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Advances in Colloid and Interface Science 145 (2009) 97 110

in Colloid and Interface Science 145 (2009) 97 – 110 Contents lists available at ScienceDirect Advances

Contents lists available at ScienceDirect

Advances in Colloid and Interface Science

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A review of the fundamental studies of the copper activation mechanisms for selective otation of the sulde minerals, sphalerite and pyrite

A.P. Chandra, A.R. Gerson

Applied Centre for Structural and Synchrotron Studies, University of South Australia, Adelaide, South Australia 5095, Australia

article info

Available online 9 September 2008

Keywords:

Flotation

Copper activation

Collector

Sphalerite

Pyrite

Contents

abstract

A review of the considerable, but often contradictory, literature examining the speci c surface reactions

associated with copper adsorption onto the common metal sul de minerals sphalerite, (Zn,Fe)S, and pyrite (FeS 2 ), and the effect of the co-location of the two minerals is presented. Copper activation , involving the surface adsorption of copper species from solution onto mineral surfaces to activate the surface for hydrophobic collector attachment, is an important step in the otation and separation of minerals in an ore. Due to the complexity of metal sulde mineral containing systems this activation process and the emergence

of activation products on the mineral surfaces are not fully understood for most sul de minerals even after

decades of research. Factors such as copper concentration, activation time, pH, surface charge, extent of pre-oxidation, water and surface contaminants, pulp potential and galvanic interactions are important factors affecting copper activation of sphalerite and pyrite. A high pH, the correct reagent concentration and activation time and a short time delay between reagent additions is favourable for separation of sphalerite from pyrite. Suf cient oxidation potential is also needed (through O 2 conditioning) to maintain effective galvanic interactions between sphalerite and pyrite. This ensures pyrite is suf ciently depressed while sphalerite oats. Good water quality with low concentrations of contaminant ions, such as Pb 2+ and Fe 2+ , is also needed to limit inadvertent activation and otation of pyrite into zinc concentrates. Selectivity can further be increased and reagent use minimised by opting for inert grinding and by carefully choosing selective pyrite depressants such as sulfoxy or cyanide reagents. Studies that approximate plant conditions are essential for the development of better separation techniques and methodologies. Improved experimental approaches and surface sensitive techniques with high spatial resolution are needed to precisely verify surface structures formed after copper activation. Sphalerite and pyrite surfaces are characterised by varying amounts of steps and defects, and this heterogeneity suggests co-existence of more than one copper sul de structure after activation.

© 2008 Elsevier B.V. All rights reserved.

1. Introduction

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98

2. Activation of sphalerite

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98

2.1. Mechanisms of Cu(II) activation .

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98

2.2. Reaction kinetics .

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100

2.3. Mechanisms of Cu(OH) 2 activation .

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100

2.4. Zeta potential and isoelectric point .

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100

2.5. Copper concentration and activation duration .

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101

2.6. The effect of sphalerite iron content on copper activation

 

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102

2.7. Sphalerite surface oxidation .

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102

2.8. Lead and iron sphalerite activation .

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103

3. Copper activation of pyrite .

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104

3.1. Unactivated otation

 

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104

3.2. Mechanisms of Cu(II) and Cu(OH) 2 activation .

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104

3.3. Effectiveness of activation

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105

Corresponding author. Tel.: +61 8 8302 3044; fax: +61 8 8302 5545. E-mail address: andrea.gerson@unisa.edu.au (A.R. Gerson).

0001-8686/$ see front matter © 2008 Elsevier B.V. All rights reserved. doi: 10.1016/j.cis.2008.09.001

98

A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110

4. Mixed pyrite and sphalerite otation .

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105

5. Summary

 

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107

Acknowledgments

 

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109

References

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109

1. Introduction

Flotation is an important and versatile mineral processing step used to achieve selective separation of minerals and gangue. It utilises the hydrophobic (aerophilic) nature of mineral surfaces and their propensity to attach to rising air bubbles in a waterore pulp as the basis for separation [1]. Metal sul de minerals, for which this process was originally developed, are generally weakly polar in nature and consequently most have a hydrophilic surface [2]. Hence, collector molecules such as xanthates and dithiophosphates are normally used to increase hydrophobicity [3] . Certain sul de minerals such as sphalerite (ZnS) do not respond well to short chain thiol collectors, due to the relative instability of zincxanthate and hence require the use of activators to enhance the adsorption between collector molecules and the sphalerite surface [2,4]. The cupric ion (Cu 2+ ), generally in the form of sulfate or nitrate, is the most widely used activator. Other heavy metal ions such as lead, silver, cadmium, mercury and Fe 2+ /Fe 3+ can also activate the sphalerite surface, but are either not used commercially or are present as impurities within the sphalerite lattice or in process water [5,6]. Separation of sphalerite through copper activation becomes problematical when other minerals within the pulp are inadvertently activated along with the sphalerite. Pyrite (FeS 2 ) is one such mineral that responds to copper activation and can be oated together with sphalerite [2] . Being the most abundant sulde mineral pyrite is undesirably associated, and in most cases ne grained and intimately intergrown, with minerals of economic value [7] . This gangue pyrite is a cause of reduced concentrate grade and increased smelting costs, for most minerals such as sphalerite, chalcopyrite and galena. Pyrite is also a primary contributor towards the substantial environmental problem of acid mine drainage resulting in acidication of natural water systems. Mining industry treatment costs, in the US alone, are over $1 million/day [8]. Sphalerite and pyrite frequently occur together in ore deposits along with galena and copper containing ores such as chalcopyrite. The common practice in mine otation is to rst oat the copper containing minerals (if present) followed by galena [2,9]. The tails from the galena otation are then used to oat sphalerite away from pyrite primarily using copper activation. Effective separation is needed to minimise iron in the nal zinc concentrate that may occur through pyrite copper activation and otation. Loss of selectivity and unwanted activation can also occur due to contaminants present in the mine water used for separation of these minerals. Despite continuous process improvements the problem of pyrite misreporting to sphalerite concentrates still remains [10,11]. A review of the key factors affecting copper activation of sphalerite and pyrite is presented herein. Special attention is given to the role of sphalerite iron content. A discussion of the proposed activation products as identied by various fundamental studies is provided as is an examination of the literature regarding the activation and otation response of the mixed sphalerite/pyrite system. While only sphalerite and pyrite activation is discussed, the issues raised may also apply to other sul de minerals.

2. Activation of sphalerite

The activation of sphalerite has been studied extensively over several decades [5,1214]. While there is general agreement on the overall process of copper activation, the actual mechanism and surface reaction products controlling activation/otation still remains controversial.

It has been well established that copper activation of sphalerite follows an ion exchange mechanism where the uptake of Cu(II) 1 results in approximately 1:1 release of Zn 2+ into the solution [5,13,15] and is generally represented by Eq. (1) [16].

