Adsorption characteristics of Pb(Ⅱ)ions on sulfidized hemimorphite surface under ammonium sulfate system

In this work,the effect of ammonium sulfate on the adsorption characteristics of low-concentration Pb(Ⅱ)ions on the sulfidized hemimorphite surface was comprehensively investigated.The results showed that ammonium sulfate could increase the maximum recovery of hemimorphite from 69.42%to 88.24%under a low concentration of Pb(Ⅱ)ions.On the hemimorphite surface pretreated with ammonium sulfate,the adsorption of Pb(Ⅱ)ions was enhanced and the main species of Pb adsorbed was changed from Pb―O/OH to PbS.This was due to the larger amount of ZnS providing more effective adsorption sites for Pb components to generate Pb S.Meanwhile,the intensity of ZnS decreased with the formation of PbS,demonstrating that ZnS was covered by PbS which formed later on the mineral surface.It was beneficial for the adsorption of butyl xanthate on the hemimorphite surface to form more hydrophobic substances.As a result,ammonium sulfate played a crucial role in realizing the efficient recovery of hemimorphite.

Effect of ammonium sulfate on the formation of zinc sulfide species on hemimorphite surface and its role in sulfidation flotation

Effectively strengthening the surface sulfidation is essential for recovering hemimorphite by froth flotation.In this work,inductively coupled plasma optical emission spectrometer(ICP-OES)measurements,Visual MINTEQ calculation,X-ray photoelectron spectroscopy(XPS)analysis,time of flight secondary ion mass spectrometry(ToF-SIMS)analysis,and micro-flotation experiments were explored to systematically investigate the effect of ammonium sulfate((NH_(4))_(2)SO_(4))on the formation of zinc sulfide species on hemimorphite surface and its role in sulfidation flotation.The results showed that(NH_(4))_(2)SO_(4)exhibited a positive influence on hemimorphite sulfidation flotation.It was ascribed to the number of zinc components in the form of Zn^(2+)and[Zn(NH_(3))_(i)]^(2+)(i=1–4)increased in the flotation system after hemimorphite treatment with(NH_(4))_(2)SO_(4),which was beneficial to its interaction with sulfur species in solution,resulting in a dense and stable zinc sulfide layer generated on the hemimorphite surface.[Zn(NH_(3))_(i)]^(2+)participated in the sulfidation reaction of hemimorphite as a transition state.In addition the sulfidation reaction of hemimorphite was accelerated by(NH_(4))_(2)SO_(4).Thus,(NH_(4))_(2)SO_(4)presents a vital role in promoting the sulfidation of hemimorphite.

Preparation of metal zinc from hemimorphite by vacuum carbothermic reduction with CaF_2 as catalyst

Zn reduction was investigated by the vacuum carbothermic reduction of hemimorphite with or without CaF2 as catalyst.Results indicate that CaF2 can catalyze the carbothermic reduction of zinc silicate,decrease the reaction temperature and time.The lower the reaction temperature and the more the amount of CaF2,the better the catalytic effect.The optimal process condition is obtained as follows：the addition of about 10% CaF2,the reaction temperature of 1373 K,the molar ratio of C to ZnTotal of 2.5,the pressure of system lower than 20 kPa,the reaction time of about 40 min.Under the optimal process condition,the zinc reduction rate is about 93% from hemimorphite.

Solubility of hemimorphite in ammonium sulfate solution at 25 °C

The solubility of natural hemimorphite in ammonium sulfate solution was measured by isothermal solution method at 25 °C and the dissolved residue of hemimorphite was investigated by X-ray powder diffraction （XRD）, scanning electron microscopy （SEM） and Fourier transform infrared spectroscopy （FTIR） methods. The results show that zinc and silica in hemimorphite simultaneously dissolve in ammonium sulfate solution. The solubility of zinc in solution increases rapidly from 4.5381 mmol/kg in 0.5469 mol/kg ammonium sulfate solution to 11.5083 mmol/kg in 3.7038 mol/kg ammonium sulfate solution. The solubility of silica in solution increases slowly from 2.5509 mmol/kg in 0.5469 mol/kg ammonium sulfate solution to 7.2891 mmol/kg in 3.7038 mol/kg ammonium sulfate solution. The dissolved residue is the characteristic of hemimorphite Zn4Si2O7（OH）2·H2O based on the results of the XRD, SEM and FTIR. Thus, no phase transition occurs in the dissolution process of hemimorphite in ammonium sulfate solution.

