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.

Investigation of Asphaltene Adsorption onto Zeolite Beta Nanoparticles to Reduce Asphaltene Deposition in a Silica Sand Pack

“…This figure demonstrates that the adsorption of asphaltene increased widely at lower asphaltene concentrations and reached to constant value by increasing the asphaltene concentrations. This characteristic confirmed the monolayer adsorption of asphaltene onto nanoparticles [25]. Therefore the Langmuir adsorption equation was used to model the equilibrium asphaltene adsorption data.…”

“…Because it is lower than critical clustering concentration of asphaltene in toluene (≈2000 mg/L) [24]. Therefore, with selection of this concentration, the contribution of the asphaltene selfassociation to the adsorbed mass of the asphaltene was decreased [25]. Next, the prepared solutions were being shaken at 200 rpm until the equilibrium was achieved.…”

“…The Langmuir isotherm model was used to correlate the experimental equilibrium data of asphaltene adsorption onto zeolite beta nanoparticles [11,13,14,20,25]. The Langmuir model is presented as follows [27]:…”

Model molecules mimicking asphaltenes

“…Asphaltenes often concentrate the major part of the heteroatoms (Nitrogen, Oxygen and Sulfur) and metallic elements (Nickel, Vanadium) present in a crude oil. It is well established that asphaltenes contain both acid and basic functionalities since they have both total base and acid numbers (TBN and TAN) [66][67][68] . The basic components are mainly derivatives of pyridines and its benzologs 69,70 while carboxylic acid and phenolic functions has been indentified in asphaltenes 2 .…”

“…Reprinted with permission from Nordgård et al 28 . 66,67 . Therefore the asphaltene model compounds aims to represent only a fraction of asphaltenes which corresponds to acid molecules.…”