In this study, ethylene diamine phosphate (EDP) was employed as an activator to improve the sulfidization and flotation of chrysocolla. The micro-flotation experiment results indicated that EDP could greatly increase the flotation recovery of chrysocolla. BET and TEM measurements confirmed that the porous structure of the chrysocolla’s surface would lead to large amounts of the reagents. ICP-AES analysis revealed that the addition of EDP caused more active Cu sites formed on the chrysocolla’s surface, enhancing the adsorption of S²⁻ on its surface. Meanwhile, a redox reaction occurred between the S²⁻ and [Cu(en)₂]²⁺ ions causing the Cu, S, and N in the solution to counter-adsorb onto the chrysocolla’s surface by forming new complexes. During this reaction, the Cu(II) species reduced to Cu(I) species and the sulfide ions in the form of S²⁻, S₂²⁻, S_n²⁻, and SO₄²⁻ appeared on the mineral surface. The zeta potential measurements further revealed that the EDP-activated chrysocolla surfaces adsorbed more sulfide species and xanthate species, thereby improving the floatability of the chrysocolla.

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.

Ammonium ions have positive effects on the sulfidization flotation of malachite; however, the underlying mechanisms remain poorly understood. In the present work, micro-flotation tests, field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and solution analysis for ammonium nitrogen were carried out. The flotation results showed positive effects of ammonium on the sulfidization flotation of malachite. Macroscopically, the sulfidized malachite produced with ammonium exhibited a darker color than that without ammonium, whereas the opposite appeared to be true for their corresponding residual liquids. FESEM images highlighted the larger particle size and higher converge density of the sulfidization product when the presence of ammonium. Furthermore, XPS results indicated a higher sulfur concentration on malachite surfaces when the presence of ammonium. XRD results showed that Cu₃₁S₁₆ (djurleite) and Cu₇S₄ (anilite) comprised the sulfidization products, regardless of the presence or absence of ammonium. However, neither EDS nor XPS analysis showed nitrogen on malachite surfaces; moreover, the residual-ratio results for ammonium nitrogen clearly demonstrated that most ammonium continued to be held in solution before and after malachite sulfidization. Based on these findings, we inferred that ammonium ions may mediate the nucleation and growth of sulfidization product during malachite sulfidization, rendering larger sulfidization product particles. The larger size of sulfidization products may result in a darker, stabler and denser sulfidization product coating layer, and then may reduce the generation of colloidal copper sulfide in the residual liquids. Ultimately, ammonium facilitates better performance of sulfidization flotation of malachite.

The crystal of hemimorphite is a non-conductor. The Si–O bond in the crystal is strong, whereas the Zn–O bond is weak. These properties lead to the easy breakage of the Zn–O bond in the crushing process of hemimorphite. Thus, the interaction between minerals and polar water molecules is strong, and natural floatability of ores is poor. This study systematically investigated the characteristics of hemimorphite and its action mechanism with Na₂CO₃. Results of SEM-EDS showed that the surface of hemimorphite dissolved after interacting with Na₂CO₃, and the contents of Si and O decreased, whereas Zn and C increased. XPS analysis showed that the carbonate group was detected. The interaction between CO₃²⁻ and hemimorphite was calculated using the first principles calculation based on density functional theory. The results indicate that an O atom in CO₃²⁻ interacted with Zn²⁺ from the (100) plane of hemimorphite. The interaction between Zn and O atoms was not strong, and the Zn atoms were not completely displaced, which was proven by density of state analysis and the EDS and XPS results. The Mulliken population showed that the O–Zn bond was the atomic bonding of CO₃²⁻ with Zn²⁺ and exhibited properties of ionic bonds. Thus, hemimorphite transformed to smithsonite-like mineral (ZnCO₃) when acting with CO₃²⁻.

The purpose of this study was to investigate the reaction mechanism of wulfenite with an aqueous sodium sulfide solution and thereby provide guidance for the sulfidization flotation and sodium sulfide leaching of wulfenite. For this purpose, dissolution/leaching behavior analysis, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and field-emission scanning electron microscopy (FESEM) were performed. The dissolution/leaching analysis indicated that sodium sulfide can induce the dissolution of PbMoO₄. The XRD and Raman spectra results demonstrated that PbMoO₄ was replaced by PbS at the wulfenite–sodium sulfide solution interface, and the sulfidized wulfenite particles had a PbMoO₄/PbS core–shell structure. The XPS results also indicated the transformation of PbMoO₄ to PbS. The FESEM images showed the growth of PbS nanoparticles on the surface of wulfenite and the dissolution pits after treatment with sodium sulfide solution. These findings showed that wulfenite sulfidization proceeds through an interface-coupled dissolution–precipitation mechanism. In the presence of sodium sulfide solution, the less stable PbMoO₄ dissolves, and the more stable PbS phase precipitates, both of which are coupled at the wulfenite–sodium sulfide aqueous solution interface.