International Journal of Mineral Processing 98 (2011) 202–207

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International Journal of Mineral Processing

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j m i n p r o

An investigation into the flotation behaviour of pyrrhotite☆

S.A. Allison, C.T. O'Connor ⁎
Centre for Minerals Research, Department of Chemical Engineering, University of Cape Town, Private Bag X3, Rondebosch, 7701, Cape Town, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: It is well-known that pyrrhotite is a slow floating mineral and there are many studies investigating its
Received 6 December 2010 behaviour in the presence of pentlandite with which it most frequently occurs. In the treatment of massive
Accepted 12 December 2010 sulphides the process often aims to depress the pyrrhotite whereas in other applications such as the treatment
Available online 21 December 2010
of platinum group elements (PGE) losses of the mineral may result in losses of PGEs as well as a reduced
availability of sulphides required for smelter operation. The causes of pyrrhotite's poor floatability and
Keywords:
Pyrrhotite
reagent usage and the conditions encountered at the pHs typical of circuits treating pyrrhotite bearing ores
Flotation are still a subject of considerable research. The present study was undertaken to measure the extent and
Reagents rate of reaction of a relatively pure pyrrhotite sample using a standard xanthate collector at different pHs
and conditioning times. The role of copper sulphate as an activator and guar as a depressant were also
investigated. The effect of these treatments on the hydrophobicity of the pyrrhotite was determined by
microflotation tests. This study has shown that under most conditions surface coverage of SIBX-originated
species on the pyrrhotite equates to multi-layer coverage and that this is promoted by the pre-treatment with
copper sulphate. Longer conditioning times increase surface coverage and recovery. Guar when added before
copper sulphate using different addition regimes will depress the pyrrhotite. The findings and their
significance for pyrrhotite flotation on flotation plants are discussed.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction The typical reagent suites employed by concentrators in the

Pyrrhotite is one of the most abundant sulphide minerals and in
flotation processes is frequently rejected to tailings. This is often
the case when massive nickel ores are being processed in a flotation
plant or in the treatment of chalcopyrite–pentlandite rich ore bodies.
In South Africa pyrrhotite occurs in significant quantities in the
Merensky, UG2 and Platreef ore bodies of the Bushveld Complex. In
the Merensky reef in particular the base metal sulphides constitute
around 1% by mass of the ore. The major sulphides and their typical
contents are pyrrhotite (Fe1 − xS: ~ 45%), pentlandite ((Fe,Ni)9S8:
~ 32%) and chalcopyrite (CuFeS2: ~ 16%). Minor amounts of pyrite
(FeS2) and other sulphides also occur. In the case of pyrrhotite, x is
typically about 0.125. There have been suggestions that pyrrhotite
losses result in significant losses of platinum group minerals but
recently this appears to be no longer as significant as previously sus-
pected. Of considerable importance in the PGM operations, however,
is the need to recover the pyrrhotite as an extra source of sulphur to
be used in smelters when UG2 material is being treated since the
latter ore body is deficient in sulphides.
☆ Presented at the XXV IMPC, 5–9 September, 2010 and reprinted with the
permission of The Australasian Institute of Mining and Metallurgy.
⁎ Corresponding author. Tel.: +27 216505515; fax: +27 216505501.
E-mail address: cyril.oconnor@uct.ac.za (C.T. O'Connor).
treatment of platinum group minerals (PGMs) focus largely on
recovering the sulphides using typically sodium iso-butyl xanthate
as the primary collector often, in the case of PGM concentrators, in
conjunction with a secondary collector such as a dithiophosphate.
Many, but not all, of the flotation plants add copper sulphate as an
activator. Generally these concentrators use a polysaccharide depres-
sant, either a carboxymethyl cellulose (CMC) or a modified guar gum,
to reduce the recovery of naturally floating gangue minerals such as
talc, pyroxene, plagioclase, etc. The flotation is carried out at the
natural pH of the milled ore which may vary between 7.5 and 9 but is
typically closer to the higher value.
As is well-known the chalcopyrite is fast floating and pentlandite,
although not as fast floating as the former, tends to float readily.
Pyrrhotite on the other hand is well-known to be "notoriously slow
floating" (Hochreiter et al., 1985) and the residence time in the flo-
tation circuit is often extended to accommodate this. It is also worth
noting that in many operations pyrrhotite may be an undesirable
gangue mineral and considerable effort is expended in attempting
to achieve its depression rather than its recovery. On the other
hand in some cases about 10% of the nickel is in the pyrrhotite and
its loss in the tailings is undesirable (Kerr, 2002). Hence either
recovery or depression of pyrrhotite can become a major operational
driver depending on the ore being processed and a better under-
standing of the flotation behaviour of this mineral is hence of great
importance.

