Low-temperature oxidation reactions of crude oils using TGA-DSC techniques

Kök, Mustafa Verşan
Varfolomeev, Mikhail A.
Nurgaliev, Danis K.
In this research, combustion behaviour of three crude oils with different degrees API gravities was analysed. The thermogravimetric analyser (TGA) and differential scanning calorimeter (DSC) experiments were performed using three different heating rates (2, 5, and 10 degrees C min(-1)) under air atmosphere. The reaction regions, burn-out temperatures, and peak temperatures were determined accordingly. Two main reaction regions, particularly the low-temperature oxidation (LTO) and high-temperature oxidation (HTO) reactions, were figured out in TGA and DSC curves, which suggested exothermic behaviour. Kinetic parameters of the crude oils were determined using model free methods (Ozawa-Flynn-Wall, OFW, and Kissinger-Akahira-Sunose, KAS), which allows the calculation of kinetic properties at progressive conversion degrees without the requirement of any reaction models and f(alpha) estimations. The variation in activation energy with respect to the conversion degree pointed out that the LTO reaction stage can be subdivided into three subzones. The results indicated that the activation energies were changing depending on the conversion degree, which is an indication of complex reaction mechanisms. The change in activation energy with respect to conversion degree showed slight variation for heavy crude oil compared with that in light crude oil.