Improved hemimorphite flotation using xanthate as a collector with S(Ⅱ) and Pb(Ⅱ) activation

The flotation of hemimorphite using the S(Ⅱ)–Pb(Ⅱ)–xanthate process,which includes sulfidization with sodium sulfide,activation by lead cations,and subsequent flotation with xanthate,was investigated.The flotation results indicated that hemimorphite floats when the S(Ⅱ)–Pb(Ⅱ)–xanthate process is used; a maximum recovery of approximately 90% was obtained.Zeta-potential,contact-angle,scanning electron microscopy–energy-dispersive spectrometry(SEM–EDS),and diffuse-reflectance infrared Fourier transform spectroscopy(DRIFTS) measurements were used to characterize the activation products on the hemimorphite surface and their subsequent interaction with sodium butyl xanthate(SBX).The results showed that a Zn S coating formed on the hemimorphite surface after the sample was conditioned in an Na2 S solution.However,the formation of a Zn S coating on the hemimorphite surface did not improve hemimorphite flotation.With the subsequent addition of lead cations,Pb S species formed on the mineral surface.The formation of the Pb S species on the surface of hemimorphite significantly increased the adsorption capacity of SBX,forming lead xanthate(referred to as chemical adsorption) and leading to a substantial improvement in hemimorphite flotation.Our results indicate that the addition of lead cations is a critical step in the successful flotation of hemimorphite using the sulfidization–lead ion activation–xanthate process.

Dissolution mechanism and solubility of hemimorphite in NH_3-(NH_4)_2SO_4-H_2O system at 298.15 K

The dissolution mechanism of hemimorphite in NH3-（NH4）2SO4-H2O system at 298.15 K was investigated by X-ray powder diffraction （XRD）, scanning electron microscopy （SEM）, Fourier transform infrared spectroscopy （FTIR） and X-ray photoelectron spectroscopy （XPS） analysis. The results show that hemimorphite is soluble in NH3-（NH4）2SO4-H2O system and its residue exists in the form of an amorphous SiO2 layer on the hemimorphite surface. The XPS data also indicate that the Si 2p3/2 and O ls spectra of the hemimorphite are broadened and shift to higher binding energies and their binding energies are closer to silica with an increase of total ammonia and time. Solubility of hemimorphite in NH3-（NH4）2SO4-H2O system was measured by means of isothermal solution method at 298.15 K based on the study of the dissolution mechanism of hemimorphite. The results show that the solubility of zinc in solution increases firstly and then decreases with the increase of cr（NH3） （total ammonia concentration） at different NH3/NH4^＋ ratios. The solubility of silicon in solution decreases from 0.0334 mol/kg in ct（NH3）-4.1245 mol/kg NH3-（NH4）2SO4-H2O solution to 0.0046 mol/kg in cT（NH3）=7.6035 mol/kg NH3-（NH4）2SO4-H2O solution.

A review of major non-sulfide zinc deposits in Iran

The numerous non-sulfide zinc ore deposits were the historical basis for the development of zinc mining in Iran.They include the Mehdiabad,Irankouh and Angouran world-class deposits,as well as the Zarigan and Haft-har deposits.These deposits were formed by supergene oxidation of primary sulfide minerals during the complex interplay of tectonic uplift,karst development,changes in the level of the water table,and weathering.Zn(Pb)carbonates,Zn-hydrosilicates and associated hydrated phases directly replace the primary ore bodies or fill cavities along fractures related to uplift tectonics.Direct replacement of primary sulfides is accompanied by distal precipitation of zinc non-sulfide minerals in cavities or internal sediments filling.The mineralogy of the non-sulfide mineralization in all six deposits is generally complex and consists of smithsonite,hydrozincite,and hemimorphite as the main economic minerals,accompanied by iron and manganese oxy-hydroxides and residual clays.Commonly,non-sulfide minerals in these deposits consist of two types of ore:red zinc ore(RZO),rich in Zn,Fe,Pb-(As)and white zinc ore(WZO),typically with very high zinc grades but low concentrations of iron and lead.Typical minerals of the RZO are Fe-oxyhydroxides,goethite,hematite,hemimorphite,smithsonite and/or hydrozincite and cerussite.Common minerals of the WZO are smithsonite or hydrozincite and only minor amounts of Fe-oxyhydroxides and hemimorphite.