ZnS ð s Þ þ Cu 2þ

ðaqÞ CuS ð s Þ þ Zn 2þ

ð aqÞ

ð1Þ

Cu(II) on the sphalerite surface is subsequently reduced to Cu(I) with the resulting oxidation of the surface sulde. Collector molecules, such as xanthates, then react with the surface copper sulde species formed, thus increasing the otation response [17]. Cu(I)xanthate is the main surface product formed, especially at low pH [15]. The uptake of copper and subsequent otation of sphalerite is seen to depend on impurities, such as iron, present within natural sphalerite, surface oxidation, copper and xanthate concentration, activation time, solution O 2 concentration (pulp potential) and most importantly on pH. Under contrasting pH conditions either an abundance of hydro- phobic (collector absent) or hydrophilic species maybe present on the sphalerite surfaces [14]. Hydrophobic species such as polysul des (S

)

and elemental sulfur (S ) appear to predominate at mildly acidic conditions while hydrophilic species such as zinc hydroxide and copper hydroxide, along with some sulte/sulfate, occurs at higher pH [14,15,18] . Polysul des or elemental sulfur forms as a result of oxidation of metal-decient sul de on sphalerite surfaces, however it is still unclear if one or both of these products form and their relative abundance on the surface [14,18,19]. The presence of such hydrophobic species tends to promote collectorless otation of sphalerite which is more prevalent at low pH [5,15]. Collectorless otation of sphalerite may also be seen when impurities such as copper and iron, diffuses from the bulk to the surface under acidic conditions [20]. This happens after zinc dissolution when bulk cationic impurities migrate to the metal-decient (sulfur-rich) sphalerite surface resulting in a self- activatingmechanism. Surface hydrophilic species are seen to reduce recovery by otation with xanthate collectors, only within the pH range where such species are stable [14]. Fig. 1 shows the various processes that may take place simulta- neously during copper activation of sphalerite that result in the production of hydrophobic and hydrophilic species. These processes may also occur during activation of other suldes. Selective adsorption of Cu(II) is the desired process. However, depending on activation conditions, precipitation of hydrophilic copper containing hydroxide species onto sphalerite surface takes place. In addition, aqueous Cu 2+ and/or Cu(OH) 2 also reacts with collector molecules leading to non- selective adsorption of hydrophobic CuX or dixanthogen (X 2 ) on sphalerite surfaces.

2

n

0

n

2.1. Mechanisms of Cu(II) activation

It has been noted that out of the many stable and metastable intermediates present in a copper/sulfur system, researchers have mainly considered CuS (covellite) and Cu 2 S (chalcocite) as possible end products of copper activation of sphalerite (Buckley et al. [20]). Buckley et al. [21] found a Cu 2p 3/2 Auger parameter of 1850.0 eV on copper-activated sphalerite which was about 0.3 eV lower than that for covellite and hence suggest that even if a CuS-like phase forms it is not same as covellite. They also did not nd any evidence of elemental sulfur formation. Buckley et al. [20] describe the activated sphalerite

1 The nomenclature (I), (II) or (III) is used throughout to denote surface or bulk species while superscript oxidation state numbers are used to denote aqueous species.

A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110

99

in Colloid and Interface Science 145 (2009) 97 – 110 99 Fig. 1. Schematics of sphalerite

Fig. 1. Schematics of sphalerite copper activation showing the various simultaneous processes likely to occur under different activation conditions.

surface as a copper-substituted sphalerite lattice with the formation of a metal-decient sulde (sulfur-rich) surface layer in both acidic and alkaline media. This, according to them, is better represented by Eq. (2), than by Eq. (1), where the product is metastable.

ZnS ð s Þ þ x Cu 2þ

ð

aqÞ Zn 1 x Cu x S ð s Þ þ xZn 2þ

ð aqÞ

ð2Þ

Using conventional X-ray diffraction (XRD), scanning electron micro- scopy (SEM) coupled with energy dispersive spectrometry (EDS) and electron microprobe analysis (EMPA), Vinals et al. [22] found digenite (Cu 1.8 S) to be the main activation product at pH 1.1 1.3 and temperatures of 180212 °C while chalcocite appears to predominate at 225 °C. These temperatures are well above the temperatures found within mineral processing plants. Chen and Yoon [23] conducted rest potential measurements and voltammetry at pH 9.2 using a carbon matrix composite (CMC) electrode containing sphalerite particles, to show that when copper activation is carried out at open circuit conditions a CuS-like activation product forms while activation conducted at lower potentials produces a Cu 2 S-like product. They further showed that activation conducted under slightly oxidising conditions produced hydrophobic species, such as copper polysul- des, on the surface. Pattrick et al. [17] used Cu K edge and S K edge X-ray absorption spectroscopy (XAS, consisting of both extended X-ray absorption ne structure, EXAFS, spectroscopy and X-ray absorption near edge spectroscopy, XANES) data to show that copper on activated sphalerite, at pH 1012, exists in a tetrahedrally coordinated form, bonded to three sulfur atoms and one oxygen atom. However, these measurements were carried out on dry samples and hence chemad- sorbed water may have been present that is not localised on the adsorbed copper atoms within wet slurry. Upon addition of xanthate collector the oxygen of the Cu O (2.07 Å) bond is replaced by sulfur from the xanthate and a primitive covellite species forms. However, also using XAS, it was shown by Gerson et al. [13] that under mildly acidic conditions both bulk and surface copper is coordinated only to three sulfur atoms in a distorted trigonal planar geometry with a CuS average bond length of 2.27 ± 0.02 Å. These measurements were carried out using wet slurry. It was proposed that this geometry cannot be attributed to the formation of a distinct crystallographic copper sulde phase and the data could not be adequately tted to a structural model encompassing Cu O bonds. It has been further shown in Gerson et al. [24] that this distorted trigonal planar structure (CuS 3 ) on the sphalerite surface is slightly pushed up

and outwards resulting from the shorter CuS bonds as compared to bulk Zn S bonds, and elongation of the attaching Zn S bonds. It was found that the copper-activated sphalerite surface has Cu S bonds 0.009 ± 0.001 nm shorter than bulk ZnS bonds with a copper to zinc distance 0.013 ±0.006 nm longer than the zinc to zinc distance. Buckley et al. [21] recently examined a relatively pure copper- activated sphalerite surface (from Santander, Spain) using synchrotron X-ray photoelectron spectroscopy (XPS, Cu, Zn and S 2p 3/2 binding energies) and XANES (Cu L 2,3 edge). This study reconrmed that copper on activated sphalerite surface exists predominantly as Cu(I), although a higher than expected d 9 character was found. Moreover it was also found that some Cu(II) ions were present on the surface, associated with oxygen (Cu(II)O species) possibly due to chemi- sorbed water on the sphalerite surface. Buckley et al. [21] suggested the formation of a metastable phase (Zn 1 x Cu x S) with formal oxidation state of sulfur being more positive than 2. This notion of

S being more positive is consistent with the model proposed by

Gerson et al. [13]. Furthermore, on the basis of the poor correlation seen between the concentration of high binding energy sulfur and surface copper concentrations, Buckley et al. [21] suggest unsubsti- tuted (by copper) oxidative losses of zinc (Eq. (3)) from the sphalerite lattice which leads to the development of enhanced sulfur regions with oligosul de-like electronic environments.

