Interactions between sulphide minerals and xanthates,I. The formation of monothiocarbonate at galena and pyrite surfaces

The rate of decomposition of potassium ethyl monothiocarbonate has been determined at pH values between 5 and 10, and its molar absorptivity at 221 nm determined to be 1.24 · 10⁴mol/cm.A novel apparatus for use in the study of reactions between sulphide minerals, oxygen and thiol reagents has been developed, and applied to the reactions of potassium ethyl xanthate with galena and pyrite. It has been shown that both minerals react with ethyl xanthate in the presence of oxygen or oxidation products to form soluble as well as adsorbed xanthate derivatives. The soluble derivative has been identified to be ethyl monothiocarbonate. The adsorbed xanthate at a galena surface, unlike that at a pyrite surface, is gradually converted to a soluble monothiocarbonate under the action of dissolved oxygen. The effect of variables such as pH, the initial xanthate and oxygen concentrations, and the initial state of oxidation of the mineral on the formation of monothiocarbonate has been studied. It is tentatively proposed that an intermediate adsorbed mixed xanthate-hydroxide species is involved in the formation of monothiocarbonate at both galena and pyrite surfaces.The significance of the formation of monothiocarbonate to flotation practice is discussed briefly. The formation of monothiocarbonate represents a wastage of reagent, and could lead to a decrease in flotability of xanthated galena with time of exposure to aerated solutions.     

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.     

Effect of oxidation potential and zinc sulphate on the separation of chalcopyrite from pyrite

The effects of oxidation potential (Eh) and zinc sulphate on the separation of chalcopyrite from pyrite were investigated at pH 9.0. The flotation recovery of these minerals is Eh dependent with maximum separation obtained at 275 mV SHE. Zinc sulphate addition improved this mineral separation at an Eh value of 275 mV by selectively depressing pyrite flotation. A different result was obtained at lower Eh values where zinc sulphate addition improved chalcopyrite flotation but had no or little effect on pyrite flotation. These opposite effects of zinc sulphate on mineral flotation were reconciled by examining the surface species of these minerals. The selective depression of pyrite flotation by zinc sulphate was also confirmed in the flotation of two copper ores.     

Formation and recognition of alkyl xanthyl thiosulphates in sulphide ore flotation liquors

Alkyl xanthyl thiosulphates (R.OCSS.S₂O₃^?) (RXT^?) are formed in solution by mild oxidation (e.g. by I₂) of solutions containing both xanthate and thiosulphate. They can also be formed by reaction of Cu²⁺ with xanthate and thiosulphate, reaction of dixanthogen with thiosulphate, and by reaction of xanthate with tetrathionate; these last three reactions can occur in flotation pulps in slightly acid or alkaline solutions (pH 5–10).Alkyl xanthyl thiosulphates are stable in acid and neutral solution; the solutions have a UV absorption maximum at 289 nm. In strongly alkaline solution (pH 12) RXT^? decomposes within a few minutes to yield a xanthate (mostly) plus a little perxanthate. At pH 10 this decomposition to xanthate takes about 48 h. At pH 7–9 RXT^? is relatively stable. RXT^? is not extracted from aqueous solution with common solvents (chloroform, iso-octane, cyclohexane, or ether). It forms a water-insoluble adduct with cetyltrimethyl-ammonium bromide (CTAB); this adduct can be extracted into chloroform, and the extract has a UV absorption maximum at 296 nm.RXT^? was found in solutions from the gangue-sulphide flotation section at Renison Ltd, the zinc flotation circuit and the copper flotation circuit at Mount Isa Mines Ltd, and the lead flotation section of The Zinc Corporation Ltd. The presence of RXT^? in operating flotation plants has various practical and theoretical implications.     

