Академический Документы
Профессиональный Документы
Культура Документы
a r t i c l e
i n f o
a b s t r a c t
A review of the considerable, but often contradictory, literature examining the specic surface reactions
associated with copper adsorption onto the common metal sulde minerals sphalerite, (Zn,Fe)S, and pyrite
(FeS2), 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 sulde 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. Sufcient
oxidation potential is also needed (through O2 conditioning) to maintain effective galvanic interactions
between sphalerite and pyrite. This ensures pyrite is sufciently depressed while sphalerite oats. Good
water quality with low concentrations of contaminant ions, such as Pb2+and Fe2+, 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 coppersulde structure after activation.
2008 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
Introduction. . . . . . . . . . . . . . . . .
Activation of sphalerite . . . . . . . . . . . .
2.1.
Mechanisms of Cu(II) activation . . . . . .
2.2.
Reaction kinetics . . . . . . . . . . . .
2.3.
Mechanisms of Cu(OH)2 activation . . . . .
2.4.
Zeta potential and isoelectric point . . . . .
2.5.
Copper concentration and activation duration.
2.6.
The effect of sphalerite iron content on copper
2.7.
Sphalerite surface oxidation . . . . . . . .
2.8.
Lead and iron sphalerite activation . . . . .
Copper activation of pyrite . . . . . . . . . . .
3.1.
Unactivated otation . . . . . . . . . .
3.2.
Mechanisms of Cu(II) and Cu(OH)2 activation .
3.3.
Effectiveness of activation . . . . . . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
activation
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
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
98
98
100
100
100
101
102
102
103
104
104
104
105
98
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
4.
Mixed pyrite and sphalerite otation
5.
Summary . . . . . . . . . . .
Acknowledgments . . . . . . . . .
References . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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 sulde 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 sulde 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 (Cu2+),
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 Fe2+/Fe3+ 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 (FeS2) 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 sulde 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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
105
107
109
109
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
Using conventional X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS) and
electron microprobe analysis (EMPA), Vinals et al. [22] found digenite
(Cu1.8S) to be the main activation product at pH 1.11.3 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 Cu2S-like product. They
further showed that activation conducted under slightly oxidising
conditions produced hydrophobic species, such as copper polysuldes, 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 chemadsorbed 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 CuO (2.07 ) 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 . 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 CuO bonds. It
has been further shown in Gerson et al. [24] that this distorted trigonal
planar structure (CuS3) on the sphalerite surface is slightly pushed up
99
6
1:63
Cu2
Cu0:9 S1:63 Zn2 S2
2 surface
aq S2
2
S1:63
Cu0:9 S1:28 Cu0:9 S1:63
6
2
2
surface Znaq
2
2
2 0
2
1:63
Cu0:8 4:09
S2
3 Zn S Zn3 bulk Cuaq S3
bulk
2
S0:8 Zn1:63
6
3
bulk Znaq
2Cu2
aq 4EXaq 2CuEX2aq 2CuEXaq X2aq
100
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
The Cu(II) from the hydroxide may then exchange with the Zn(II)
from the sulde.
ZnSn d xCuOH2surface Znn xCux d xZnOH2surface
[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 N2-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 representative 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)).
CuOH2surface 2EXaq CuEX2surface 2OHaq
10
11
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
101
102
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
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 79 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 Zn2+ species, [Zn(OH)2(H2O)2]0n.
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 64Cu labelled CuSO4, Solecki et al. [27] showed that
adsorption of Cu2+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 Cu2+, 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 copperactivated iron-rich sphalerite preferentially adsorbs xanthate. However, 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 Cu2+ 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 Cu2+ 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 Cu2+ adsorption. A decrease in the Fe 2p3/2 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)
Synthetic (not given)
Fe content
0%
5%
40%
Synthetic (not given)
0%
5%
40%
Natural (not given)
33a
115a
Natural (125200 m)
0.38%
12%
Synthetic: ZnSe and ZnS Natural: High (exact
Fe rich (b 10 m)
values not given)
Natural (range; 45 m)
0.3%
12.5%
Natural fresh (110)surface
0.02% to 14.79%
a
Pb content Activator
(time)
Collector used
pH
Conclusion
Reference
Not
present
64
CuSO4
(not given)
[27]
Not
present
CuSO4
(20 min)
Ethyl xanthate
6, 8, 10
[49]
0.2a
24a
0.04%
0.20%
(Not
given)
0.07%
0.24%
(Not
given)
CuSO4
(1 h)
CuSO4
(not given)
CuSO4
(1 min)
CuSO4
(2 min)
CuSO4
(1 h)
9.2
[20]
Sodium isopropyl
xanthate
Sodium isopropyl
xanthate
Sodium isopropyl
xanthate
Values reported as atomic ratios ( 103) of metallic impurity elements relative to zinc.
