Advances in depressants for flotation separation of Cu–Fe sulfide minerals at low alkalinity:A critical review

The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.

Density functional theory study on natural hydrophobicity of sulfide surfaces

Adsorption of water on sulfide surfaces and natural floatability of sulfide minerals were studied using density functional theory （DFT） method. All computational models were built in a vacuum environment to eliminate the effects of oxygen and other factors. H2O molecule prefers to stay with pyrite and sphalerite surfaces rather than water, whereas for galena, chalcocite, stibnite, and molybdenite, H2O molecule prefers to stay with water rather than the mineral surfaces. On the other hand, pyrite surface favors N2 more than water, while sphalerite surface cannot adsorb N2. These results show that galena, stibnite, chalcocite, and molybdenite are hydrophobic, while sphalerite is hydrophilic. Although pyrite has certain hydrophilicity, it tends to be aerophilic because the reaction of pyrite with H2O is weaker than pyrite with N2. Thus, pyrite, galena, chalcocite, stibnite and molybdenite all have natural floatability.

Mechanism of mechanical activation for spontaneous combustion of sulfide minerals

In order to uncover the intrinsic reasons for spontaneous combustion of sulfide minerals,representative samples were collected from typical metal mines to carry out the mechanical activation experiment.The structures and heat behaviors of activated samples were characterized by scanning electron microscopy（SEM）,X-ray diffraction（XRD） analysis,and simultaneous thermal analysis（STA）.It is found that the sulfide minerals after mechanical activation show many changes with increased specific surface areas,aggregation phenomenon,decreased diffraction peak intensity,broadened diffraction peak,declined initial temperatures of heat release and self-ignition points.A new theory for explaining the spontaneous combustion of sulfide minerals is put forward：the chemical reaction activity of sulfide minerals is heightened by all kinds of mechanical forces during the mining,and the spontaneous combustion takes place finally under proper environment.

Identified the hydrochemical and the sulfur cycle process in subsidence area of Pingyu mining area using multi-isotopes combined with hydrochemistry methods

Groundwater serves as an important water source for residents in and around mining areas.To achieve scientific planning and efficient utilization of water resources in mining areas,it is essential to figure out the chemical formation process and the ground water sulfur cycle that transpire after the coal mining activities.Based on studies of hydrochemistry and D,^(18)O-H_(2)O,^(34)S-SO_(4)isotopes,this study applied principal component analysis,ion ratio and other methods in its attempts to reveal the hydrogeochemical action and sulfur cycle in the subsidence area of Pingyu mining area.The study discovered that,in the studied area,precipitation provides the major supply of groundwater and the main water chemistry effects are dominated by oxidation dissolution of sulfide minerals as well as the dissolution of carbonate and silicate rocks.The sulfate in groundwater primarily originates from oxidation and dissolution of sulfide minerals in coal-bearing strata and human activities.The mixed sulfate formed by the oxidation of sulfide minerals and by human activities continuously recharges the groundwater,promoting the dissolution of carbonate rock and silicate rock in the process.

New influence factor inducing difficulty in selective flotation separation of Cu–Zn mixed sulfide minerals

Selective flotation separation of Cu-Zn mixed sulfides has been proven to be difficult. Thus far, researchers have found no satis- factory way to separate Cu-Zn mixed sulfides by selective flotation, mainly because of the complex surface and interface interaction mecha- nisms in the flotation solution. Undesired activation occurs between copper ions and the sphalerite surfaces. In addition to recycled water and mineral dissolution, ancient fluids in the minerals are observed to be a new source of metal ions. In this study, significant amounts of ancient fluids were found to exist in Cu-Zn sulfide and gangue minerals, mostly as gas-liquid fluid inclusions. The concentration of copper ions re- leased from the ancient fluids reached 1.02 × 10-6 tool/L, whereas, in the cases of sphalerite and quartz, this concentration was 0.62 ×10-6 mol/L and 0.44 × 10-6 mol/L, respectively. As a result, the ancient fluid is a significant source of copper ions compared to mineral dissolution under the same experimental conditions, which promotes the unwanted activation of sphalerite. Therefore, the ancient fluid is considered to be a new factor that affects the selective flotation separation of Cu-Zn mixed sulfide ores.