Flotation of galena. Influence of grain size,of pulp deoxygenation,and of cleaning with ammonium acetate

The flotation of < 10, 10–20, and 20–40 μm galena fractions was studied. For uncleaned galena a given collector coverage produced better floatability with increasing grain size. Nitrogen had a detrimental effect only for the < 10 μm fraction, producing at a given collector coverage a recovery smaller than that obtained with air.Galena cleaned with 400 g/l ammonium acetate had very poor floatability, although xanthate abstraction was fairly high; this confirms that strong xanthate adsorption is necessary for flotation. Formation of monothiocarbonate was small in all cases, which points to a very minor influence, if any, of this compound in the flotation process.In blank flotation tests, or for very low residual xanthate concentrations, a peak at 208 nm and a shoulder at 255 nm were observed. The former was assigned to the uncomplexed Pb²⁺ ion, and the latter was tentatively attributed to the PbOH⁺ ion.Lead in solution results from dissolution of the oxidation products of galena, as galena itself has an exceedingly low solubility. The curve for total lead in solution vs. initial xanthate concentration, had a minimum for an initial xanthate concentration of 10^?5M, the further increase in dissolved lead is attributed to formation of complexes such as PbX⁺ (X = xanthate). Dissolved lead concentrations were nearly as high for cleaned as for uncleaned galena, which indicates a high oxidation rate of the mineral.     

Electrochemical study of the pyrite-oxygen-xanthate system

Polarograms have been determined with pyrite electrode in a buffer solution at pH 9.1, with and without potassium ethyl xanthate and dissolved air, and the resulting oxidation-reduction processes interpreted.It has been observed that the addition of dixanthogen in a nitrogenated solution does not produce any hydrophobicity at the surface of pyrite electrode and does not alter the rest potential and cathodic polarogram.The experimental observations and thermodynamic interpretations provide some support for the production of dixanthogen, developing the first hydrophobic layer, directly at the surface of the pyrite by the action of oxygen of air.     

Interaction of thionocarbamate and thiourea collectors with sulphide minerals: a flotation and adsorption study

The ability of O-isopropyl-N-ethyl thionocarbamate (IPETC), O-isobutyl-N-ethoxycarbonyl thionocarbamate (IBECTC) and butyl ethoxycarbonyl thiourea (BECTU) collectors to increase the flotation of the sulphide minerals, chalcopyrite, galena and pyrite, has been studied. For each collector, the flotation characteristics of these minerals, flotation rate constant and flotation recovery maximum, have been calculated from the flotation data and compared as a function of pH and collector concentration. Overall, the flotation performance of these collectors is stronger for chalcopyrite than for galena and pyrite. Flotation increases with collector concentration and decreasing pH values. For chalcopyrite, the collector performances of BECTU are slightly better than those of IPETC but far superior to those of IBECTC, especially at high pH values or at low collector concentrations. The flotation performance of these collectors has been shown to be in good agreement with the amount of collector adsorbed at the mineral surface. The affinity of BECTU for the various minerals has been calculated using a multilayer adsorption model.     

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.     

Flotation and depression control of arsenopyrite through pH and pulp redox potential using xanthate as the collector

The role of pH and pulp redox potential (E_H) to control the flotation and depression of arsenopyrite has been investigated through studies on microflotation of arsenopyrite crystals and batch flotation of an arsenopyritic ore using isopropyl xanthate as collector. The transition between flotation and depression of arsenopyrite is established by the reversible potential of the xanthate/dixanthogen couple. Adsorption of arsenate ions on ferric hydroxide has been studied through electrokinetics to delineate mechanisms involved in the depression of arsenopyrite using oxidants. Chemical binding between arsenate species and ferric hydroxide sites on arsenopyrite is suggested as the mechanism responsible for depression of arsenopyrite. E_H conditions are given for the flotation and depression of arsenopyite at various pH values for the arsenopyritic ore.     