10 and
12
11
5
[33]
[17]
[38]
[48]
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
103
(without exchange) of Pb2+ followed by development and precipitation of lead hydroxy species such as PbOH+ and Pb(OH)2 [51,53]. In
addition, carbonate species such as Pb3(CO3)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 PbX only in the acidic pH range. From pH 710
lead forms a ZnOPb+ 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 clarication. Synchrotron based measurements
(spatially resolved) may be better suited as the surface lead
concentrations are relatively low and may involve localised heterogeneous adsorption.
Additions of Fe2+ in the presence of oxygen can also activate the
sphalerite surfaces (through adsorption of Fe2+ 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 inuence 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 inuence collector adsorption (through solubilisation
during conditioning) under laboratory conditions. Tong et al. [59]
conducted unactivated (without copper) otation tests (2 min collection time) on high iron marmatite with varying concentrations of
butyl xanthate. The recoveries obtained for all xanthate concentrations 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 Fe2+ 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 Fe3+. 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 sulde minerals
Sulde mineral
Pyrite
Chalcopyrite
Sphalerite
Covellite
Bornite
Galena
0.66
0.56
0.46
0.45
0.42
0.40
104
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
Fig. 2. Adsorption and dixanthogen formation on unactivated pyrite surface. Redrawn from [66].
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
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
[14,26,30,31,3744]. A few studies have also reported using 100
1500 g/t collector [3739,4143] and 2503000 g/t copper containing
activator (such as nitrate or sulphate) [3739,42,70]. 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,
105
Table 3
Typical amounts of collector and activator used in otation and separation of sulde
ores at processing plants
Reagent
Name
Collector
Xanthate
Dithiophosphate
Thionocarbamate
Xanthogen formate
Xanthic ester
Mercaptobenzothiazole
Thiocarbanilide
Copper sulfate
5350
10250
1015
225
225
25250
2575
1002500
Activator
Data obtained from [9].
and plant values. Most of these studies do not state the conditioning
volume, hence it becomes difcult to convert molar concentrations
into g/t. From the studies that do express reagent concentration in g/t,
the collector concentrations used appear to be an order of magnitude
higher than normal plant practice. Studies beyond the normal
practical range are however needed to provide new perspectives for
better separation. With exception of a few studies, most references
quoted have conducted tests on single mineral system while
maintaining concentrations similar to that used in plant. Needless to
say that processing plants have mixed mineral systems with galvanic
processes which does not occur in single mineral system.
4. Mixed pyrite and sphalerite otation
Separation of pyrite and sphalerite through activated otation is
normally carried out at high pH [3,71] although some plants such as
Teck Cominco also does this at lower pH [48]. Pyrite has a higher rest
potential than sphalerite and due to this pyrite surfaces become
coated with OH products (resulting from reduction of O2) due to
galvanic coupling, making pyrite surface less hydrophobic, thus
increasing sphalerite selectivity [72]. This galvanic coupling can
however be suppressed by saturating the ore slurry with N2 gas and
using N2 gas for otation instead of air. This causes the pulp potential
to be reduced due to reduced oxygen activity [72]. The use of N2 gas to
reduce galvanic interactions can be used in reverse otation of pyrite
from sphalerite [11]. It is also used effectively in the N2TEC otation
technology for otation of auriferous pyrite by the Newmont Mining
Corporation at their Lone Tree Plant in Nevada [64]. This process was
developed initially to improve recovery of gold from low grade sulde
ores, the N2TEC process involves processing of ores (from grinding to
otation) in an inert N2 gas environment where operating potential
ranges from 100 mV to 300 mV vs. SHE (0.1 to 0.5 V vs. Ag/AgCl) and
uses potassium ethyl xanthate [64,73].
Zhang et al. [6] conducted micro-otation studies of activated
pyrite in the absence and presence of sphalerite. Activated pyrite
otation is observed to be depressed signicantly in the presence of
sphalerite at all pH values with recovery continuously decreasing to
nearly 2% at pH 11. Pyrite recovery at pH 4 is seen to be much higher
than recoveries at all other pH even when conducted in the presence
of sphalerite. Flotation without copper activation generally has no
effect on pyrite recovery as sphalerite does not combine with xanthate
without copper [6].