Zn 1 x Cu x S ð sÞ Zn 1 x y Cu x S ð s Þ þ yZn 2þ

ð aqÞ þ 2ye

ð3Þ

Kartio et al. [19] suggested that there may be difculties in assigning Cu 2p 3/2 binding energies (even from synchrotron XPS) to either CuS

or Cu 2 S. The variable XPS S 2p binding energies observed have led to

the suggestion that sulfur was present in different oxidation states (non-integer) depending on the extent of copper activation and most proposed mechanisms fail to account for this [13]. On this basis it was

proposed that increased copper activation resulted in less negative sulfur oxidation states. The reaction mechanism provided for surface substitution (Eqs. (4) and (5) for an initial and then a second copper substitution respectively) and bulk substitution (Eq. (6) for a single substitution) of zinc with copper result in the formation of a similar distorted trigonal planar geometry with copper bonded to three sulfur atoms but variable sulfur oxidation states. Note in Eq. (5) the less negative oxidation state of the bridging sulfur atom.

aqÞ þ ðZn 2þ S 2

Cu 2þ

ð

3

Þ

4

ð surfaceÞ ðCu 0:9 S 3

1 :63 Þ 4

ð surfaceÞ þ Zn 2þ

ð aqÞ

Cu 2þ

ðaq Þ þ ð S 2

1 :63 Cu 0: 9þ S 1: 63 Zn 2þ S 2Þ 6

2

ðsurfaceÞ

ðS

1: 63Cu 0: 9 þ S 1: 28 Cu 0: 9þ S 1: 63Þ 6

2

2

ðsurface Þ þ Zn 2þ

ðaq Þ

½ S 2 Zn 2þ S 2 Zn 2þ

3

3

0

ð bulkÞ þ Cu 2þ ð aqÞ ½S 3

1:63 Cu 0: 8þ 4: 09

bulkÞ

ð

þ

½ S 0: 8 Zn

1:63þ 6

3

ð bulkÞ þ Zn 2 þ

ð aqÞ

ð4Þ

ð5Þ

ð6Þ

Activation by Cu(II) results in the formation of a conducting layer (with the band gap as low as 1.1 eV) on sphalerite surfaces [14,19]. Sphalerite is naturally an insulator with a band gap of 3.5 eV. This reduced band gap aids in electron transfer reactions and allows the thiol collectors to form an insoluble collector complex on the sphalerite surface through mixed potential electrochemical reactions [19,20]. Ab initio cluster model calculations have also shown that copper atoms incorporated into the sphalerite lattice enhanced the electron acceptor ability of sphalerite [25] . Cu(I) xanthate and dixanthogen formation in solution in acidic medium is proposed to occur via Eq. (7) [26]. Dixanthogen adsorption is more prevalent on unactivated sphalerite [17] or when the Cu(II) concentration is low [4] .

2Cu 2þ

ðaqÞ 4EX

ðaqÞ 2CuEX 2 ðaqÞ 2CuEX ð aqÞ þ X 2ð aqÞ

ð7Þ

100

A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110

2.2. Reaction kinetics

The initial stage of the activation process, generally, is very fast with a high rate of copper uptake within rst 10 to 15 min [15,19,27]. This initial copper migration into the sphalerite surface can have a diffusion coef cient of 1.0 × 10 11 to 1.5 × 10 10 cm 2 ·s 1 in the temperature range of 80 to 400 °C [28]. It has been proposed that the rate of reaction is rst order with respect to copper concentration, with the rate controlled by diffusion through the solution phase [5] . Thereafter the rate of copper uptake generally slows and shows logarithmic time dependency [19] which is associated with copper diffusion into the bulk of sphalerite lattice [5,29]. Vinals et al. [22] found that this latter reaction rate followed a parabolic kinetic law at high temperatures (160 225 °C) and had a high activation energy of 147 kJ·mol 1 . This indicated a kinetic control of the reaction by solid- state counter diffusion of Cu(I) and Zn(II) ion through the copper sulde layer. The two step activation kinetics observed may be due to a difference in mechanism for the adsorption/absorption of surface and bulk copper. It has been proposed, based on EXAFS data, that copper is incorporated onto the surface via replacement of three Zn S bonds with commensurate low activation energy [13]. However, the bulk copper results from replacement of four Zn S bonds to form only three Cu S bonds which requires greater activation energy. XPS depth pro ling showed signicant Cu 2p signal even after 15 nm of argon ion etching [14,18]. Such copper diffusion processes may however reduce the formation of surface Cu(I) xanthate especially in dilute acidic solutions [26]. Popov and Vucinic [26] showed, through IR internal reection measurements, that when the activation time was long and copper was allowed to diffuse into the bulk sphalerite structure, the concentration of Cu(I) xanthate on the surface was reduced. Flotation studies however do not show any signicant decrease in sphalerite recoveries as a result of this decrease in surface xanthate (refer Section 2.5 for further details) [30].

2.3. Mechanisms of Cu(OH) 2 activation

Prestidge et al. [18] studied the activation of synthetic sphalerite, conditioned for 30 min at pH 9, using different concentrations of copper nitrate. Using conventional XPS, they showed that at high copper concentrations (10 or more monolayer coverage) the sphaler- ite surface becomes heavily coated with Cu(OH) 2 . SIMS results by Gerson et al. [13] conrmed the occurrence of colloidal Cu(OH) 2 on sphalerite particles at high pH and high nominal copper coverage. Similar results were also found by Fornasiero and Ralston [14], while Popov and Vucinic [15] also noted an apparent depressing effecton sphalerite otation at high copper concentration and alkaline pH. Prestidge et al. [18] explain that Eq. (2) is more representative of copper activation in an acidic medium where the activating species is only Cu 2+ . According to them, activation in alkaline conditions where surface Cu(OH) 2 precipitate is found to be the predominant activating species, is better represented by Eqs. (8), (9).

nZn ð s Þ þ

x CuðOH Þ 2ð pptÞ ðZnSÞ n d x CuðOH Þ 2ð surfaceÞ

ð8Þ

The Cu(II) from the hydroxide may then exchange with the Zn(II) from the sul de.