Selective separation of pyrite from chalcopyrite and arsenopyrite by biomodulation using Acidithiobacillus ferrooxidans

This paper discusses the selective depression of pyrite from chalcopyrite and arsenopyrite by biomodulation using Acidithiobacillus ferrooxidans under natural conditions of pH. The effect of bacteria–mineral interaction on the surface charge of mineral and bacterial cell was studied by microelectrophoresis. Adhesion experiments were conducted to establish the relationship between cell adhesion to specific minerals and the electrokinetic behaviour of the minerals subsequent to interaction with cells. Effect of bacterial interaction on the xanthate-induced flotation of all the minerals was assessed. Adhesion of A. ferrooxidans on pyrite was rapid and tenacious and subsequent to interaction with cells, pyrite remained hydrophilic even in presence of xanthate collector. The collector, on the other hand, was able to render good flotability to chalcopyrite even after interaction with bacterial cells. Copper activated arsenopyrite was able to retain its hydrophobicity in presence of cells due to poor attachment kinetics of cells to the mineral surface. Thus, by suitably conditioning with the cells and collector, it was possible to effectively depress pyrite from chalcopyrite and arsenopyrite.     

Oxidation-Reduction effects in the flotation of chalcocite and cuprite

A laboratory study of the batch flotation of chalcocite from chalcocite-quartz mixtures and of cuprite from cuprite-quartz mixtures with potassium ethyl xanthate as collector has shown that the oxidation-reduction state of the flotation pulp can have a pronounced influence on mineral floatabilities. At pH 11 chalcocite floated over a relatively narrow Eh range of about 300 mV; pH had no influence on the potential of the lower flotation boundary in reducing conditions but had a significant effect on the potential of the upper boundary in oxidizing conditions. Below this upper limit, the floatability was reversible with respect to Eh. Provided the Eh was in correct region chalcocite could be floated in the absence of measurable concentrations of dissolved oxygen.Cuprite displayed a high level of floatability with ethyl xanthate for which, by contrast with chalcocite, no flotation limit in reducing conditions was found; over a small range of potentials close to zero, its behaviour was strongly pH dependent.An attempt to account for the floatabilities of chalcocite and cuprite in terms of the formation of cuprous ethyl xanthate on their surfaces did not lead to correlations with the observed behaviour in reducing conditions but provided a rough correlation with the upper flotation potential limit. It is believed that more detailed and properly controlled comparative flotation studies of the chalcocite-xanthate and cuprite-xanthate systems could help to resolve some of the uncertainties associated with the effects of Eh, pH and oxygen concentration in sulphide mineral flotation.     

Depression mechanisms of sodium bisulphite in the xanthate-induced flotation of copper activated sphalerite

The effect of sodium bisulphite on the xanthate-induced flotation of copper-activated sphalerite has been studied using batch flotation testing, surface analysis techniques (XPS and ToF-SIMS), and FTIR. The various techniques have been used to identify the mechanisms of interaction of sulphite ions with both collector and the sphalerite surface. The results indicate that sodium bisulphite depressed the flotation of sphalerite particles pre-treated with copper and xanthate at pH 9 with nitrogen and air purging. It was found that sodium bisulphite interacts with the sphalerite surface, as well as with xanthate in its adsorbed state. Based on the evidence obtained in the present study, and in conjunction with previous work, the mechanisms involved in the depression of the xanthate-induced flotation of copper-activated sphalerite by sulphite are proposed. It is suggested that copper xanthate decomposition on the surface of the activated sphalerite and the decomposition of the hydrophobic copper-sulphide-like species on the sphalerite surface are the active mechanisms for sphalerite depression by sodium bisulphite.     

Sulphidizing reactions in the flotation of oxidized copper minerals,II. Role of the adsorption and oxidation of sodium sulphide in the flotation of chrysocolla and malachite

The rate of consumption of sulphide in the sulphidizing reactions of malachite and chrysocolla has been measured. The oxidation of sulphide ions at the surface of sulphidized chrysocolla was shown to take place. The influence of thiosulphate anions on the xanthate flotation of sulphidized malachite and chrysocolla was investigated and it was shown to depress the flotation of chrysocolla strongly.The result suggest, that the presence of thiosulphate as a product of simultaneous oxidation can be one of the reasons for the more difficult flotation of sulphidized chrysocolla.     