0301-7516/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2010.12.003
 S.A. Allison, C.T. O'Connor / International Journal of Mineral Processing 98 (2011) 202–207
A number of studies have shown that reaction between pyrrhotite
and xanthates produces the oxidation product dixanthogen subject
to the oxidation potential being maintained at ~200 mV/SHE. (Miller
et al., 2005). As with other sulphides, the extent and rate of this
reaction decrease with increasing pH due to the increasing formation
of oxidation products at the surface (Miller et al., 2005). At pH 9 the
oxidation reaction typically results in the formation of Fe(OH)3 and
a metal deficient sulphide, Fe(1 − x)S1.13 (Buckley et al., 1985). Masking
of the sulphide surface by the formation of hydrophilic metal
hydroxide species begins at lower pH values for iron sulphides than
for sulphides of copper or nickel. The slow flotation kinetics of
pyrrhotite at higher pH values may therefore be due to an inherently
lower surface hydrophobicity relative to that of the other sulphides
even if significant reaction with collector does occur (Ball and Rickard,
1976). A slower rate of reaction with xanthate compared to that of
the other sulphides may also effectively starve the pyrrhotite of
reagent when it is the presence of other sulphide minerals.
A number of studies have supported the contention that the
greatest contributing factor to the poor flotation of pyrrhotite in a
mixed pulp is the effect of galvanic interactions. It has been found that
in pentlandite/pyrrhotite mixtures a reduction in the surface potential
of pyrrhotite leads to greater reaction at the pentlandite surface
(Bozkurt et al., 1998). However, the opposite effect has been found
for pyrrhotite/chalcopyrite mixtures (Cheng and Iwasaki, 1992). The
net result for multi-sulphide systems is unclear.
While some studies suggest that copper activation of pyrrhotite is
not effective in the alkaline range (Nicol, 1984) improvements in its
flotation rate and recovery after copper sulphate activation have been
observed (Allison et al., 1972; Corrans et al., 1992; Wiese et al., 2005)
and copper activation is widely used in practice. Many of the studies
on copper activation of sulphides, including pyrrhotite, have been
made in the acid range where the copper is present as copper ions
and few investigations have focused on the alkaline range where, for
example at pH N 8, it would be present predominantly as precipitated
copper hydroxide. By analogy with other studies an initial layer of
copper sulphide may be formed fairly rapidly (Weisener and Gerson,
2000) but it is probable that, in the times that would be of interest in
flotation systems, the bulk of the products of activation are not the
same as in the acid range and consist largely of adsorbed monovalent
copper hydroxy species or precipitated copper hydroxide or copper
xanthate. The reaction products formed between thiols and copper
activated surfaces and between thiols and copper hydroxy species
in solution or suspension in the alkaline range are however still
not clearly understood (Finkelstein, 1997).
Pyrrhotite has been shown to strongly adsorb other metal hydroxy
species, such as iron hydroxides, that are formed in the alkaline pH
range and may be present in flotation systems following mild steel
milling (Allison et al., 1972). This suggests that the mineral may in
turn have a greater tendency to adsorb polysaccharide depressants
than other sulphides. In summary, the "pyrrhotite flotation system is
very complicated, resulting from variation in pyrrhotite composition/
structure, pyrrhotite and thiocarbonate oxidation, Eh/pH, minerals
contacted/associated with it and activation reactions" (Miller et al.,
2005).
The present study was aimed at resolving some of these questions
by measuring the rates and extent of reaction of a xanthate collector
(viz. SIBX) with pyrrhotite in the absence of any other sulphides
under various conditions and then using microflotation as an
indicator of the resultant hydrophobicity.
