Interaction and Inhibition Mechanism of Sulfuric Acid with Fluorapatite (001) Surface and Dolomite (104) Surface: Flotation Experiments and Molecular Dynamics Simulations

The natural wettability of apatite and dolomite and the effect of sulfuric acid (H2SO4) and sodium oleate (NaOl) on the floatability and wettability of both minerals were studied using single-mineral flotation and contact angle measurement. The flotation experiments demonstrated that adding NaOl, apatite, and dolomite had good floatability. After adding H2SO4, the floatability of apatite decreased significantly. H2SO4 effectively inhibits apatite flotation. Contact angle measurements show that the use of H2SO4 induces a significant difference in surface wettability between apatite and dolomite. The moderate addition of H2SO4 can increase the contact angle of dolomite. In order to study the selective inhibition mechanism of H2SO4 in phosphorite flotation, molecular dynamics simulations (MDSs) were conducted to investigate the interaction between H2SO4 and fluorapatite and dolomite at the atomic-molecular level. The results of MDSs reveal that H2SO4 interacts with Ca sites on both fluorapatite and defective dolomite surfaces, hindering the interaction of NaOl with Ca sites on both mineral surfaces. SO42- ions cannot prevent the interaction of oleate ions with Mg sites on dolomite surface. It is worth mentioning that SO42- ions occupy the defective vacancies formed due to the dissolution of CO32- on the surface of dolomite and interact with Ca sites. The remaining H2SO4 is subsequently adsorbed onto the surface of dolomite. Experimental and simulation results show that, due to the interaction of H2SO4 and NaOl, the surface of apatite can still undergo hydration forming a water molecule layer and maintaining a macroscopic hydrophilic property. In contrast, the oleate ions form an adsorption layer on dolomite transitioning it from a hydrophilic to a hydrophobic state. During the phosphate flotation process, the addition of an appropriate amount of sulfuric acid can further diminish the hydration of the dolomite surface, so that the surface of dolomite is more hydrophobic.