ðZnSÞ n d x CuðOH Þ 2ð surfaceÞ Zn n xCu x d xZnðOHÞ 2ð surfaceÞ

ð9Þ

The zinc hydroxide formed undergoes dissolution and/or dispersion, the extent of which controls the surface hydrophobicity [14,18]. The resulting Cu(II) sulde then undergoes redox disproportionation to form Cu(I) sulfur products. These products may then form Cu(I)xanthate upon collector addition by combining with xanthate [17]. At increased copper concentration the copper-substituted zinc sul de layer becomes coated with an inhibiting copper hydroxide over-layer

[18]. A similar process has also been observed for pyrite [31] however Cu(I) was observed on the pyrite surface prior to Cu(OH) 2 deposition. There has been suggestions that X-ray based techniques (especially in ultrahigh vacuum, e.g. XPS) may cause an increase in the Cu(I) signal from activated sphalerite, through photoreduction of Cu(II) to Cu(I) [5,18]. Such a reduction process has now been shown to be conned only to Cu(OH) 2 over-layers, at extended X-ray irradiation time, and does not affect Cu(II) involved with activation [32]. An associated reduction in the surface concentration of oxygen was however observed, and authors have suggested the use of a N 2 -cooled sample holder to minimise this loss. An additional experimental uncertainty may result from the necessity to conduct measurements on dry samples where the surface species may not necessarily be represen- tative of those in mineral slurry. The use of in situ techniques such as IR will be ideal as it eliminates the need to house samples in ultrahigh vacuum. Some researchers believe that for sphalerite in alkaline media the surface Cu(OH) 2 directly interacts with the xanthate, where the OH ion is exchanged with the xanthate ion [4,15]. The resulting product then decomposes to form Cu(I)xanthate and dixanthogen on the surface (Eqs. (10) and (11)).

CuðOH Þ 2ð surfaceÞ þ 2EX ð aqÞ CuðEX Þ 2ð surfaceÞ þ 2OH ðaqÞ

2CuðEXÞ 2ð surfaceÞ 2CuEX ð surfaceÞ þ ðEX Þ 2ð surfaceÞ

ð10Þ

ð11Þ

2.4. Zeta potential and isoelectric point

The zeta potential and the isoelectric point (iep) of sphalerite are also in uenced by the surface speciation resulting from variations in pH, conditioning time, reagent, and reagent concentrations [14,15,33,34]. Popov and Vucinic [15] used microelectrophoresis and performed electrokinetic measurements on sphalerite particles, conditioned with different reagents of varying concentration, as a function of pH. It was found that sphalerite on its own had positive zeta potential in acidic conditions and negative zeta potential in alkaline conditions with the iep at pH 6.5. This remained the same when sphalerite was conditioned with xanthate. However conditioning sphalerite with copper sulfate solution yielded a different zeta potential pH curve with copper solutions of different concentrations resulting in different sphalerite zeta potential pH dependencies. Zeta potential for sphalerite was negative below pH 6 for all copper concentrations used, which according to Popov and Vucinic [15] showed the exchange of Cu(II) with Zn(II) from the sphalerite lattice. The negative zeta potential value suggests that the surface was stabilised and no H + adsorption took place. Zeta potential of sphalerite conditioned with higher copper concentration (8.0 ×10 4 mol·dm 3 ) showed two charge reversals with increasing pH. According to Popov and Vucinic [15], the rst charge reversal from negative to positive at pH 6 was due to adsorption and precipitation of positive hydrolysed copper ion species (Cu 2 (OH) 2+ 2 , Cu(OH) + ) pre- dominantly on the sphalerite surface while the second charge reversal from positive to negative at pH 7.6 resulted from deprotonation of the copper hydroxide that predominantly covered the sphalerite surface. This behaviour is in contrast to the less concentrated copper solution

showed a signicant decrease to more

(1.56 × 10 4 mol·dm 3 ) which

negative zeta potential values from pH 6 to 8 and no charge reversals. Sphalerite conditioned with copper and xanthate showed negative zeta potential throughout the pH range (5.8 to 9.2) due most likely to the adsorption of xanthate (X ) onto the sphalerite surface. Charge reversals are usually common in mineral oxides, silicates and suldes in the presence of adsorbing metal ions and this behaviour can vary depending on type of metal ion, its salt and its concentration [35]. Zhang et al. [34] used a similar technique to study the zeta potential of sphalerite alone and conditioned with various concentra- tions of ferrous ion and xanthate as a function of pH. While basic zeta

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potentialpH trends obtained by Zhang et al. [34] were similar to those from Popov and Vucinic [15], the sphalerite zeta potential values of Zhang et al. [34] were predominantly negative for all conditions studied throughout the pH range (212) and the iep of sphalerite was located at pH 2.5. A signicant difference in these two studies was the iron content of sphalerite samples used. Popov and Vucinic [15] used a natural sphalerite sample containing approximately 13 wt.% iron while Zhang et al. [34] also used a natural sphalerite sample but containing only 2.8 wt.% iron. Sphalerite samples with different iron contents are known to exhibit different zeta potential values [33]. Gigowski et al. [33] demonstrated that the zeta potential and iep of sphalerite varies non- linearly with the iron content of sphalerite. Mirnezami et al. [36] also suggests the likelihood of iron content inuencing iep (and hence zeta potential) of sphalerite. While investigating the aggregation mechan- ism of sphalerite particles Mirnezami et al. [36] measured the electrophoretic mobilities of sphalerite of different iron contents and found that the iep of the sample with low iron (mineral sample) was at a lower pH than the samples with higher iron content (plant concentrates). This was attributed to the presence of increased concentrations of zinc oxidation products on the plant concentrates, however the added inuence of iron was also suggested. Sphalerite surface charge thus appears to be an important factor to be considered in the differential activation/otation response of sphalerite with different iron contents (refer Section 2.6), normally observed in fundamental studies. In a recent study, Fornasiero and Ralston, [14] measured electro- phoretic mobilities of sphalerite, conditioned at either pH 6.0 or 8.5, with increasing copper concentrations and used XPS measurements to identify the surface species causing the observed change in zeta potential with pH. The zeta potential trend with pH was similar to those found by Popov and Vucinic [15] and Zhang et al. [34]. At pH 6.0, polysuldes were one of the species found on the surface of sphalerite responsible for decreasing the zeta potential to negative values. These polysuldes may have appeared as a result of the formation of metal- decient sulfur-rich phases formed on metal dissolution and may possibly exist as (Cu + ) 2 S 6 [19] or as (Cu + ) 2 S 2 [18]. In addition, at this pH, Fornasiero and Ralston, [14] also identied zinc and cupric suldes as important species which were also responsible for the low zeta potential. The sphalerite surface conditioned at pH 8.5 was dominated by zinc and copper hydroxide/oxide and sulte/sulfate species. The abundance of these species at pH 8.5 increases further with increasing concentration of conditioning copper. These species are responsible for making zeta potential values less negative above pH 5 and positive above pH 6.5.

