Effects of the N, O, and S heteroatoms on the adsorption and desorption of asphaltenes on silica surface: A molecular dynamics simulation

Abstract The adsorption and desorption of asphaltene on silica surface is highly dependent on the heteroatoms present in its structure. Herein, some model asphaltene molecules with different heteroatoms (i.e., N, O, S) at different positions (in the aromatic cores, in the middle and termination of alkane side chains) are selected as the adsorbates to investigate their adsorption and desorption behaviors on silica surface through molecular dynamics (MD) simulation. Results reveal that the characteristic adsorption configuration of asphaltenes is ascribed to the competition between the asphaltene-silica interaction and π–π stacking interaction among the asphaltene polyaromatic rings. The presence of heteroatoms is found to be able to strengthen the interactions between asphaltenes and silica, depending on their type and location. For example, the terminal polar groups, especially the carboxyl (COOH), exhibit the greatest contribution to the electrostatic interaction (increasing from −81 to −727 kJ/mol). The S atoms are also found to increase the van der Waals interaction energies by 25%. According to the equilibrium desorption conformation and density profile, the presence of heteroatoms is found to significantly hinder the desorption of asphaltenes from silica due to the enhanced polar interactions. The impeded desorption is also confirmed by the slower detachment of asphaltenes based on the time-dependent interaction energies and center of mass (COM) distances analysis. Additionally, the terminal polar groups lead to extraordinary desorption properties of asphaltenes. It is observed that the strong asphaltene-silica and asphaltene-water interactions coexist in these systems due to the high polarity and hydrophilicity of the terminal polar groups.