2. Experimental procedure
2.1. Mineral samples
Samples of pyrrhotite obtained from Wards Scientific Establish-
ment were pulverized in a Sieb apparatus and screened into [−106 +
203
38] μm and −38 μm fractions. XRD analysis showed that the main
impurity was siliceous and carbonaceous material. The purity was
determined to be 77% and this was calculated from an analysis of
the iron and sulphur content. The BET surface area of the [−106 +
38] μm fraction was 0.173 m2/gm and of the −38 μm fraction was
1.39 m2/gm. Although not determined specifically the samples were
probably hexagonal or orthorhombic pyrrhotite (Lambert, 2010).
2.2. Reagents
Unless otherwise stated the tests were conducted at pH 9 which is
close to the natural pH found in most Merensky ore flotation plants.
De-ionised water was used to make up the reagent solutions and for
the microflotation tests and was buffered to the required pH using
either a borate (pH ≥ 9) or a phosphate buffer (pH b 8). A number of
preliminary tests in which only sodium hydroxide was used to adjust
the pH did not show different results from those using the buffer
solutions.
The collector used in the tests was sodium iso-butyl xanthate
(SIBX) supplied by Senmin. It was purified by dissolution in acetone
and re-precipitation with benzene. Copper sulphate was used as an
activator. Two different polymeric depressants were used, viz. a guar
depressant (Stypress 504) supplied by Chemquest and a CMC
depressant (Depramin 267) supplied by Akzo Nobel. For comparative
purposes a number of microflotation tests were performed using a
sample of synthetic plant water made up by the addition of various
salts to de-ionised water to produce an ionic concentration typical
of that found on concentrators processing PGE ores of the Bushveld
Complex (Shackleton et al., 2003).
2.3. Adsorption measurements
The rate and extent of reaction of SIBX with the mineral samples
were determined by monitoring the change in the xanthate
concentration by measuring the absorption at its characteristic UV
absorption wavelength, i.e. λ = 301 nm, using an Ultrospec 2100 UV
spectrophotometer. In these tests, a weighed amount of the −38 μm
mineral sample, used as obtained, was first pre-treated as required
and transferred to 500 ml of xanthate solution of known concentra-
tion. Timing was begun and 3 ml of solution was drawn off at intervals
using a syringe to which a filter was attached effectively preventing
removal of mineral particles and providing a clear sample for the UV
measurement. All the adsorption tests were conducted at 25 °C in a
temperature controlled bath.
2.4. Microflotation procedure
The relative hydrophobicity of the mineral surface was measured
by determining the rate and extent of recovery in a microflotation
system. These results are not regarded as a true indicator of
floatability as this is a resultant of all the relevant interacting param-
eters including the froth phase which is absent in such a cell. However
the results do indicate the extent to which the mineral particles
successfully attach to bubbles generated in the system and essentially
report to the pulp–froth interface. The apparatus has been described
previously (Bradshaw and O'Connor, 1996). The standard deviation in
these tests was always less than 2%. In these tests the [−106 + 38] μm
fraction was used. Trahar and Warren (1976) have shown that the
optimum size range for flotation of pyrrhotite is 20–70 μm and hence
particle size should not be a constraint in these flotation tests. In order
to clean the mineral surface of ultrafines and to remove as much of the
iron hydroxides as possible, samples were subjected to sonification for
15 s and washed twice with the buffer solution. The sample was then
transferred to 500 ml of pH buffered water in a beaker, 10 ml of
reagent solution added and reaction continued for a set time. To stop
further reaction the solution was decanted off and the sample washed
204 S.A. Allison, C.T. O'Connor / International Journal of Mineral Processing 98 (2011) 202–207

