Molecular dynamics simulations of the nickel removal from crude oil by neutral and charged spherical polymer brushes

[Display omitted] •Submicron polybutadiene grafted by polyacrylamide was prepared and characterized.•The nickel removal mechanism by polymer brushes was explored on the molecular level.•Sandwiched π–π stacking structures between Ni2+ and porphyrin rings were formed. Nickel in crude oil adversely affects the refining process for rapidly deactivating the hydrogenation and cracking catalysts. Polymer brushes bearing high-density ligands have shown promising nickel removal ability. In this work, submicron polybutadiene (PB) grafted by polyacrylamide (PAM@PB) was prepared and characterized by the transmission electron microscope, dynamic light scattering, and elemental analysis, which was also compared with the PB latex grafted by polyacrylic acid (PAA@PB) synthesized in our previous work. The nickel removal rates by both brushes were evaluated through the electric desalination process. Theresults show that the nickel removal capacity of PAA@PB is higher than that of PAM@PB. By the molecular dynamics simulations, the stretching and competitive chelation of polymer brush models PAA@PB-M and PAM@PB-M were investigated. Charged polyacrylic acid brushes usually have a higher thickness layer and a lower ligand density under the electrostatic repulsion and hydrogen bonding. The electrostatic interaction plays a more important role than the van der Waals interactions on nickel removal. PAA@PB-M is more attractive against Ni2+ ions than PAM@PB-M. The inevitable formation of stable sandwiched π-π stacking structures between Ni2+ ions and multiple porphyrin rings causes great difficulty in nickel removal during the electric desalination process. Adding protons to the oil phase can reduce the formation of the sandwiched structures and further improve nickel removal rates. In this paper, molecular dynamics simulation is innovatively applied to the mechanism of demetallization of polymer brushes, revealing the differences in structure and demetallization between charged and neutral polymer brushes, which provides guidance for the design of core–shell polymer brushes with high demetallization efficiency.