Catalytic Decomposition of n-C7 Asphaltenes Using Tungsten Oxides–Functionalized SiO2 Nanoparticles in Steam/Air Atmospheres

Abstract

A wide range of technologies are being developed to increase oil recovery, reserves, and perform in situ upgrading of heavy crude oils. In this study, supported tungsten oxide nanoparticles were synthesized, characterized, and evaluated for adsorption and catalytic performance during wet in situ combustion (6% of steam in the air, in volumetric fraction) of n-C7 asphaltenes. Silica nanoparticles of 30 nm in diameter were synthesized using a sol–gel methodology and functionalized with tungsten oxides, using three different concentrations and calcination temperatures: 1%, 3%, 5% (mass fraction), and 350 °C, 450 °C, and 650 °C, respectively. Equilibrium batch adsorption experiments were carried out at 25 ℃ with model solutions of n-C7 asphaltenes diluted in toluene at concentrations from 100 mg·L−1 to 2000 mg·L−1, and catalytic wet in situ combustion of adsorbed heavy fractions was carried out by thermogravimetric analysis coupled to FT-IR. The results showed improvements of asphaltenes decomposition by the action of the tungsten oxide nanoparticles due to the reduction in the decomposition temperature of the asphaltenes up to 120 °C in comparison with the system in the absence of WOX nanoparticles. Those synthesis parameters, such as temperature and impregnation dosage, play an important role in the adsorptive and catalytic activity of the materials, due to the different WOX–support interactions as were found through XPS. The mixture released during the catalyzed asphaltene decomposition in the wet air atmosphere reveals an increase in light hydrocarbons, methane, and hydrogen content. Hydrogen production was prioritized between 300 and 400 °C where, similarly, the reduction of CO, CH4, and the increase in CO2 content, associated with water–gas shift, and methane reforming reactions occur, respectively. The results show that these catalysts can be used either for in situ upgrading of crude oil, or any application where heavy fractions must be transformed.