8
with fresh buffer solution. As required further water and reagent were
added and the process repeated. Unless otherwise stated the 7

microflotation tests were performed with 2 g of mineral sample and
reacted, as described above, with 500 ml of 0.02 g/l SIBX solution.
This is equivalent to 5000 g of reagent/t of sulphide – which is similar
to that in a typical Merensky float where the sulphide content of
the ore is approximately 1%.
In a number of tests the sample was treated with a copper sulphate
solution buffered to pH 9 and added either before or after reaction
with SIBX. The concentration of copper sulphate was equivalent
to an addition of 50 g/t. The sample was then transferred to the
microflotation cell, the cell filled with buffer solution at the required
pH value and the cone placed in position. The peristaltic pump
flow rate was set to maintain a good suspension of the particles and
flotation began.
Even without collector addition the degree of natural hydropho-
bicity of the sulphide minerals gives a measure of floatability in the
microflotation cell. Since depressants did reduce the overall float-
ability of the samples they were added to some of the tests described
below to amplify the differences in hydrophobicity resulting from
different pre-treatments. As required, 2 ml of depressant solution
was added prior to filling and the sample conditioned for a further
2 min. The effect of different depressants on the hydrophobicity was
separately assessed. From the results obtained for mineral recovery
with time in the microflotation tests, the rate constant was calculated
using a first order model (Klimpel, 1980). This provides a comparison
for the effect of different conditions on the hydrophobicity of the
mineral samples.
3. Results
3.1. Adsorption measurements
Fig. 1 shows the extent of adsorption of SIBX as a function of time
at pH values between 6.5 and 10. The results here (and in Figs. 2–4)
are expressed as pseudo-monolayers of adsorbed xanthate calculated
on the assumption that one xanthate molecule occupies ~30 A2 of
surface (Granville et al., 1972) and the values corrected for sample
purity. The reaction curves are similar to those found in other studies
for the formation of dixanthogen at sulphide surfaces (Harris and
Finkelstein, 1997).
Fig. 2 compares the adsorption of SIBX of constant molar dosage on
to samples of different masses, and hence surface areas, of pyrrhotite.
In the case of 1 g and 2 g samples, analysis of the residual solution
showed that all the SIBX was ultimately adsorbed after 50 and 82 min
respectively. In the case of the 0.5 g sample, 40% of the original
concentration of SIBX remained in solution after almost 100 min. This
5 4
monolayers SIBX
6
5
4
3
2
1
0
0 10 20 30 40 50 60 70
mins
1/2g 1g 2g
Fig. 2. Number of pseudo-monolayers of products of SIBX interaction (assuming 30 A2
footprint) as determined by differences in SIBX concentration in solution before and
after contact with pyrrhotite as a function of sample size (constant SIBX dosage of
0.01 g).
last result suggests that after the equivalent of 7 pseudo-monolayers
had adsorbed onto the pyrrhotite the adsorption was of a weak
physisorbed nature and was essentially at equilibrium. On the other
hand in the case of the 1 g and 2 g samples there was ample surface
area available to enable complete adsorption of all molecules onto the
mineral surface.
Fig. 3 shows the effect of copper activation on the rate of
adsorption of SIBX onto pyrrhotite. In the case of the 1 g sample
where the reagent: surface area ratio is relatively high, within the first
few minutes after copper activation there is a rapid adsorption of SIBX
onto the mineral sample followed by a continuing formation of multi-
layers of surface product but at a reduced rate compared to that
observed in the absence of copper activation. This observation was
much less pronounced in the case of 2 g of pyrrhotite i.e. for a sample
with twice the surface area and lower reagent: surface area ratio. This
may be indicative of the selective adsorption of Cu2+ at certain surface
sites thus allowing for parallel adsorption of SIBX at non-activated
sites.
Experiments were carried out to determine the effect of the
addition of depressant at various times after the start of the reaction
between a pyrrhotite sample and SIBX. The depressant reduced the
extent of the ongoing adsorption but did not inhibit it entirely. Both
guar and CMC were found to give similar results. It is clear that the
depressant molecules do not cause any desorption of adsorbed
xanthate species but may passivate sites on which further xanthate
adsorption could have occurred. This is consistent with studies done
4.5
3.5
Monolayers SIBX

4
Monolayers SIBX

3 2.5
2
2 1.5
1
1
0.5

0 0
0 10 20 30 40 50 60 70 0 5 10 15 20 25 30 35
Mins Mins
pH 6.5 pH 7.5 pH9 pH 10 1g no Cu 1g + Cu 2g no Cu 2g +Cu

Fig. 1. Number of pseudo-monolayers of products of SIBX interaction (assuming 30 A2 Fig. 3. Number of pseudo-monolayers of products of SIBX interaction (assuming 30 A2
footprint) as determined by differences in SIBX concentration in solution before and footprint) as determined by differences in SIBX concentration in solution before and
after contact with pyrrhotite as a function of pH. after contact with copper sulphate.
 S.A. Allison, C.T. O'Connor / International Journal of Mineral Processing 98 (2011) 202–207 205

