 equals 207.90 kJ/mol. In comparison, the mean activation energy of the mixture of Crude Oil 1 and 10% copper nanoparticles by mass equals 59.11 kJ/mol. Nonetheless, when the proportion of copper nanoparticles is increased, the activation energy values also rise. For example, the mean activation energy of the mixture of Crude Oil 1 and 10% copper nanoparticles by mass equals 59.11 kJ/mol. In comparison, the mean activation energy of the mixture of Crude Oil 1 and 20% copper nanoparticles by mass equals 102.03 kJ/mol. Moreover, incorporating of limestone into one oil sample results in a decrease in activation energy, whereas its addition to a different oil sample causes an increase in activation energy. For example, the mean activation energy of Crude Oil 1 equals 207.90 kJ/mol. In comparison, the mean activation energy of the mixture of Crude Oil 1 and crushed limestone equals 222.28 kJ/mol.

Subject Keywords

Thermogravimetry, Differential scanning calorimetry, Combustion, Nanoparticles, Kinetic analysis

URI

https://hdl.handle.net/11511/110454

Collections

Graduate School of Natural and Applied Sciences, Thesis