Adsorption and Subsequent Oxidation of Colombian Asphaltenes onto Nickel and/or Palladium Oxide Supported on Fumed Silica Nanoparticles

• Published in: Energy & fuels 2013-12, Vol.27 (12), p.7336-7347
• Main Authors: Franco, Camilo A, Montoya, Tatiana, Nassar, Nashaat N, Pereira-Almao, Pedro, Cortés, Farid B
• Format: Article
• Language: English
• Subjects: Adsorption; Asphaltenes; Catalysts; Fumed silica; Nanoparticles; Palladium; Sorption; Surface chemistry
• ISSN: 0887-0624; 1520-5029
• DOI: 10.1021/ef4018543

High asphaltene content in heavy crude oil normally generates adverse rheological properties that affect the flow through the reservoir, preventing optimal hydrocarbon production. It has been demonstrated that using nanoparticles may improve the mobility of oil. Nanoparticles may be used as adsorbents and catalysts in the oil industry for in situ upgrading. The main objective of this study was to investigate the sorption kinetics and the thermodynamic equilibrium for asphaltene sorption onto nickel and/or palladium oxides supported on fumed silica that was nanoparticulated at different times, temperatures, and concentrations. After adsorption, thermally cracked asphaltenes from Colombian crude oil were investigated using catalytic oxidation. The asphaltenes adsorbed onto the selected nanoparticles were subjected to thermal decomposition up to 700 °C in a thermogravimetric analyzer. This study was realized using an experimental design with a measured simplex–centroid of the three components by varying the wt % of the palladium and nickel oxides as well as the fumed silica as the support. The silica nanoparticles were characterized using N2 adsorption at 196 °C and X-ray diffraction. The Langmuir and Freundlich models were used to correlate the experimental sorption equilibrium data. The experimental asphaltene adsorption isotherm data were adequately adjusted using the Freundlich model. The adsorption of asphaltenes on NiO and/or PdO supported on fumed silica was much higher than that over fumed silica over the range of the tested equilibrium concentrations. Pseudo-first- and pseudo-second-order kinetic models were applied to the experimental data obtained at different asphaltene concentrations from 100 to 1500 mg/L for the virgin fumed silica (S) and fumed silica-supported materials (SHSs); better fits were found for the pseudo-second-order model. However, the nanoparticles significantly decreased the asphaltene decomposition temperature and activation energy. The catalyst kinetics was calculated using the Ozawa–Flynn–Wall Model (OFW). All of the nanoparticles demonstrated high catalytic activity toward asphaltene decomposition in the following order at 0.2 mg/m2 asphaltene concentration on nanoparticle surfaces: SNi1 < SNi1Pd1< SNi0.66Pd0.66 < SPd1 < SPd2 < SNi2 < S. Consequently, using nanoparticles significantly enhanced the thermal decomposition of asphaltenes, improving the mobility of heavy oils in situ.