A Density Functional Based Tight Binding (DFTB+) Study on the Sulfidization-Amine Flotation Mechanism of Smithsonite

"Sulfidization-amine is the most effective method for the recovery of smithsonite (ZnCO3), however the interface interaction details remain unclear. The sulfidization-amine flotation mechanism of smithsonite has been studied by Density Functional based Tight Binding (DFTB+) method in this paper. The slab model of ZnCO3 (101) surface was built and the adsorptions of a monolayer of HS- and S2- ions were conducted to model the sulfidization effect on the ZnCO3 (101) surface adsorption. DDA hardly interacts with the hydrated ZnCO3 (101) surface. Under the low concentration of Na2S, HS- ions form a Zn-SH-SH structure on the ZnCO3 (101) surface, which hinders the interaction between DDA and surface Zn atoms. Under the high concentration of Na2S, a layer of ZnS is formed on ZnCO3 (101) surface, which is favorable for the adsorption of DDA on the surface. This is consistent with the flotation practice where smithsonite flotation requires a large amount of sodium sulfide. The results could provide a microscopic investigation into the sulfidization-amine flotation mechanism of smithsonite.INTRODUCTIONSmithsonite (ZnCO3) is an important and typical oxide mineral of zinc. It is a semi-soluble salt mineral with a solubility product constant of 1.46 × 10-10 (Weast, 1973). The most common and effective method to recover oxidized zinc ores is froth flotation (Caproni et al., 1979; Pereia and Peres, 2005; Kashani and Rashchi, 2008). It is well known that the flotation of oxidized zinc minerals is much more difficult than the flotation of zinc sulphide minerals (Hosseini and Forssberg, 2007).The recovery of zinc oxide ores with poor floatability attracts more and more attention due to the depletion of easy-recovered of zinc sulfide ores.Sulfidization-amine flotation, which using Na2S as sufidizing agent and amine as collector (Mckenna et al., 1949; Rey, 1954; Abramov, 1961; Rey, 1979; Hosseini and Forssberg, 2007). This method is the most successful technology used for zinc oxide minerals flotation in large-scale industrial applications since it was invented in the 1950s (Önal et al., 2005; Pereira and Peres, 2005). There have been numerous experimental researches on the sulfidization-amine flotation of smithsonite. Shi et al., (2013) studied solution chemistry of smithsonite flotation system. Feng and Wen (2017) studied the formation of zinc sulfide species on smithsonite surfaces and its response to flotation performance. Wu et al., (2017) investigated the sulfidization behavior of smithsonite with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic (XPS). Their measurement results confirms the chemisorption of sulfur ions and the formation of ZnS film on the smithsonite surface after Na2S treatment, however the influence of HS- ions on the surface and the influence of sulfidization on the amine adsorption have not been discussed."