An electrochemical investigation of pyrite flotation and depression

The oxidation of ethyl xanthate on pyrite electrodes, and the influence of the flotation depressants hydroxide, cyanide, and sulphide, have been investigated using cyclic voltammetry. A layer of a hydrated iron oxide has been identified on pyrite surfaces. Xanthate does not interact with this layer but is oxidized to dixanthogen at positive potentials. An increase in pH results in an increase in the background current due to oxidation of the mineral, and at pH=11 this reaction becomes faster than xanthate oxidation. Cyanide interacts with the electrode to form a surface species which inhibits xanthate oxidation. Sulphide gives rise to an anodic wave preceding the wave due to xanthate oxidation. The flotation and depression of pyrite are interpreted in terms of mixed-potential mechanisms.     

On the cathodic reaction coupled with the oxidation of xanthates at the pyrite/aqueous solution interface

The adsorption of ethyl, propyl and butyl xanthates on pyrite has been studied through electrokinetics, batch adsorption tests, and quantification of Fe²⁺ ions in solution. Adsorption isotherms for the three alkyl xanthates indicate that their adsorption to dixanthogen produces Fe²⁺ ions in solution and decreases the pyrite zeta potential negatively. It seems that the oxidation reaction of xanthates to dixanthogen on pyrite is coupled with the reduction reaction of surface-ferric hydroxide to ferrous ions, leading to the dissolution of hydrophilic ferric hydroxide and growth of hydrophobic dixanthogen on the surface of pyrite. Flotation of pyrite is presented as a function of pH using various ethyl xanthate concentrations. The floatability results are explained in terms of the surface coverage relationship between ferric hydroxide and dixanthogen, which is pH dependent.     

Experimental study on prevention of acid mine drainage by silica coating of pyrite waste rocks with amorphous silica solution

Acid mine drainage (AMD) is a widespread environmental problem associated with working and abandoned mining operations. It results from the microbial oxidation of pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Pyrite microencapsulation, utilizing silica coating, is a novel approach for controlling AMD that has been shown to be very effective in controlling pyrite oxidation. The roles of the solution pH and silica concentration in the formation mechanism for the AMD-preventing coating were investigated. A silica coating can be formed from silica solution at pH 7, at which the amount of Fe eluted from pyrite into the solution is small. No coating was formed at other pH values, and the amounts of eluted Fe were larger than at pH 7, especially at pH 11. The silica coating forms from 2,500 to 5,000 mg/L silica solutions, but not from 0 or 1,000 mg/L silica solutions. The coating formation rate was slower in the 2,500 mg/L silica solution than in the 5,000 mg/L silica solution. The formation of silica coating on pyrite surfaces depends on three main steps: formation of Fe(OH)₃ on the surface of pyrite, reaction between Fe(OH)₃ and silicate in the solution on the pyrite surface, and growth of the silica layer on the first layer of silica. The best pH condition to enable these steps was around 7, and the silica coating formation rate can be controlled by the concentration of silica.     

Surface potential and dixanthogen stability on chalcopyrite surface

Contact angle measurements, ultraviolet (UV) spectroscopy and voltammetry were used in this investigation to study the effect of various externally applied potentials on the stability of dixanthogen at synthetic and natural chalcopyrite surfaces.The results of contact angle measurements indicate that synthetic and natural chalcopyrites have similar wettabilities. Their hydrophobic potential range in a 7 × 10^− 4 M PAX solution was + 0.04 V to + 0.44 V vs. NHE at pH 10 and was − 0.01 V to + 0.54 V at pH 7.UV spectroscopic results show that dixanthogen began to form on the chalcopyrite surface at a potential of + 0.04 V vs. NHE at pH 10 and − 0.01 V vs. NHE at pH 7. The amount of dixanthogen formed on the chalcopyrite surface initially increased with the increase of the applied potential and then decreased with the increasing potential. The optimum potential range for dixanthogen formation on the chalcopyrite surface was from + 0.14 V to + 0.34 V vs. NHE at pH 10 and from + 0.14 V to + 0.44 V vs. NHE at pH 7. It was difficult to completely remove the dixanthogen film on the chalcopyrite surface.     