100 where less SIBX adsorbed on the larger surface area sample in
90 equivalent time. It is interesting to observe that although longer times
k=0.57
k=0.52 for xanthate adsorption may have been associated with a greater
80
70 degree of surface oxidation, the recoveries were nevertheless very
Recovery, %

high. On the other hand a contact time of 1 min resulted in a recovery

60
k=0.3 which was hardly different to that observed with no collector.
50 Fig. 6 shows the recoveries obtained when the pyrrhotite was
k=0.1
40 exposed variously to the sequence of SIBX addition followed by
30 guar, or Cu–SIBX–guar, SIBX–Cu–guar and [SIBX/Cu premixed]–guar
20 respectively. The highest recoveries were obtained when the sample
was first activated with Cu2+ and then the collector added followed
10
by the depressant. This result is consistent with the surface coverage
0 results shown in Fig. 3 and the depressant results. Addition of guar
0 5 10 15 20 25
either in the absence of Cu2+ or after pre-mixing of SIBX and Cu2+
Mins
resulted in a poorer flotation recovery. The lowest recovery
pH5.5 pH7 pH9 pH10 was observed when guar was added at the end (after SIBX followed
by Cu2+). However guar had little depressing effect when added after
Fig. 4. Pyrrhotite recovery obtained in a microflotation cell at different pHs and the sequence Cu2+ followed by SIBX.
equivalent SIBX concentrations (2 g of mineral sample; 500 ml of 0.02 g/l SIBX With regard to the use of depressants such as CMC it is known that
solution).
the effectiveness of these depressants may be significantly affected by
the ions present in typical plant water. A number of tests were carried
of the interactions between guar and xanthate in the presence of out, both with and without depressant addition, in which the
chalcopyrite (Rath et al., 2001). synthetic plant water described above was used instead of deionised
water to make up the buffer solutions. No significant differences were
3.2. Microflotation tests found.
Solid precipitates of ferric hydroxide, arising from corrosion
The microflotation tests were performed at various conditions in products produced in milling and processing, are likely to be present
order to determine the influence of factors such as pH, conditioning in flotation systems at alkaline pH values. In a set of tests to inves-
time, copper activation and the presence of depressant on the tigate semi-quantitatively the effect of adding such iron hydroxides
recovery of pyrrhotite. Fig. 4 shows the percent recovery of pyrrhotite to the pulp on the flotation was evaluated. A significant reduction
with time at different pH values for equivalent SIBX concentrations. In in the flotation rate and recovery was observed with the first order
these tests there was no addition of copper sulphate or depressant. rate constant measured as k = 0.12 min−1 compared to the value of
The first order rate constants are also shown for each test. A significant 0.3 min−1 for the standard float at pH = 9 (Fig. 4). This was taken to be
reduction in the flotation rate of pyrrhotite occurred as the pH indicative of the negative effect which the presence of iron hydroxides
increased. These results are consistent with previous studies of the had on the flotation either as a result of direct oxidation of the surface
effect of pH on contact angles for a pyrrhotite–SIBX system (Miller of the pyrrhotite or as a result of being present following a mild steel
et al., 2005) and with the fact that at the higher pHs the pyrrhotite milling process.
is most likely to be significantly oxidized. These results are also
consistent with the lower surface coverage observed at pH = 10 4. Discussion
(Fig. 1).
Fig. 5 shows the effect of increasing the extent of surface coverage The adsorption and microflotation results were aimed at devel-
on recovery at pH = 9 by increasing the SIBX conditioning times prior oping an understanding of why, in flotation circuits, pyrrhotite is
to flotation. The first order rate constants are also shown. Clearly observed to be slow floating and its recovery poor. Notwithstanding
greater recoveries were obtained after longer conditioning times. This the well-known fact that at alkaline pHs pyrrhotite rapidly oxidizes
may be indicative of a slow surface reaction between the pyrrhotite and may be covered with iron hydroxide species these results have
and the xanthate and is consistent with the results shown in Fig. 2 shown that even in this pH range there is a fairly rapid reaction of
pyrrhotite with xanthate as indicated by the reduced solution
90
80
k=0.24 100
70 90
80
Recovery, %

60
k=0.12
Recovery, %

70
50 k=0.318
60
40 50
k=0.086 k=0.043 k=0.09
30 40
k=0.086
30 k=0.047
20 k=0.035
20
10 10
0
0 0 5 10 15 20 25
0 5 10 15 20 25
Mins Mins

no coll 1 min 2 min 5 min 25.5 min sibx-guar Cu-sibx-guar sibx-Cu-guar sibx/Cu-guar