2.5. Copper concentration and activation duration

Fornasiero and Ralston [14] showed (under their reaction conditions) that maximum collectorless otation recovery can be obtained at copper concentrations of 2 × 10 6 mol·dm 3 /g of 38 b x b 75 μ m sphalerite while Popov and Vucinic [15] found 3 × 10 5 to 2.5 ×10 5 mol·dm 3 Cu 2+ concentration better for 104 b x b 208 μm sphalerite otation using xanthate. Typically copper concentrations ranging from 1 × 10 4 to 1 × 10 6 M have been used to conduct activation and otation studies of sphalerite [26,30,31,3744]. Section 3.3 provides typical plant concentrations used for copper activation. The copper concentration needed to give maximum otation response will differ depending on the activation conditions, origin of the mineral sample and available surface area for activation. This ideal copper concentration needs to be established through experimentation at xed activating conditions. Fornasiero and Ralston [14] found that increased Cu 2+ concentration had the effect of continuously decreasing the otation of sphalerite (in the absence of collector), with maximum reduction seen at pH 8.5 10, probably due to the formation of Cu(OH) 2 precipitates. The thickness of this Cu(OH) 2 layer generally increases

with increasing copper concentration at mildly acidic conditions [18]. The effect of increasing copper concentration on otation is not evident above pH 12 where Cu(OH) 3 is the stable species (not Cu(OH) 2 ppt ) and below pH 5 where only Cu 2+ is the stable copper species [14] . High copper concentrations may also interact with xanthate collectors in the pulp preventing adsorption onto the activated sphalerite surfaces [15] . To minimise this side reaction, effectively causing reagent loss, sequential addition ( rst Cu 2+ , then collector followed by lime) is now the preferred technique at Noranda Group operations (Section 4.0) [11] . Prestidge et al. [18] found that an increase in activation time or aging had the effect of reducing the Cu(OH) 2 over-layer, evident from the absence of high binding energy components and satellites from the Cu(II) 2p XPS signal. They proposed that happens due to migration of copper into the bulk sphalerite as surface Cu(OH) 2 continues to transform into the copper-substituted zinc sulde structure with prolonged activation. Increasing the activation time therefore increases the copper uptake with subsequent increase in the release of Zn 2+ [19] while increasing collector concentrations increases collector adsorption onto the surface [4,5]. However, increased copper uptake may not be equally benecial for surface xanthate adsorption Popov and Vucinic [26] conducted oatability and infrared internal reection studies on a high iron (13 wt.%) containing sphalerite (104 b x b 208 μm) in weakly acidic medium and investigated the effects of prolonged activation time and copper concentration. For the short activation time (2 min) it was found that Cu(I)xanthate was the dominant species on the surface with a small concentration of Cu(II)xanthate. However, the amount of Cu(I) xanthate decreased with increasing activation time, evident from reduced peak intensity (at 1197 cm 1 ) in the IR spectra. Prolonged activation time also resulted in a slow diffusion of Cu(I) into the bulk sphalerite structure. Increased copper adsorption was observed when the copper concentration was increased in solution with long activation times, however Cu(I) xanthate formation was still lower at than at short activation times. Interestingly, the otation recovery of sphalerite was greater for samples activated for prolonged periods and/or with increased activating copper concentration. Lascelles et al. [30] demonstrated that an increased time delay between Cu 2+ addition and xanthate addition decreased the amount of collector adsorbed on to the sphalerite surface at high pH (9.2) but not at neutral or mildly acidic pH. At high pH it is known that Cu 2+ can also adsorb as Cu(OH) 2 colloids [18]. On the basis of XPS measure- ments, Lascelles et al. [30] suggested that on delay between Cu 2+ and xanthate addition, colloidal Cu(OH) 2 adsorbed onto the sphalerite surface is lost to the solution resulting in decreased surface xanthate adsorption. There was no (as was expected) decrease in the otation response of sphalerite with reduced surface xanthate probably due to collectorless otation, however the authors suggest early addition of xanthate. The presence of both copper and xanthate (and their quantity) may also inuence interactions between sphalerite and gangue particles. Duarte and Grano [39] conducted batch otation, zeta potential measurements and rheological studies on silicate gangue minerals (d 85 of 1.0 μm) and ultrane sphalerite (d 85 of 7.9 μm) to show that at pH 9 silica can misreport to sphalerite concentrates through a combination of entrainment and aggregation (with sphalerite parti- cles) but not through true otation via surface hydrophobisation. Under their reaction conditions, Duarte and Grano [39] found that when no reagents were added in a mixed mineral system (silica and sphalerite), silicate gangue minerals misreport to sphalerite concen- trate primarily through entrainment. However, when 1800 g/t copper sulfate is present with 1500 g/t isopropyl xanthate, silicate gangue minerals misreport via a combination of entrainment and aggregation as determined from batch otation and cryogenic SEM analysis. In addition, rheological studies were used to show that particle interactions increased upon copper sulfate and xanthate addition.

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They also found that the zeta potential of silica became less negative upon addition of copper sulfate and xanthate. They theorised that reagents modied the surface characteristics of silica causing the surface charge to become less negative to values near the iep of silica, where electrostatic repulsive forces are relatively low. This allowed sphalerite and silica particles to interact and form aggregates that report to the concentrates along with entrainment. It has previously been shown that aggregation of sphalerite particles can occur through occulation [36]. Mirnezami et al. [36], on the basis of settling velocity, suspension analysis and optical microscopy, showed the presence of aggregates in sphalerite particles at pH 7 9 as a mechanism of sphalerite misreporting to lead and copper concentrates in the processing of PbCuZn sulde ores. They found that sphalerite releases sufcient zinc ions in solution (which forms hydroxide in the pH range 79) and causes aggregation. A occulating mechanism of aggregation was suggested involving polymeric zero-charge Zn 2+ species, [Zn(OH) 2 (H 2 O) 2 ] 0 n .

2.6. The effect of sphalerite iron content on copper activation

Pure sphalerite (cubic ZnS) contains nearly 67 wt.% Zn and 33 wt.% S [45]. However, natural ZnS normally contains iron (along with other minor impurities) substituted for zinc atoms [46], amounts of which depend on the temperature and chemistry of the crystallisation environment [45,47]. The presence of iron decreases the band gap of sphalerite, which is naturally an insulator, and affects its reactivity [48] . The iron content of sphalerite has been seen to inuence the activation and subsequent otation behaviour of sphalerite during fundamental studies; however contradictory results have been reported [20,27,33,38,48,49]. Table 1 provides a summary of copper activation and otation studies conducted over the last two decades with sphalerite samples of various iron and lead (where this data is available or lead is present) contents. This table also lists the various conditions (where available) used for these studies. The pH, activator and collector used are fairly consistent. However, other important factors such as activation time and particle size are quite different. Using synthetic sphalerite containing various iron contents (up to 40 wt.%) and 64 Cu labelled CuSO 4 , Solecki et al. [27] showed that adsorption of Cu 2+ decreased with increasing concentration of iron in sphalerite. In another study, Szczypa et al. [49] further demonstrated, with synthesised sphalerite, that increasing the iron content also results in decreasing attachment of xanthate to copper-activated sphalerite, primarily due to reduced copper on the sphalerite surface. XPS studies by Buckley et al. [20] on two natural sphalerite samples with different (high and low) iron contents also appear to support these ndings. However, they acknowledged the gradient in lead

