Improved Understanding of the Sulfidization Mechanism in Amine Flotation of Smithsonite: An XPS, AFM and UV-Vis DRS Study

Sulfidization is required in the amine flotation of smithsonite; however, the sulfidization mechanism of smithsonite is still not fully understood. In this work, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS) were used to characterize sulfidized and unsulfidized smithsonite. The XPS and UV-vis DRS analyses showed that smithsonite sulfidization is a transformation of ZnCO3 to ZnS on the smithsonite surfaces. However, this transformation is localized, resulting in the coexistence of ZnCO3 and ZnS or in the formation of ZnS island structures on the sulfidized smithsonite surfaces. AFM height imaging showed that sulfidization can substantially change the surface morphology of smithsonite; in addition, AFM phase imaging demonstrated that sulfidization occurs locally on the smithsonite surfaces. Based on our findings, it can be concluded that smithsonite sulfidization is clearly a heterogeneous solid-liquid reaction in which the solid product attaches at the surfaces of unreacted smithsonite. Smithsonite sulfidization involves heterogeneous nucleation and growth of ZnS nuclei. Moreover, the ZnS might nucleate and grow preferentially in the regions with high reactivity, which might account for the formation of ZnS island structures. In addition, sphalerite-structured ZnS is more likely to be the sulfidization product of smithsonite under flotation-relevantconditions, as also demonstrated by the results of our UV-vis DRS analyses. The results of this study can provide deeper insights into the sulfidization mechanism of smithsonite.