Kinetics and thermochemistry of amyl xanthate adsorption by pyrite and marcasite

The kinetics and thermochemistry of the xanthate adsorption reaction on pyrite and marcasite were evaluated with respect to the existing theory. The rate of xanthate adsorption was studied in a stirred reactor and the xanthate concentration was determined by UV spectrophotometry as a function of time. The heat of the adsorption reaction was measured with a microcalorimeter. The results from both experiments indicate that xanthate adsorption by pyrite or marcasite involves the formation of dixanthogen by an electrochemical reaction at the solid surface which supports the conclusions of other investigators:

$\text{1}\text{2}\text{O}{}_2\text{(aq) =}\text{1}\text{2}\text{O}{}_2\text{(ad) 2X + 2H}{}^{\mathrm{+}}\text{+}\text{1}\text{2}\text{O}{}_2\text{→ X}{}_2\text{(ad) + H}{}_2\text{O}$

The rate of the adsorption reaction was found to be approximately one-half order with respect to the xanthate concentration and to have an activation energy of 7.5 kcal/mole. Additionally, the rate was found to have a slight dependence on pH under certain conditions. In view of these results, it appears that the adsorption reaction is controlled by electrochemical discharge at the pyrite surface. Analysis of the data in terms of an electrochemical kinetic model successfully explained the observed rate phenomena.The measured heat of the adsorption reaction at low pH was found to be between ?63 and ?56 kcal/mole of adsorbed dixanthogen and independent of surface coverage. These experimental heats of adsorption agree with the value of ?57 kcal/mole of dixanthogen calculated for the oxidation of xanthate by oxygen from thermodynamic data reported in the literature.     

Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy

The nature of the surface oxidation phase on pyrite, FeS₂, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur L_III edge, and iron L_II,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS₂ can be detected in the X-ray absorption spectra. In a 1.667 × 10⁻³ mol/L Fe³⁺ solution with ferric iron present as FeCl₃ in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.     

Comparison of dissolution under oxic acid drainage conditions for eight sedimentary and hydrothermal pyrite samples

The abiotic oxidative dissolution behaviors of eight natural pyrite samples, five sedimentary and three hydrothermal, from various geological environments were compared under oxic conditions at pH 3 and 6 in a highly controlled batch reactor dissolution system. The three sedimentary pyrite samples associated with coal had greater specific surface areas and also exhibited greater apparent dissolution rates and extent than the other two sedimentary and three hydrothermal samples under both pH conditions. However, after normalizing for surface area, the dissolution rate constants for the different pyrite samples were similar; the greatest difference was between the two non-coal sedimentary pyrite samples. Pyrite morphology and the presence of trace metals could contribute to the differences in dissolution behavior as reflected in the normalized dissolution rates. The sulfur:iron ratio observed in the aqueous solution at pH 3 increased with time, but was always less than 2.0 (predicted from the stoichiometry of dissolution) for all the pyrite samples during the 24-h experimental duration. This can be explained by the disproportionation dissociation of thiosulfate, an initial product of pyrite dissolution, to elemental sulfur and sulfate which does not occur in a 1:1 ratio. The results of this work indicate the importance of extracting and using the specific pyrite(s) relevant to particular mining areas in order to understand pyrite dissolution rates and the influence of environmental conditions on those rates.     

The adsorption of gold(I) hydrosulphide complexes by iron sulphide surfaces

The adsorption of gold by pyrite, pyrrhotite, and mackinawite from solutions containing up to 40 mg/kg (8 μm) gold as hydrosulphidogold(I) complexes has been measured over the pH range from 2 to 10 at 25°C and at 0.10 m ionic strength (NaCl, NaClO₄). The pH of point of zero charge, pH_pzc, has been determined potentiometrically for all three iron sulphides and shown to be 2.4, 2.7, and 2.9 for pyrite, pyrrhotite, and mackinawite, respectively. In solutions containing hydrogen sulphide, the pH_pzc is reduced to values below 2. The surface charge for each sulphide is therefore negative over the pH range studied in the adsorption experiments. Adsorption was from 100% in acid solutions having pH < 5.5 (pyrite) and pH < 4 (mackinawite and pyrrhotite). At alkaline pH’s (e.g., pH = 9), the pyrite surface adsorbed 30% of the gold from solution, whereas the pyrrhotite and mackinawite surfaces did not adsorb.The main gold complex adsorbed is AuHS°, as may be deduced from the gold speciation in solution in combination with the surface charge. The adsorption of the negatively charged Au(HS)₂⁻ onto the negatively charged sulphide surfaces is not favoured. The X-ray photoelectron spectroscopic data revealed different surface reactions for pyrite and mackinawite surfaces. While no change in redox state of adsorbent and adsorbate was observed on pyrite, a chemisorption reaction has been determined on mackinawite leading to the reduction of the gold(I) solution complex to gold(0) and to the formation of surface polysulphides. The data indicate that the adsorption of gold complexes onto iron sulphide surfaces such as that of pyrite is an important process in the “deposition” of gold from aqueous solutions over a wide range of temperatures and pressures.     