Using micro-otation, laboratory batch, and in-plant minicell
experiments, Dichmann and Finch [70] observed similar behaviour
during combined otation of activated pyrite and sphalerite. From
these studies it appeared that during mixed activation/otation
sphalerite preferentially consumed copper and xanthate while pyrite
becomes depressed when in the presence of sphalerite. According to
Dichmann and Finch [70], addition of copper increases galvanic
coupling between sphalerite and pyrite particles, and this favours
xanthate adsorption on sphalerite while pyrite becomes coated with
hydrophilic hydroxide ions. The effectiveness of this electrochemical
106
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
1
SO2
3aq 2O2aq YSO4aq 2e
12
13
Cu2
aq 2OHaq CuOH2surface
14
Fig. 3. Sphalerite and pyrite recoveries obtained at pH 8.5 with [Cu2+] and [KEX] =
2 10 5 moldm 3 and [Na2SO3] = 2 10 4 moldm 3. Adopted from [69].
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
107
108
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
109
110
A.P. Chandra, A.R. Gerson / Advances in Colloid and Interface Science 145 (2009) 97110
[16] Sutherland KL, Wark IW, editors. Principles of otation. Melbourne: Australasian
Institute of Minning and Metallurgy; 1955.
[17] Pattrick RAD, England KER, Charnock JM, Mosselmans JFW. Int J Miner Process
1999;55:247.
[18] Prestidge CA, Skinner WM, Ralston J, Smart RSC. Appl Surf Sci 1997;108:333.
[19] Kartio IJ, Basilio CI, Yoon RH. Langmuir 1998;14:5274.
[20] Buckley AN, Woods R, Wouterlood HJ. Int J Miner Process 1989;26:29.
[21] Buckley AN, Skinner WM, Harmer SL, Pring A, Lamb RN, Fan L, et al. Can J Chem
2007;85:767.
[22] Vinals J, Fuentes G, Hernandez MC, Herreros O. Hydrometallurgy 2004;75:177.
[23] Chen Z, Yoon RH. Int J Miner Process 2000;58:57.
[24] Gerson AR, Cookson DJ, Prince KC. In: Riviere JC, Myhra S, editors. Handbook of
surface and interface analysis: methods for problem solving, 2nd Edition; 2008.
Chapter 10.
[25] Porento M, Hirva P. Surf Sci 2005;576:98.
[26] Popov SR, Vucinic DR. Colloids Surf 1990;47:81.
[27] Solecki J, Komosa A, Szczypa J. Int J Miner Process 1979;6:221.
[28] Bacaksiz E, Dzhafarov TD, Novruzov VD, Ozturk K, Tomakin M, Kucukomeroglu T,
et al. Phys Status Solidi. A Appl Res 2004;201:2948.
[29] Buckley AN, Woods R. Appl Surf Sci 1987;27:437.
[30] Lascelles D, Sui CC, Finch JA, Butler IS. Colloids surf, A Physicochem Eng Asp
2001;186:163.
[31] Weisener C, Gerson A. Miner Eng 2000;13:1329.
[32] Skinner WM, Prestidge CA, Smart RSC. Surf Interface Anal 1996;24:620.
[33] Gigowski B, Vogg A, Wierer K, Dobias B. Int J Miner Process 1991;33:103.
[34] Zhang Q, Rao SR, Finch JA. Colloids Surf 1992;66:81.
[35] Rao SR, editor. Surface chemistry of froth otation. Fundamentals, 2nd edition.
New York: Kluwer Academic/Plenum Publishers; 2004.
[36] Mirnezami M, Restrepo L, Finch JA. J Colloid Interface Sci 2003;259:36.
[37] Boulton A, Fornasiero D, Ralston J. Int J Miner Process 2003;70:205.
[38] Boulton A, Fornasiero D, Ralston J. Miner Eng 2005;18:1120.
[39] Duarte ACP, Grano SR. Miner Eng 2007;20:766.
[40] He S, Fornasiero D, Skinner W. Miner Eng 2005;18:1208.
[41] He S, Skinner W, Fornasiero D. Int J Miner Process 2006;80:169.
[42] Huang G, Grano S. Miner Eng 2005;18:1152.
[43] Khmeleva TN, Skinner W, Beattie DA. Int J Miner Process 2005;76:43.
[44] Wang XH, Forssberg KSE. Miner Eng 1996;9:527.
[45] Dana JD, Hurlbut CS, Klein C, editors. Manual of mineralogy (after James D. Dana).
19th ed. New York: Wiley; 1977.
[46] Harmer SL, Goncharova LV, Kolarova R, Lennard WN, Munoz-Marquez MA,
Mitchell IV, et al. Surf Sci 2007;601:352.
[47] Wenk H-R, Bulakh AG, editors. Minerals: their constitution and origin. Cambridge;
New York: Cambridge University Press; 2004.
[48] Harmer SL, Mierczynska-Vasilev A, Beattie DA, Shapter JG. Miner Eng in press,
doi:10.1016/j.mineng.2008.02.014.
[49] Szczypa J, Solecki J, Komosa A. Int J Miner Process 1980;7:151.
[50] Weisener CG, Smart RSC, Gerson AR. Int J Miner Process 2004;74:239.