Flotation of calcareous Mussorie phosphate ore

Separation of Mussorie rock phosphate (P₂O₅ = 20%) from Uttar Pradesh, India, containing pyrite, calcite and other carbonaceous impurities by flotation has been successfully attempted to upgrade the phosphate values. Based on Hallimond cell flotation results of single and synthetic mineral mixtures of calcite and apatite using oleic acid and potassium phosphate, conditions were obtained for the separation of calcite from apatite which is considered to be the most difficult step in the beneficiation of calcareous phosphates. Further studies using 250 g of the mineral (?60 +150 and ?150 mesh fractions, deslimed) in laboratory size Fagergren subaeration machine employed a stagewise flotation viz. carbonaceous materials using terpineol, pyrite using potassium-ethyl xanthate and calcite using oleic acid respectively. Separation was, however, found to be unsatisfactory in the absence of a depressant.Among starch, hydrofluosilicic acid and dipotassium hydrogen phosphate, which were tried as depressants for apatite in the final flotation stage, dipotassium hydrogen phosphate proved to be superior to others. However, the tests with the above fractions did not yield the required grade. This was possibly due to insufficient liberation of the phosphate mineral from the ore body and different experimental conditions due to scale up operations. Experiments conducted using ?200 mesh deslimed fractions has yielded an acceptable grade of 27.6% P₂O₅ with a recovery of about 60%. The results have been explained in terms of the specific adsorption characteristics of phosphate ions on apatite and the liberation size of the mineral.     

The iron-coating role on the oxidation kinetics of a pyritic sludge doped with fly ash

The present study examines the processes that control the oxidation attenuation of a pyrite-rich sludge (72 wt% pyrite) from the Iberian Pyrite Belt by the buffer capacity of a fly ash from Los Barrios power station (S Spain), using saturated column experiments. In addition, in order to understand the behaviour of both materials inside these experiments, a fly-ash leaching test and flow-through experiments with pyritic sludge were carried out. The fly-ash leaching test showed that after leaching this material with a slightly acid solution (Millipore MQ water; pH 5.6) the pH raised up to 10.2 and that the metals released by the fly-ash dissolution did not increase significantly the metal concentrations in the output solutions. The flow-through experiments with the pyritic sludge were performed at pH 9, 22 °C and O₂ partial pressure of 0.21 atm, to calculate the dissolution rate of this residue simulating the fly-ash addition. In the experiments Fe bearing oxyhydroxides precipitated as the sludge dissolved. In two non-stirred experiments the iron precipitates formed Fe-coatings on the pyrite surfaces preventing the interaction between the oxidizing agents and the pyrite grains, halting pyrite oxidation (this process is known as pyrite microencapsulation), whereas in two stirred experiments, stirring hindered the iron precipitates to coat the pyrite grains. Thus, based on the release of S (aqueous sulphate) the steady-state pyritic sludge dissolution rate obtained was 9.0 ± 0.2 × ⁻¹¹ mol m⁻² s⁻¹.In the saturated column experiments, the sludge dissolution was examined at acidic and basic pH at 22 °C and oxygen-saturated atmosphere. In a saturated column experiment filled with the pyritic sludge, pyrite oxidation occurred favourably at pH approx. 3.7. As the leachates of the fly ash yielded high basic pH, in another saturated column, consisting of an initial thick layer of fly-ash material and a layer of pyritic sludge, the pyrite dissolution took place at pH approx. 10.45. In this experiment, iron was depleted completely from the solution and attenuation of the sludge oxidation was produced in this conditions. The attenuation was likely promoted by precipitation of iron-bearing phases upon the pyritic surface forming Fe-coatings (of ferrihydrite and/or Fe(III) amorphous phases) that halted the pyrite oxidation (as in non-stirred flow-through experiments). Results suggest that buffering capacity of fly ash can be used to attenuate the pyrite-rich sludge oxidation.     