Flotation of germanium n and p with potassium ethyl xanthate

Steady-state potential of the germanium electrode, flotation tests and results of spectrophotometric ATR (Attenuated Total Reflection) measurements of germanium surface in the presence and absence of potassium ethyl xanthate are presented.On the basis of the steady-state potentials of the germanium electrode in ethyl xanthate solutions, the standard potential E⁰ of the reaction: Ge + 2EtX^? = Ge (EtX)₂ + 2e is estimated. The pH ranges of the dixanthogen (EtX)₂ and the germanium xanthate Ge(EtX)₂ species predominance in the bulk solution are calculated. It has been established that flotation of germanium is greater than the natural floatability (in the absence of collectors) in the pH ranges where (EtX)₂ or Ge (EtX)₂ are present in the bulk solution. Spectrophotometric results reveal the presence of (EtX)₂ and Ge (EtX)₂ on the surface in the same pH ranges as is calculated for the bulk reactions.No significant differences in the surface properties and the flotation behaviour between germanium n and p have been found.     

Role of hydrogen peroxide and hydroxyl radical in pyrite oxidation by molecular oxygen

Hydrogen peroxide and hydroxyl radical are readily formed during the oxidation of pyrite with molecular oxygen over a wide range of pH conditions. However, pretreatment of the pyrite surface influences how much of the intermediates are formed and their fate. Acid-washed pyrite produces significant amounts of hydrogen peroxide and hydroxyl radical when suspended in air-saturated water. However, the hydrogen peroxide concentration shows an exponential decrease with time. Suspensions made with partially oxidized pyrite yield significantly lower amounts of hydrogen peroxide product. The presence of Fe(III)-oxide or Fe(III)-hydroxide patches facilitates the conversion of hydrogen peroxide to oxygen and water. Hence, the degree to which a pyrite surface is covered with patches of Fe(III)-oxide or Fe(III)-hydroxide patches is an important control on the concentration of hydrogen peroxide in solution.Hydrogen peroxide appears to be an important intermediate in the four-electron transfer from pyrite to molecular oxygen. Addition of catalase, an enzyme that decomposes hydrogen peroxide to water and molecular oxygen, to a pyrite suspension reduces the oxidation rate by 40%. By contrast, hydroxyl radical does not appear to play a significant role in the oxidation mechanism. It is estimated on the basis of a molecular oxygen and sulfate mass balance that 5-6% of the molecular oxygen is consumed without forming sulfate.     

Galvanic interaction between galena and pyrite in an open system

1IntroductionMost sulfide minerals in nature have perfect con-ductivity and possess semiconducting properties.Gal-vanic corrosion may occur when two sulfide mineralswith different potentials are connected together in thesolution.The mineral with the highe…     

开放体系下方铅矿和黄铁矿之间原电池反应的实验研究

金属硫化物矿物之间的原电池反应对于酸性矿山排水的形成、硫化物矿床的次生富集作用、地球电化学勘探以及湿法冶金过程等都有很重要的影响。通过改变溶液中氧化剂组分F e3 的浓度、pH值、溶液的流动状况以及溶液的盐度(如N a2SO4的浓度),采用精密的电流计和电位计,对作为阳极的黄铁矿与作为阴极的方铅矿所形成的原电池反应的电流密度和整个原电池的混合电位进行研究,结果表明:溶液中[F e3 ],pH值以及溶液的流动状况对黄铁矿和方铅矿之间原电池反应的影响很大,而溶液的盐度对反应的影响不是很显著。实验还发现,当黄铁矿电极表面存在微小裂纹时,其电极电位可降低至同条件下方铅矿的电极电位以下。这一实验结果在混合电位理论和Bu tler-V o lm er方程中得到了理论上的解释。     

Simulating experiment on the hydrothermal superimposing metallogenesis of the Dongguashan strata-bound copper deposit