[51] Morey MS, Grano SR, Ralston J, Prestidge CA, Verity B. Miner Eng 2001;14:1009.
[52] Rashchi F, Sui C, Finch JA. Int J Miner Process 2002;67:43.
[53] Sui CC, Lee D, Casuge A, Finch JA. Miner Metall Process 1999;16:53.
[54] Yeomans T. Copper concentrate quality improvements at Myra Falls. In: Orford I,
editor. 40th Annual meeting of the Canadian mineral processors 2224 January.
Ottawa: Canadian Institute of Mining, Metallurgy and Petroleum; 2008.
[55] Basilio CI, Kartio IJ, Yoon RH. Miner Eng 1996;9:869.
[56] Pattrick RAD, Charnock JM, England KER, Mosselmans JFW, Wright K. Miner Eng
1998;11:1025.
[57] O'Dea AR, Prince KE, Smart RSC, Gerson AR. Int J Miner Process 2001;61:121.
[58] Finkelstein NP. Int J Miner Process 1999;55:283.
[59] Tong X, Song S, He J, Rao F, Lopez-Valdivieso A. Miner Eng 2007;20:259.
[60] Majima H. Can Metall Q 1969:269.
[61] Zielinski PA, Larson KA, Stradling AW. Miner Eng 2000;13:357.
[62] Lascelles D, Finch JA. Miner Eng 2002;15:567.
[63] Wong G, Lascelles D, Finch JA. Miner Eng 2002;15:573.
[64] Miller JD, Kappes R, Simmons GL, LeVier KM. Miner Eng 2006;19:659.
[65] Pecina ET, Uribe A, Nava F, Finch JA. Miner Eng 2006;19:172.
[66] Valdivieso LA, Sanchez Lopez AA, Song S. Int J Miner Process 2005;77:154.
[67] Weisener C, Gerson A. Surf Interface Anal 2000;30:454.
[68] Hicyilmaz C, Emre Altun N, Ekmekci Z, Gokagac G. Miner Eng 2004;17:879.
[69] Shen WZ, Fornasiero D, Ralston J. Int J Miner Process 2001;63:17.
[70] Dichmann TK, Finch JA. Miner Eng 2001;14:217.
[71] Shen WZ, Fornasiero D, Ralston J. Miner Eng 1998;11:145.
[72] Rao SR, editor. Surface chemistry of froth otation. Reagents and Mechanisms, 2nd
edition, New York: Kluwer Academic/Plenum Publishers; 2004.
[73] Miller JD, Du Plessis R, Kotylar DG, Zhu X, Simmons GL. Int J Miner Process
2002;67:1.
[74] Hart B, Biesinger M, Smart RSC. Miner Eng 2006;19:790.
[75] Pease JD, Curry DC, Young MF. Miner Eng 2006;19:831.
[76] Rashchi F, Finch JA. Colloids Surf, A Physicochem Eng Asp 2006;276:87.
[77] Kocabag D, Gler T. Miner Eng 2007;20:1246.
[78] Fuerstenau MC, Chander S, Woods R. In: Fuerstenau MC, Jameson G, Yoon RH,
editors. Froth otation: a century of innovation. Colorado: Society for Mining,
Metallurgy, and Exploration, Inc.; 2007.
[79] Valdivieso LA, Celedn Cervantes T, Song S, Robledo Cabrera A, Laskowski JS. Miner
Eng 2004;17:1001.
[80] Rao KH, Forssberg KSE. In: Fuerstenau MC, Jameson G, Yoon RH, editors. Froth
otation: a century of innovation. Colorado: Society for Mining, Metallurgy, and
Exploration, Inc.; 2007.
[81] Rao SR, Nesset JE, Finch JA. Activation of sphalerite by Cu ion produced by cyanide
action on chalcopyrite. In: Khosla NK, Jadhav GN, editors. Proceedings of the
International Seminar on Mineral Processing Technology (MPT) 2007. New Delhi:
Allied Publishers; 2007.
[82] Levay G, Smart RSC, Skinner WM. J S Afr Inst Min Metall 2001;101:69.
[83] Rao SR, Finch JA. Miner Eng 1989;2:65.
[84] Ozkan SG, Acar A. Water Res 2004;38:1773.
[85] Espinosa-Gomez R, Finch JA, Laplante AR. Colloids Surf 1987;26:333.
[86] Seke MD, Pistorius PC. Miner Eng 2006;19:1.
[87] Stn P, Parvinen P, Miettinen M, Luukkanen S, Kaskiniemi V, Aaltonen J. Miner Eng
2003;16:229.
[88] El-Shall H, Zhang P, Snow R. Miner Metall Process 1996;13:135.
[89] Rodrigues RT, Rubio J. Int J Miner Process 2007;82:1.