Fig. 5. Pyrrhotite recovery obtained in a microflotation cell after prior contact with SIBX Fig. 6. Pyrrhotite recovery obtained in a microflotation cell after various combinations
for varying times prior to flotation (pH = 9). of addition of SIBX, copper sulphate and guar.
206 S.A. Allison, C.T. O'Connor / International Journal of Mineral Processing 98 (2011) 202–207
concentration of SIBX when contacted with pyrrhotite thus implying
the formation of multiple pseudo-monolayers of xanthate reac-
tion product at the surface. The precise nature of the interaction
between sulphide mineral surfaces and xanthates continues to be an
area of on-going research. These interactions are related to well-
defined reactions leading to the formation of sparingly soluble surface
chemical complexes at the mineral surface. The other mode of
interaction is strongly related to electrochemical interactions (Rao,
2004).
As referred to above, the pyrrhotite/xanthate reaction product has
been shown to be dixanthogen (Miller et al., 2005), subject to the
oxidation potential being maintained at a certain value. However the
formation of dixanthogen is reduced as pH increases. Hence a
combination of increasing coverage by hydroxides and reduced
dixanthogen formation at higher pHs will result in a reduced extent
of surface reactions (higher residual concentration of SIBX as shown
in Fig. 1) and lower recoveries as shown in Fig. 4. The initial rate of
disappearance of SIBX (Fig. 1) also correlates well with the reduced
rate of flotation (Fig. 4). However the surface coverage by reaction
products of SIBX at the higher pHs is not very significantly less than
observed at pHs of 5.5–6.5 and so it is unlikely that reduced surface
coverage can account for the slower flotation. At alkaline pHs the
zeta potential of pyrrhotite is strongly negative and hence there is
little chance of an electrostatic interaction between the xanthate
ion and the surface. Hence presumably the conversion to dixanthogen
probably continues but to a lesser extent thus reducing the hydro-
phobicity as observed in the lower recoveries. This reduced formation
of dixanthogen may be associated with the increased formation of
ferric hydroxide which is favoured at the higher pHs (Belzile et al.,
2004). Speciation diagrams, in the pH of range 9–11, show that both
the solid forms of Fe(OH)3 and Fe(OH)2 are dominant although Fe
(OH)+ is also present in significant concentrations. It may be possible
that this latter species forms an Fe(OH)X complex and this will be
discussed later. However the surface hydroxide precipitates will
contribute to a reduction in the overall hydrophobicity of the mineral.
Pyrrhotite is known to be highly reactive and it is also possible that
at the higher pHs the oxidation of the surface is very fast thus also
leading to reduced xanthate adsorption/reaction and reduced flota-
tion rates.
In a flotation system a typical addition of xanthate is 30–50 g/ton
which is equivalent to 3000–5000 g/t of the sulphide mineral content
in Merensky ore and would be sufficient to produce a surface coverage
of between 3 and 5 pseudo-monolayers. These were the concentra-
tions used in the present study. Fig. 2 showed that even when the
ratio of SIBX to surface area was at its lowest (the 2 g sample) it
was still possible to produce coverage of 3 pseudo-monolayers. It was
observed that provided xanthate was available in solution the rate
of formation of surface layers of reaction products of SIBX was
independent of concentration suggesting that increasing the dosage of
collector but keeping the conditioning time constant would not
increase the rate of flotation or the recovery of pyrrhotite. Even at
low contact times (e.g. b5 min) equivalent monolayer coverage was
achieved. Fig. 5 showed that a significant increase in recovery was
found with extended conditioning times indicating that the formation
of reaction product continues as long as collector is present and that
this does increase surface hydrophobicity. It should be noted of course
that these studies were carried out in the absence of other sulphides
and hence there is no competition for the xanthate. In a real system
the other sulphides would preferentially adsorb the xanthate and
hence the poor recovery of pyrrhotite in real ores could be due to the
lack of sufficient xanthate in the system. Nevertheless it is worth
emphasizing again that even at low xanthate to pyrrhotite surface
area dosages the equivalent of a monolayer coverage is attained in a
relatively short time.
Fig. 3 showed that the presence of copper sulphate resulted in an
increase in the surface coverage by reaction products of SIBX
especially at low contact times. This was reflected in Fig. 6 in the
case of copper sulphate being added first followed by SIBX and then
guar. This case gave the highest recovery in that set of experiments.