Series of sedimentary hydrothermal-diplogenetic copper deposits have been found scattering in the region along the middle-lower reaches of the Yangtze River, and their metallogenetic mechanism is still in hot debate. In order to reveal the ore-forming kinetics of sedimentary process and hydrothermal superimposition, and evaluate the role of sedimentary pyrite in the enrichment and precipitation of copper, a set of simulating experiments on the reaction between pyrite and CuCl2 solution were conducted. According to the physicochemical characteristics of the ore-forming fluid of the Dongguashan copper deposit, Anhui Province, 100 MPa was selected as the experimental pressure, and the experimental temperatures were set at 450, 350, 250 and 150°C, respectively. The reactions between pyrite grains isolated from the Shimenkou strata-bound pyrite deposit and the solution with 0.2 mol/L CuCl2 and 1.0 mol/L NaCl were experimentally simulated. Then, variations in surface topography and surface chemistry of the experimental pyrite grains were documented using scanning electronic microscopy (SEM), atomic force microscopy (AFM), Auger electron spectrometry (AES) and X-ray photoelectron spectroscopy (XPS), and the solution and newly formed minerals were analyzed using inductively coupled plasma (ICP-AES) and X-ray diffraction (XRD) techniques. Desulphurization of pyrite surface was observed and new copper minerals were detected. It is proposed that pyrite can act as a geochemical barrier for the enrichment and precipitation of copper from the solution under the experimental conditions. Furthermore, the ore-forming mechanism of sedimentary hydrothermal-diplogenetic copper deposits was discussed.     

硫化物氧化过程中金的富集实验研究

室温条例上将海绵金用王水溶解形成金氯酸溶液,再用纯净的不含金黄铁矿吸附溶液中的金,粉干后用过氧化氢溶液将其分解,发现溶液中出现粒状、片状及壳皮状金。对溶液中金和铁的含量测定结果表明,随着黄铁矿的分解溶液中铁含量增加,金含量也随之增加,但当溶注保出现小金粒或金片后,溶液中的金含量急剧下降,并保持相对稳定。     

Interaction of finely ground galena and potassium amylxanthate in relation to flotation, 3. Influence of acid and neutral grinding

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Hallimond tube flotation and microelectrophoresis have been utilized to investigate the reactions in the adsorption-abstraction of K-amylxanthate on finely ground galena. The mineral was ground in a laboratory stainless steel rod mill under controlled conditions (pH 4.0 and 7.0) using HCl as a pH regulator. X-ray photoelectron spectroscopic (XPS) studies have been carried out in order to characterize the surface oxidation products after grinding (weak amounts of S_n and PbS₂O₃). The two-stage adsorption process discovered in previous studies was confirmed. For low concentrations or submonolayer capacity, the layer is formed with 1:1 monocoordinated lead xanthate and dixanthogen. For higher values of surface coverage, it is composed of lead xanthate (stoichiometric at pH 7 and non-stoichiometric at pH 4), amyldixanthogen and amylcarbonate disulphide. In the second stage mainly dixanthogen is formed. This stage corresponds to complete flotation and to a sharp decrease in zeta potentials.     

纳米金的迁移富集与黄铁矿富金关系

黄铁矿是金矿床中常见的矿物,也是重要的载金矿物之一,有的黄铁矿富金,有的黄铁矿不含金或含微量金。为什么黄铁矿对纳米金的吸附作用强？讨论了纳米微粒金与黄铁矿的关系后指出,半导体型黄铁矿有Ｎ型和Ｐ型两种。前者具负热电动势、带负电;后者具正电位带正电荷。当其与ＳｉＯ２水溶液迁移时,若与带正电荷的Ｐ型黄铁矿相遇,即被Ｐ型黄铁矿吸附沉淀成矿。带负电荷的黄铁矿不能吸附带负电荷的纳米金,因而不能成矿。     

Iron oxyhydroxide coating of pyrite for acid mine drainage control

When pyrite oxidizes at near neutral pH in the presence of sufficient alkalinity, Fe oxyhydroxide coatings develop on the surface. As these coatings grow thicker and denser they block oxidant transport from the solution to the pyrite surface and reduce the rate of pyrite oxidation. The authors’ measurements of pyrite oxidation rates in a NaHCO₃ solution show that the coating grows in two stages. In the first stage Fe oxyhydroxide colloids form and then attach to the pyrite surface to produce a slight reduction in oxidant transport. In the second stage interstitial precipitation of Fe oxyhydroxide material between the colloidal particles reduces the oxidant’s diffusion coefficient by more than five orders of magnitude. This causes the pyrite oxidation rate to decline as the square root of time. The kinetic predominance diagram, which compares the rates of Fe transformation reactions, shows that when pyrite oxidation releases Fe quickly enough for the total Fe concentration to rise to about 10⁻⁸ m, ferrihydrite forms but lower rates of Fe release will not produce coatings. Extrapolation of the results to longer times predicts that pyrite-bearing materials need to be treated with an extra source of alkalinity for several decades to produce coatings that are thick enough to be sustained by alkalinity levels typical of groundwater. However, once the coatings develop no additional treatment is needed and further pyrite oxidation simply causes the coating to grow thicker and denser until the entire pyrite grain is pseudomorphically replaced by goethite.     

