Energy & Fuels, Vol.30, No.7, 5617-5629, 2016
Kinetic Study of Preoxidized Asphaltene Hydroprocessing in Aqueous Phase
The solubilized asphaltene in water (SAW) was prepared by low-temperature oxidation in aqueous phase and used as a feedstock of hydroprocessing reaction. Hydroprocessing experiments were carried out in a 100 mL batch reactor within the temperature range of 280-320 degrees C in the presence of presulfided NiMo/gamma-Al2O3 catalyst. A lumped kinetic model with four components including water-soluble fractions, water-insoluble fractions, liquid hydrocarbons, and gas products was proposed, which accurately predicted the experimental results. The activation energy of global reaction was calculated to be 83 kJ/mol. At 320 degrees C, the liquid hydrocarbons yield increased around 8% by prolonging the residence time from 1 to 6 h. For 3 h residence time, by increasing the reaction temperature from 280 to 320 degrees C, the liquid yield was increased 5% and the conversion was enhanced by 8%. Increasing the reaction temperature affected the quality of products; that is, liquid hydrocarbons with lower boiling point distribution were obtained at higher reaction temperatures. At 320 degrees C, phenol derivative products disappeared, indicating the progress of deoxygenation at higher reaction temperatures. Fourier transform infrared analyses confirmed that disappearance of carboxylate functional groups through decarboxylation or protonation was the main reason for the production of water-insoluble fractions after the hydroprocessing. An extended Henry's law with gamma-phi approach was implemented to predict the thermodynamics status of the system at reaction conditions. The occurrence of reaction in the liquid phase was confirmed, where at 320 degrees C more than 80 wt % of water remained in the liquid phase and the liquid level in the reactor increased 25%.