title: Asphaltene adsorption onto acidic/basic metal oxide nanoparticles toward in situ upgrading of reservoir oils by nanotechnology.
abstract: The effects of surface acidity and basicity of metal oxide nanoparticles on the thermodynamics of asphaltene adsorption were studied. Three different categories of metal oxides/salts with acidic (WO3 and NiO), amphoteric (Fe2O3 and ZrO2), and basic (MgO and CaCO3) surfaces were synthesized, and their textural, structural, and acid-base properties were characterized. Asphaltenes were extracted from a dead oil sample and characterized by X-ray powder diffraction and Fourier transform infrared spectroscopy. The acid and base numbers of the asphaltenes were measured. The nanoparticles were added to the asphaltene-toluene solutions, and the amount of adsorbed asphaltene was obtained through centrifugation followed by UV-vis spectroscopy of the supernatant liquid and temperature-programmed oxidation analysis of the precipitated solid. The concentrations of organic acid and base groups in the asphaltenes are 2.75 and 12.34 mg of KOH/g, respectively, indicating that the asphaltenes are more basic in nature. Isotherms of the asphaltene adsorption onto the six metal oxides/salts fit the Langmuir model closely. The asphaltene adsorption capacity of the nanoparticles is 1.23-3.67 mg/m(2) and decreases in the order of NiO > Fe2O3 > WO3 > MgO > CaCO3 > ZrO2, concomitant with the synergetic effects of acidity and the net charge of the surfaces. High-resolution transmission electron microscopy illustrates that the asphaltenes are spread out over the surfaces with no short-range/long-range order. The adsorption of the asphaltenes onto the six samples is exothermic and spontaneous with the Gibbs energy change of -27.80 to -28.79 kJ/mol at 25 °C. The absolute value of the enthalpy change of the adsorption is calculated to be within the range of 5-20 kJ/mol. Acid-base interaction and electrostatic attraction seem to be the dominant forces contributing to the adsorption of the asphaltenes onto the metal oxide/salt surfaces.
authors.affiliation: Catalysis and Nanostructured Materials Research Laboratory, School of Chemical Engineering, College of Engineering, University of Tehran , P.O. Box 11155/4563, Tehran, Iran.
authors.forename: Negahdar
authors.initials: N
authors.lastname: Hosseinpour
authors.forename: Abbas Ali
authors.initials: AA
authors.lastname: Khodadadi
authors.forename: Alireza
authors.initials: A
authors.lastname: Bahramian
authors.forename: Yadollah
authors.initials: Y
authors.lastname: Mortazavi