双室电化学体系中产电微生物与黄铁矿单晶协同电子转移反应

通过构建产电微生物—黄铁矿双室体系, 应用电化学方法对以黄铁矿单晶电极作为产电微生物电子受体时, 两者间的电子转移过程进行表征和分析.结果显示, 与惰性石墨电极相比, 以黄铁矿单晶作为产电微生物电子受体时, 体系最大功率密度提升132.9%;电化学阻抗谱显示, 黄铁矿单晶电极极化电阻降低98.8%, 表现出优良的电化学反应特性, 表明产电微生物与黄铁矿单晶间具有良好的电子转移活性.籍由产电微生物对底物的氧化作用, 与黄铁矿单晶接受产电微生物电子在0.34 V(相对于饱和甘汞电极)处发生的还原反应, 构成了两者间完整的协同电子转移过程.      

Soft X-ray spectroscopic studies of the reaction of fractured pyrite surfaces with Cr(VI)-containing aqueous solutions

We have used synchrotron-based soft X-ray core-level photoemission and adsorption spectroscopies to study the reaction of aqueous sodium chromate solutions with freshly fractured pyrite surfaces. Pyrite surfaces were reacted with 50 μM sodium chromate solution at pH 7 for reaction times between 1 min and 37 hr. Additional experiments were performed at pH 2 and pH 4 with 50 μM sodium chromate solutions and at pH 7 with 5 mM solutions. At chromate concentrations of 50 μM, all chromium present on the pyrite surface was in the form of Cr(III), while at 5 mM, both Cr(III) and Cr(VI) were present at the pyrite surface. Minor quantities of oxidized sulfur species (sulfate, sulfite, and zero-valent sulfur) were identified as reaction products on the pyrite surface. The amount of oxidized sulfur species observed on the surface was greater when pyrite was reacted with 5 mM Cr(VI) solutions because the rate of chromium deposition exceeded the rate of dissolution of pyrite oxidation products, effectively trapping Cr(VI) and oxidized sulfur species in an overlayer of iron(III)-containing Cr(III)-hydroxide. This work shows that pyrite, an extremely cheap and readily available waste material, may be suitable for the removal of hexavalent chromium from acidic to circumneutral waste streams. The reduced chromium ultimately forms a coating on the pyrite surface, which passivates the pyrite surface towards further oxidation.     

Redox potential (Eh) and anion effects of pyrite (FeS2) leaching at pH 1

Pyrite plays the central role in the environmental issue of acid rock drainage. Natural weathering of pyrite results in the release of sulphuric acid which can lead to further leaching of heavy and toxic metals from other associated minerals. Understanding how pyrite reacts in aqueous solution is critical to understanding the natural weathering processes undergone by this mineral. To this end an investigation of the effect of solution redox potential (Eh) and various anions on the rate of pyrite leaching under carefully controlled conditions has been undertaken.Leaching of pyrite has been shown to proceed significantly faster at solution Eh of 900 mV (SHE) than at 700 mV, at pH 1, for the leach media of HCl, H₂SO₄ and HClO₄. The predominant effect of Eh suggests electrochemical control of pyrite leaching with similar mechanism(s) at Eh of 700 and 900 mV albeit with different kinetics. Leach rates at 700 mV were found to decrease according to HClO₄ > HCl > H₂SO₄ while at 900 mV the leach rate order was HCl > HClO₄ > H₂SO₄. Solution Fe³⁺ activity is found to continually increase during all leaches; however, this is not accompanied by an increase in leach rate.Synchrotron based photoemission electron microscopy (PEEM) measurements showed a localised distribution of adsorbed and oxidised surface species highlighting that pyrite oxidation and leaching is a highly site specific process mediated by adsorption of oxidants onto specific surface sites. It appears that rates may be controlled, in part, by the propensity of acidic anions to bind to the surface, which varies according to , thus reducing the reactive or effective surface area. However, anions may also be involved in specific reactions with surface leach products. Stoichiometric dissolution data (Fe/S ratio), XPS and XRD data indicate that the highest leach rates (in HCl media at 900 mV Eh) correlate with relatively lower surface S abundance. Furthermore, there are indications that solution Cl⁻ assists oxidation especially at higher Eh through the prevention of surface S⁰ buildup at reactive surface sites.