content of the two samples, where the sample with higher iron content also had higher lead content, could also be exerting an effect. Recent studies by Boulton et al. [38] also support the notion of iron content of sphalerite reducing the rate of copper-activated sphalerite otation. By carrying out otation studies (at pH 11) on two natural sphalerite samples, with high iron (12.5 wt.%) and low iron (0.3 wt.%), Boulton et al. [38] concluded that the presence of iron in the sphalerite lattice reduces the exchange sites (zinc) for Cu 2+ , with this effect being more pronounced for coarser particles presumably due to the lower surface area to volume ratio. They however found that iron content had no inuence on maximum recovery and otation rate constant at low copper concentrations. However, Gigowski et al. [33] and Harmer et al. [48] have reported contrasting trends to those found by Solecki et al. [27], Szczypa et al. [49], Buckley et al. [20] and Boulton et al. [38]. Using natural sphalerite with varying iron content (up to 12 wt.%) they showed that copper- activated iron-rich sphalerite preferentially adsorbs xanthate. How- ever, despite this no direct relationship between oatability, iron content and copper concentration was found [33]. Recent studies by Harmer et al. [48] demonstrated that as the iron content of sphalerite increased the amount of Cu 2+ adsorbing onto the sphalerite surface also increased. Using a combination of electron microprobe analysis (EPA), atomic force microscopy (AFM) and XPS on ve different sphalerite samples with varying iron content (Table 1 ), they showed that as the iron content of the sample increased the number of surface defects and steps along with the size of surface oxidation products also increased. The increased surface defect sites allow more Cu 2+ to be adsorbed compared to samples with low iron content (less defect sites). In addition samples with higher iron content undergo a more rapid oxidation than those with lower iron content, hence iron further aids in Cu 2+ adsorption. A decrease in the Fe 2p 3/2 doublet intensity was also noted compared that of the zinc, suggesting copper replaced iron in the sphalerite preferentially over zinc.

2.7. Sphalerite surface oxidation

The sphalerite surface is characterised by steps and defects, size and frequencies of which tends to increase with impurities such as iron [48]. Therefore, sphalerite surface preparation for activation and the degree of pre-oxidation of the surface may affect the available surface area for the uptake of copper and xanthate, and are thus also important factors to be considered. Harmer et al. [46] studied a high iron sphalerite surface (110) using electron probe microanalysis (EMPA), Rutherford backscattering (RBS), PIXE, XPS, and medium energy ion scattering (MEIS) and found that vacuum fractured and air fractured samples undergo varying degrees of relaxations and

Table 1 Copper activation and otation studies conducted over the past two decades and conclusions reached using sphalerite samples with different iron and lead contents

Sample (size)

Fe content

Pb content Activator (time)

Collector used

pH

Conclusion

Reference

Synthetic (not given)

0%

Not

64

CuSO 4

8

Increase in Fe causes decrease in Cu adsorption

[27]

5%

present

(not given)

 

40%

Synthetic (not given)

0%

Not

CuSO 4

Ethyl xanthate

6, 8, 10

Increase in Fe reduces xanthate adsorption due to lower Cu adsorption

[49]

5%

present

(20 min)

 

40%

Natural (not given)

33 a

0.2 a

CuSO 4

9.2

Cu uptake by high Fe sample was less than for the low Fe sample

[20]

115 a

24 a

(1 h)

 

Natural (125200 μ m)

0.38%

0.04%

CuSO 4

Sodium isopropyl

Fe rich sphalerite adsorbs more Cu and preferentially binds to xanthate Fe inhibits initial Cu activation but catalyses

[33]

12%

0.20%

(not given)

xanthate

Synthetic: ZnSe and ZnS Natural:

High (exact

(Not

CuSO 4

Sodium isopropyl

10 and

[17]

Fe rich ( b 10 μm) Natural (range; 45 μm)

values not given) given)

(1 min)

xanthate

12

covellite formation upon xanthate addition

0.3%

0.07%

CuSO 4

Sodium isopropyl

11

Fe is detrimental to copper activation which reduces collector adsorption

[38]

 

12.5%

0.24%

(2 min)

xanthate

Natural fresh (110)surface

0.02% to 14.79%

(Not

CuSO 4

5

Fe enhances Cu adsorption

   
 

given)

(1 h)

 

a

Values reported as atomic ratios (×10 3 ) of metallic impurity elements relative to zinc.

 
   

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103

reconstructions resulting in possible S S (dimer) type bonding. However these surfaces are likely to be considerably different to those exposed to an aqueous environment. Leaching studies conducted by Weisener et al. [50] have shown iron-rich sphalerite to be more oxidised and to leach more rapidly than low iron containing sphalerite, suggesting greater reactivity of iron-rich sphalerite surfaces. Recent AFM images have shown the occurrence of larger and more frequent oxidation features on air exposed high iron sphalerites (compared to low iron sphalerite), conrming higher reactivity of high iron sphalerite [48]. Solecki et al. [27] established that surface oxidation prior to activation had a greater effect on copper adsorption onto the low iron sphalerite in comparison to the high iron sphalerite. Szczypa et al. [49] demonstrated that the copper/xanthate uptake was much greater onto unoxidised than oxidised sphalerite surfaces for both high and low iron sphalerite and that the effect of iron content was more pronounced for unoxidised as compared to oxidised surfaces. Gigowski et al. [33] however found that copper activation of sphalerite surfaces was more in uenced by iron content than by the degree of oxidation. These results suggest that while both increased oxidation and increased iron content are detrimental to otation it is the latter which has the more profound effect. Using XAS Pattrick et al. [17] showed that activated natural (Zn,Fe)S was more oxidised than ZnS, and that surface iron in (Zn,Fe)S existed as FeO. Similar FeO structures were observed by Buckley et al. [20] on freshly fractured sphalerite samples, which were believed to have existed prior to the fracture. According to Pattrick et al. [ 17 ], the existence of FeO had the effect of accelerating the formation of CuO and covellite (CuS), which is proposed by some authors to be among the major products of activation and xanthate addition. Additionally, the EXAFS Fe K edge data revealed that iron also reacts with the sulfur of xanthates forming FeS, thus adding further evidence to the notion of preferential xanthate adsorption on high iron sphalerite. These ndings also provide a possible explanation for the observation made by Gigowski et al. [33].