Sulfide mineral bioleaching:Understanding of microbe-chemistry assisted hydrometallurgy technology and acid mine drainage environment protection

Bioleaching is regarded as an essential technology to treat low grade minerals,with the distinctive superiorities of lower-cost and environment-friendly compared with traditional pyrometallurgy method.However,the bioleaching efficiency is unsatisfactory owing to the passivation film formed on the minerals surface.It is of particular interest to know the dissolution and passivation mechanism of sulfide minerals in the presence of microorganism.Although bioleaching can be useful in extracting metals,it is a double-edged sword.Metallurgical activities have caused serious environmental problems such as acid mine drainage(AMD).The understanding of some common sulfide minerals bioleaching processes and protection of AMD environment is reviewed in this article.

DFT calculation on relaxation and electronic structure of sulfide minerals surfaces in presence of H_2O molecule

First-principles calculations are performed to investigate the relaxation and electronic properties of sulfide minerals surfaces(MoS2, Sb2S3, Cu2 S, ZnS, PbS and FeS2) in presence of H2 O molecule. The calculated results show that the structure and electronic properties of sulfide minerals surfaces have been influenced in presence of H2 O molecule. The adsorption of the flotation reagent at the interface of mineral-water would be different from that of mineral surface due to the changes of surface structures and electronic properties caused by H2 O molecule. Hence, the influence of H2 O molecule on the reaction of flotation reagent with sulfide mineral surface will attract more attention.

Galvanic coupling and its effect on origin potential flotation system of sulfide minerals

The galvanic coupling formed in origin potential flotation systems of sulfide minerals can be divided （into） three types: sulfide mineral-sulfide mineral-water system; sulfide mineral-steel ball-water system; and sulfide mineral-sulfide mineral-collector system. In this paper, taking lead, zinc, iron sulfide mineral systems for examples, several models of galvanic coupling were proposed and the effects of galvanic coupling on flotation were discussed. A galvanic contact between galena （or sphalerite） and pyrite contributes to decreasing the content of zinc in lead concentrate, and enhances remarkably the absorption of collector on the galena surface. During grinding, due to galvanic interactions between minerals and steel medium, Fe（OH）3 formed covers on the cathodic mineral surface, affecting its floatability.

Comprehensive recovery of gold and base-metal sulfide minerals from a low-grade refractory ore

The comprehensive recovery of small amounts of valuable minerals such as gold and base-metal sulfide minerals from a low-grade refractory ore was investigated. The following treatment strategy was applied to a sample of this ore： gold flotation-gold concen- trate leaching-lead and zinc flotation from the gold concentrate leaching residue. Closed-circuit trials of gold flotation yielded a gold concen- trate that assayed at 40.23 g·t-1 Au with a recovery of 86.25%. The gold concentrate leaching rate was 98.76%. Two variants of lead-zinc flotation from the residue--preferential flotation of lead and zinc and bulk flotation of lead and zinc--were tested using the middling processing method. Foam from the reflotation was returned to the lead rougher flotation or lead-zinc bulk flotation, whereas middlings from reflotation were discarded. Sulfur concentrate was a byproduct. The combined strategy of flotation, leaching, and flotation is recommended for the treatment of this kind of ore.

Mechanism of influence of chloride ions on electrogenerative leaching of sulfide minerals

A dual cell system was used to study the influence of chloride ions on the electrogenerative leaching of sulfide minerals. The results show that the influences of chloride ions on a series of electrogenerative leaching system are similar, and chlorine ion is involved in the electrogenerative leaching process of sulfide minerals directly. The output power increases with the increase of Cl^- concentration. The influence on the electrogenerative leaching rate decreases when the Cl^- concentration reaches a certain value. The mechanisms of anodic reaction are deduced based on the reasonable hypothesis, and kinetic equations with respect to chlorine ions for each sulfide mineral are obtained. The kinetic equations show that when concentration of Cl^- is relatively low, the electrogenerative leaching rates are predicted to have 2/5,3/7,1/3 and 1/3 order dependence on Cl^- concentration for chalcopyrite concentrate,nickel concentrate, sphalerite and galena. As concentration of Cl^- increases, the correlative dependence of electrogenerative leaching rate on concentration of Cl^- becomes weak.