Influence of frothers on floatability. I. Flotation of single minerals (quartz and synthetic chalcocite)

The flotation and sorption properties of chalcocite and quartz in potassium ethyl xanthate (EtXK), frothers (α-terpineol and n-amyl alcohol), and (xanthate + frother) mixed solutions were investigated. Surface tension and frothing properties of the solutions were also measured.Floatability and sorption properties of the minerals investigated strongly depended on any controlled or uncontrolled change occurring at the mineral surface. Surface oxidation of chalcocite was shown to be an especially important parameter.The frothers studied showed some collecting properties in respect to chalcocite and quartz and influenced the xanthate sorption on chalcocite.Comparison of the flotation recoveries in frother solutions respectively with and without xanthate indicated an occurrence of noticeable collector-frother interactions during formation of the bubble/chalcocite grain aggregate. No such interactions were found for quartz.Influence of the frothers on floatability of the minerals was observed at different frother concentrations but at close values of surface pressure (π) and of retention time (rt).     

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.     

The effect of thermal treatment on the flotation of chrysocolla

Flotation studies using a Hallimond tube have been carried out on purified samples of chrysocolla. The results confirm that by heating the sample to 550°C, flotation of the sulphidized sample with amyl xanthate is considerably improved. Flotation with sodium dodecyl sulphate is also considerably higher. The recovery with cationic collectors is not modified by the thermal treatment.Electrophoretic mobility measurements and flotation studies using benzene instead of air for the collection of the particles suggest that the increase in flotation after thermal treatment is a consequence of (1) an increase in the solubility of copper ions and their adsorption on to the surface of the particles, and (2) an increase of the intrinsic hydrophobicity of the particles due to condensation of some of the free silanol groups on their surface.     

Characterisation of sphalerite and pyrite flotation samples by XPS and ToF-SIMS

The surface analytical techniques of X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) have provided information on the type and concentration of species on the surface of sphalerite and pyrite particles in flotation concentrate and tail samples, but also on their distribution on each particle and across particles of different sizes. From this surface analytical study, a more accurate interpretation of the flotation results of sphalerite and pyrite minerals in a mixed mineral system could be made as a function of the concentrations of copper sulphate activator and xanthate collector, and particle size. In particular, it was found that sphalerite particles reporting to the concentrate are larger in size and contain less iron hydroxide on their surface than particles reporting to the tail. As for the pyrite particles, their lower recovery than the sphalerite particles is the result of a larger proportion of iron hydroxide on their surface inhibiting copper and collector adsorption.     

Electrochemical studies of sulphides,I. The electrocatalytic activity of galena,pyrite and cobalt sulphide for oxygen reduction in relation to xanthate adsorption and flotation

The electrocatalytic activity of galena, pyrite and Co₃S₄ for oxygen reduction has been studied by potentiostatic methods. Open circuit potentials of the sulphide electrodes have also been measured as a function of pH in nitrogen, air and oxygen atmospheres and also in the presence of H₂O₂ and ethyl xanthate. The adsorption of xanthate on sulphides was followed by observing bubble attachment to the electrodes.The catalytic activity for oxygen (or H₂O₂) reduction (the cathodic currents), the electrode potentials and the xanthate adsorption as shown by bubble attachment within certain pH limits, all varied as $\text{Co}{}_3\text{S}{}_4\text{> pyrite (≈ PbS in H}{}_2\text{O}{}_2\text{) ? PbS}$ indicating considerable dependence of the redox processes in flotation on the d - electron character of the sulphides.In the absence of oxygen, xanthate is probably bonded to the water structure of the surface through hydrogen-bonding, thus keeping the surface hydrophilic. Such adsorption reduces the electrode potential and inhibits oxygen reduction.