2.8. Lead and iron sphalerite activation

Sphalerite containing a high iron concentration also generally has higher lead content. Addition of, or the presence of, lead ions (Pb 2+ ) in the otation slurry can directly activate sphalerite and promote otation [5153]. Pb 2+ can be present due to dissolution from galena and also through recycling of plant water, which can lead to inadvertent lead activation and misreporting of sphalerite to copper and lead concentrates [11,54]. The presence of greater lead content in high iron sphalerite (compared to low iron sphalerite) is likely to contribute towards higher otation response seen in studies with high iron sphalerite (Section 2.6). Pb 2+ on the sphalerite surface (either present naturally as part of sphalerite lattice or adsorbed from the solution) promotes otation by reacting with xanthate forming stable xanthate and/or dixanthogen [55]. Basilio et al. [55] using kinetic studies and spectroscopic analysis (XPS, XRF and FTIR) suggested that lead activation of sphalerite occurred through an exchange mechanism involving exchange of Pb 2+ with Zn 2+ (similar to copper activation) on the sphalerite surface. This exchange mechanism is however not supported by other studies as accommodat- ing lead in place of zinc sites would require considerable relaxations of local structure as lead is much larger than zinc (or copper) [53,56]. Computer (atomistic) simulations by Pattrick et al. [56] showed that lead is incompatible in zinc sites in a sphalerite lattice (both surface and bulk) and the exchange process is not energetically favourable. Further uorescence REFLEXAFS study by Pattrick et al. [56] favoured a mechanism involving the formation of Pb-oxide species which become a point of attachment of xanthate sulfur to the lead. A high pH (9.2) normally favours more lead adsorption on sphalerite surface and it may occur through direct adsorption

(without exchange) of Pb 2+ followed by development and precipita- tion of lead hydroxy species such as PbOH + and Pb(OH) 2 [51,53] . In addition, carbonate species such as Pb 3 (CO 3 ) 2 (OH) 2 precipitates can also occur at high pHs and under prolonged exposure to air, which is typical in processing circuits. This is evident from solution speciation calculations of O'Dea et al. [57]. The Pb(OH) 2 may then react with xanthate to form lead xanthate through an ion exchange mechanism [51]. Rashchi et al. [52] however found through micro- otation tests that lead activation of sphalerite was signicant below pH 7 and progressively decreased to zero at pH 11. Based on their results and those from the literature, Rashchi et al. [52] suggested a mechanism where lead exchanges with zinc in the sphalerite lattice and reacts with xanthate to form Pb X only in the acidic pH range. From pH 710 lead forms a ZnO Pb + species on the surface through adsorption of Pb(OH) + but also forms the same PbX species with xanthate. Beyond pH 10 the Pb(OH) 2 precipitates dominates which can render sphalerite surface hydrophilic thus depressing otation. The mechanism of lead activation of sphalerite remains poorly understood and further surface studies involving both spectroscopic (XPS, ToF-SIMS, NEXAFS, EXAFS) and electrochemical kinetic studies are needed for clari cation. Synchrotron based measurements (spatially resolved) may be better suited as the surface lead concentrations are relatively low and may involve localised hetero- geneous adsorption. Additions of Fe 2+ in the presence of oxygen can also activate the sphalerite surfaces (through adsorption of Fe 2+ as Fe(OH) + followed by anodic oxidation to Fe(OH) 2+ ) and aid sphalerite oatation by forming

a ferric hydroxy complex with collector molecules at moderately

alkaline pH [34,58]. Such results with ferrous activation via aqueous

addition may provide insight regarding the possible in uence of iron

in the sphalerite structure (bulk and surface) with evidence of FeO [17]

type structures on the sphalerite surface and also the possible inuence of the presence of iron containing minerals such as pyrite, which can contribute to the pulp iron concentration through solubilisation. The use of steel grinding media however contributes to a larger portion of pulp iron content through oxidation of steel (corrosion) during grinding (Section 4.0). However, iron or lead within the sphalerite lattice do not appear to signicantly in uence collector adsorption (through solubilisation during conditioning) under laboratory conditions. Tong et al. [59] conducted unactivated (without copper) otation tests (2 min collec- tion time) on high iron marmatite with varying concentrations of butyl xanthate. The recoveries obtained for all xanthate concentra- tions used were extremely low with percent recoveries less than 5%. Similar results were also found by Boulton et al. [38] for ZnS and (Zn, Fe)S using the collector SIPX. Zhang et al. [34] found that activation

effect of Fe 2+ in the pulp solution was more pronounced between 1 and 2 ppm and that their effect continuously decreased above 2 ppm.

They also did not nd any activation effect by Fe 3+ . Under laboratory conditions of activation, iron or lead within the sphalerite lattice may not be solubilising sufciently to produce similar effects to those seen

in studies with aqueous additions of these ions into the mineral slurry. Within a otation circuit these ions (lead and iron) possibly occur

as a result of dissolution from minerals that predominantly contain these elements. Table 2 shows rest potential values of some common

Table 2 Rest potential of some common sul de minerals

Sul de mineral

Rest potential (SHE) V

Pyrite

0.66

Chalcopyrite

0.56

Sphalerite

0.46

Covellite

0.45

Bornite

0.42

Galena

0.40

Obtained from [60].

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sulde minerals [60]. In a mixed mineral system (as in plants) galvanic interactions occur, with minerals of higher rest potential being cathodic and those with lower rest potential being anodic. Anodic mineral are prone to oxidation unlike cathodic minerals. Galena, with the lowest rest potential, will undergo oxidative dissolution in a mixed mineral system and may be a signicant source of Pb 2+ in otation circuits. Pyrite will be cathodic and will not contribute as much iron to the system. The source of iron in mineral circuits may be from other sources such steel grinding media (Section 4.0). Zielinski et al. [61], using SEM-EDS analysis, found evidence of preferential misreporting only of low-iron sphalerite into lead concentrates within three Cominco lead otation circuits, most likely through activated otation with collector adsorption. Its was envisaged that the low-iron particles (both coarse and ne size fractions) were activated possibly by lead solubilised from the ore within the slurry and that preferential activation of only low iron sphalerite particles could have been due to greater oxidation of high iron sphalerite particles due to their higher reactivity. Such studies highlight the complexity of the activation and otation process used for mineral separation in actual plant environment which may be missed under controlled laboratory conditions.

3. Copper activation of pyrite

Unlike sphalerite, pyrite responds well to thiol collector molecules in the absence of activation [4,6], however pyrite can be activated when copper is present in the slurry. In either case, inadvertent pyrite otation can result, either during otation of copper bearing minerals/ores due to partial dissolution [62] or during activated otation of sphalerite especially where the concentration of sphaler- ite in the slurry is low [6] . Secondary copper bearing ores such as chalcocite, covellite and bornite pose greater risk of inadvertent pyrite activation and otation compared to chalcopyrite, as evident from rest potential values in Table 2 [60,62,63]. It is therefore important to understand the controlling mechanisms of pyrite activation and the otation of pyrite into copper or zinc concentrates. In addition to Cu 2+ , pyrite can also be activated by Pb 2+ , Fe 2+ and Ca 2+ which can lead to inadvertent pyrite otation causing it to misreport to copper, zinc or lead concentrates [6,64,65] . As for sphalerite, pyrite activation and otation is also in uenced by pH, copper concentration and activation time.