Metal affinities in single and multiple ion adsorption reaction at sulfide mineral surfaces

Sulfide minerals are found in porous media in both aerobic and anaerobic environments, they should have a high affinities for certain metals. The relative binding affinities and reaction processes for 10 metal/metalloid ions reacting with four sulfide mineral surfaces has been defined.The order of reactivity is chalcocite > pyrite > galena >> sphalerite. For any particular metal and mineral, the greater reactivity occurs in the single-ion metal system except Ag(I) on pyrite and Cu(II) on galena.Both precipitation and adsorption reaction can decrease metal ion mobility on porous media, the order of metal mobility in the presence of the four sulfide minerals is predicted to be: Zn(II), Cd(II) and Ni(II) - mobile; Cu(II), Pb(II), Fe(III), As(III) and Cr(III) - variable mobility and Ag(I) - immobile.MINTEQA1 predictions on metal phase distribution / partitioning compared quite well with those observed experimentally. Solubility product considerations, intrinsic acidity constant of the mineral, EH, pH and the carbonate equilibrium are major factors controlling the phase distribution of metals reacting singularly or in combination with sulfide mineral surfaces.

Adsorption and desorption of lanthanum at sulfide mineral surface

Batch adsorption experiment with four sulfide minerals - Chalcocite galena, pyrite and sphalerite - were used to study for the adsorption and desorp-tion behavior of La (III) in the presence of EDTA, a model humic matter. Linear adsorption was found in all cases.The presence of soluble organic complexing ligand should reduce the mobility of La (III) in porous media and its transport to groundwater in the percolating soil solution. Binding mechanism is proposed to account for this preferential binding behavior.

Effect of radiation on wettability and floatability of sulfide minerals

The feasibility for modifying the wettability and floatability of sulfideminerals by electron beam irradiation has been studied experimentally. The wettability ofcrystalline pyrite and floatability of some sulfide as pyrite, arsenopyrite, chalcopyrite andmarmatite after irradiation were examined by flotation in a modified Hallimond tube. Experimentalresults show that the hydrophobicity of crystalline pyrite enhances with the increase of irradiationdose in a low dose range. And the flotation responses of sulfide minerals on irradiation dose varywith the mineral species and particle size. The floatability of minerals can be regulated byaltering irradiation dose. An explanation for the mechanism has been suggested based on theprinciple of radiation chemistry.

Typical roles of metal ions in mineral flotation:A review

In flotation,metal ions possess significant roles that are usually fulfilled by either selectively activating or depressing the target minerals.Despite that tremendous efforts have been made to address the roles of metal ions in flotation,it still lacks a comprehensive review,especially to compare various ions instead of focusing on a specific one.This review begins by elaborately categorizing the factors involved in affecting the roles of metal ions in flotation.After that,well-accepted mechanisms are updated and discussed from the ore type.Furthermore,typical approaches to explore the underlying mechanisms are emphasized,including traditional techniques such as micro-flotation,contact angle measurement,zeta potential measurement,and other recent prevailing methodologies,like computational method,solution chemistry calculation,and cyclic voltammetry.This work will pave the way to promote flotations via activities like selectively adding/reducing metal ions,choosing reagents,and regulating the slurry chemistry.

Electrochemical and spectroscopic study of interfacial interactions between chalcopyrite and typical flotation process reagents

Comparative voltammetry and differential double-layer capacitance studies were performed to evaluate interfacial interactions between cnalcopyrite（CuFeS2） and n-isopropyl xanthate（X） in the presence of ammonium bisulfite/39wt%SO2 and caustic starch at different pH values.Raman spectroscopy,Fourier transform infrared（FTIR） spectroscopy,contact angle measurements,and microflotation tests were used to establish the type and extent of xanthate adsorption as well as the species involved under different mineral surface conditions in this study.The results demonstrate that the species that favor a greater hydrophobicity of chalcopyrite are primarily CuX and S^0,whereas oxides and hydroxides of Cu and Fe as well as an excess of starch decrease the hydrophobicity.A conditioning of the mineral surface with ammonium bisulfite/39wt%SO2 at pH 6 promotes the activation of surface and enhances the xanthate adsorption.However,this effect is diminished at pH ≥ 8,when an excess of starch is added during the preconditioning step.