3.1. Unactivated otation

Pyrite has a natural otability and a small percentage of it can usually be recovered without any use of activators or collectors [40,65]. Much higher recoveries can be achieved with collectors. It has been shown by Leppinen [4] that adsorption of xanthate onto the

pyrite surface without activation reaches a maximum at pH 5 and a minimum at pH 7. Flotation results showed that as much as 80 to 90% of pyrite can be recovered through otation (without activation) at pH 4 to 5, while recovery is much lower at other pH values [4,6]. Surface analysis by Leppinen [4], of unactivated pyrite samples conditioned with ethyl xanthate conrmed the occurrence of ironxanthate with diethyl dixanthogen at monolayer coverage on the pyrite surface. A clear distinction as to whether the ironxanthate is in the Fe(II) or Fe(III) form was not made by Leppinen [4] however some Fe(III) character was evident. Studies by Valdivieso et al. [66] have shown that adsorption of xanthate onto unactivated pyrite surface increases aqueous Fe 2+ . The surface oxidation of xanthate to dixanthogen results in a corresponding reduction of the surface Fe(III) hydroxide with conversion to Fe 2+ . This mechanism proposed by Valdivieso et al. [66] is shown in Fig. 2 . According to this mechanism as the hydrophobic dixanthogen develops on the pyrite surface there is a subsequent reduction in hydrophilic surface hydroxide.

3.2. Mechanisms of Cu(II) and Cu(OH) 2 activation

There are important structural and electronic differences between pyrite and sphalerite and as such it is no surprise that the copper activation of pyrite follows a different mechanism from that of sphalerite. It was shown by Weisener and Gerson [67] that copper uptake during pyrite activation does not results in a related 1:1 (or any) iron release from pyrite, thus ruling out an ion exchange activation mechanism. Pyrite activation follows a single fast step involving Cu(II) adsorption onto the reactive sulfur sites only on the surface with no migration into the bulk pyrite [67]. During adsorption Cu(II) is reduced to Cu(I) with subsequent oxidation of surface sulde. Boulton et al. [37], conrmed that copper adsorbs only to the surface and does not migrate to the bulk, as is case for sphalerite. Using Fourier transform infrared spectroscopy employing attenu- ated total reection (FTIR-ATR), Leppinen [4] suggested that the pyrite surface upon activation is fully covered with coppersulde like products which resemble Cu 2 S more than CuS. However, subsequent EXAFS data analysis has indicated that copper on the activated pyrite surface has a distorted trigonal planar position between three sulfur atoms [67] with an average Cu S bond length of 2.27 ± 0.02 Å. Weisener and Gerson [31,67] studied pyrite activation using EXAFS, XPS, angle resolved XPS and time of ight secondary ion mass spectrometry (ToF-SIMS) and found Cu(I) to be present for all pH and all copper concentrations studied, with Cu(II) occurring (as hydroxide) and overlaying the Cu(I) activated surface only at alkaline pH. Moreover, no further copper uptake was observed after 5 min of activation. At alkaline pH, along with the distorted trigonal planar copper moiety, Cu(OH) 2 precipitates were also found with a CuO bond length of 2.00 Å.

were also found with a Cu – O bond length of 2.00 Å. Fig. 2. Adsorption

Fig. 2. Adsorption and dixanthogen formation on unactivated pyrite surface. Redrawn from [66].

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Zhang et al. [6] suggested through zeta potential and FTIR (ATR) measurements that copper is chemisorbed to the surface. It was however shown by Hicyilmaz et al. [68] that the interaction between copper and pyrite is solely an electrochemical process while the interaction between activated copper and collector, and the pyrite surface and collector is primarily chemical in nature. Results from Pecina et al. [65] have also conrmed the chemical interaction of collectors with activated and unactivated pyrite surfaces. Leppinen [4] , through IR internal reection surface analysis of activated pyrite surfaces conditioned with ethyl xanthate collector, showed Cu(I)ethyl xanthate to be the dominant activation product with monolayer coverage. Shen et al. [69] also reported cuprous xanthate as the only xanthate product formed under their reactions conditions. Leppinen [4] found copper concentration and pH dependency of xanthate adsorption and subsequent otation of pyrite. They showed at pH 7 that when equal amounts of copper and xanthate are used, copper xanthate is the only product formed, however when either relatively higher or lower concentrations of copper is used, signicant amounts of dixanthogen also forms. Some Cu(II)xanthate like compounds were also observed at higher copper concentrations. Oxidation of xanthate to dixanthogen has also been reported by [6].

3.3. Effectiveness of activation

The amount of xanthate adsorbed on activated pyrite surfaces was seen to increase from a minimum at pH 45 to a maximum at pH 8 [4] . The adsorption decreased drastically above pH 8. This can also be observed from the data of Zhang et al. [6] and Dichmann and Finch [70] where percentage recovery of activated and unactivated pyrite, with and without xanthate, undergoes a similar decrease after pH 89. They however obtained a signicantly higher recovery than Leppinen [4] at pH 4. Generally, activation by copper results in signicant increases in recovery only within the pH range of 610 [4,6,70]. At mildly acidic pH a higher than expected recovery of unactivated pyrite is observed owing, most probably, to the emergence of sulfur-rich products (due to the dissolution of iron). Hence, in these studies, the maximum otation, using xanthate collector, of unactivated pyrite at pH 4 is seen to exceed otation of activated pyrite at pH 8. This may have very limited practical implications as most plants don't operate at a low pH of 4. It is generally seen that hydrophobicity of pyrite surfaces increases at low pH (compared to higher pH under similar conditions) with either activation or collector addition or both [68], thus resulting in higher recovery. Flotation of both activated and unactivated pyrite generally follows rst-order kinetics [63]. He et al. [40] have shown pulp oxidation potential (Eh) to be an important factor in determining recoveries and speciation on pyrite surfaces, with maximum recoveries obtainable at the conditioning oxidation potential of 35 mV (SHE) at pH 9. EDTA extraction and surface studies (XPS) revealed that Eh inuences the production of hydrophilic (iron oxide/hydroxide) and hydrophobic (Cu(I)S) species, and also promotes formation of Cu(I)xanthate species on pyrite surface The presence and relative abundance of such surface species has a corresponding effect on pyrite recovery. Typically copper and xanthate concentrations from 1 × 10 4 to 1 × 10 6 M are used to conduct fundamental lab-based studies [14,26,30,31,37 44]. A few studies have also reported using 1001500 g/t collector [3739,4143] and 2503000 g/t copper containing activator (such as nitrate or sulphate) [37 39,42,70]. Table 3 gives names of some collectors and their typical addition rate along with the dose of copper sulfate used in otation of sulde ores in processing plants. A range of collector and copper concentrations is used depending on the exact mineralogy of the ore being processed and the target minerals. It is however difcult to compare the values given in literature, which are normally expressed in molar concentrations,

Table 3 Typical amounts of collector and activator used in otation and separation of sul de ores at processing plants