Interestingly when the surface area is doubled (the 2 g experiment)
the effect of copper sulphate addition on surface coverage is less
significant and this may simply be due to a concentration of sites
available for xanthate adsorption. It may be possible that species such
as Cu(OH)2 occupy sites on which xanthate species may otherwise
have adsorbed or otherwise Cu2+ ions may be reacting with xanthate
to form CuX2 although the yellow colour usually associated with
the formation of such a precipitate was not observed.
Although the question of whether pyrrhotite can be activated with
copper sulphate has been questioned, these results are consistent
with those observed by previous workers (Kelebek et al., 1996;
Leppinen, 1990). In the presence of xanthates at alkaline pHs, Cu2+
firstly forms Cu(OH)2 which then subsequently reacts with xanthate
ions to form CuX2. Activation is however generally thought to be
dependent on the formation of Cu1+ species (Shackleton et al., 2003)
and this occurs through the subsequent conversion of 2CuX2 to Cu2X2
and X2. When copper was added after reaction with collector (Fig. 6)
the hydrophobicity was not enhanced suggesting that the presence of
metal hydroxide inhibited the activation role of the Cu2+. From a
mechanistic view, Hodgson and Agar (1989) have proposed the
following steps for the reaction between xanthate and pyrrhotite
(Po):
þ þ
Po þ H2 O→½PoðOHÞðSÞ þ H þ e ð1Þ
þ −
½PoðOHÞðSÞ þ X →PoðOHÞðSÞðXÞ ð2Þ
−
PoðOHÞðSÞðXÞ þ X →PoðOHÞðSÞðXÞ2 þ e ð3Þ
Thus the overall reaction is proposed to be:
− þ
Po þ H2 O þ 2X →PoðOHÞðSÞðXÞ2 þ H þ 2e ð4Þ
This mechanism allows for the formation of hydroxides at the
surface while also accounting for the reaction with xanthate. This
½reaction is coupled with the following reduction reaction:
1
= −
2 O2 þ H2 O þ 2e→2OH ð5Þ
2+
When copper sulphate is added, the Cu will compete for the
xanthate as in the following reaction:
2CuX2 →Cu2 X2 þ X2 ð6Þ
Reaction (6) results in the formation of the activating monovalent
copper species. Hence when xanthate is added before the Cu2+,
reactions (2) and (3) may be the primary reactions involving
xanthate, reaction (6) will hardly occur and copper activation will
be minimal. This could explain the low recoveries observed for such a
situation in Fig. 6. It is also interesting to observe that, in the case of
the SIBX–Cu–guar addition sequence, recoveries were worse than for
SIBX–guar which may point to some interaction between guar and the
Cu2+. Guar added after the addition of SIBX resulted in low recoveries.
This is consistent with the findings of Rath et al. (2001) in a study of
the interaction of guar with xanthate on a chalcopyrite surface where
they showed that when xanthate and guar are present in such a
system they mutually enhance the adsorption of each species but that
the depressant effect of guar remains dominant. Adding a pre-mixed
solution of xanthate and copper sulphate resulted in a similar low
recovery and this may be due to the formation of copper xanthate in
solution thus reducing the concentration of free xanthate available
for promoting hydrophobicity. However as previously stated there
were no visible signs of the yellow colour typical of copper xanthate
precipitates.
 S.A. Allison, C.T. O'Connor / International Journal of Mineral Processing 98 (2011) 202–207
From the perspective of plant practice it is commonly observed
that there is little residual guar in the recycled process water whereas
there is certainly often a significant concentration of Cu2+. This
situation would thus be favourable in operations where increased
recovery of pyrrhotite is desirable since the Cu-SIBX-guar sequence of
addition resulted in high pyrrhotite recovery. This would specifically
be favourable in the treatment of PGM ores. However when pyrrhotite
depression is required there would be a need to carefully manage
copper sulphate addition.
5. Conclusions
This study has shown that adequate surface coverage of SIBX-
originated species on the surface of pyrrhotite occurs over a wide
range of pH values and that this surface reaction is promoted by the
pre-treatment with copper sulphate especially at short conditioning
times. Hence the observed slow floating nature of pyrrhotite does not
appear to be a result of inadequate coverage by xanthate products.
Recoveries in a microflotation cell followed the same trends as surface
coverage by xanthate species at different pHs. Longer conditioning/
exposure times to SIBX resulted in a greater degree of surface cov-
erage and also greater recoveries. Guar, when added after copper
sulphate, did not reduce recovery but when added in any other
sequence resulted in significant reductions in recovery.
A number of these findings have implications for plant practice.
Maintaining an adequate concentration of collector in the system will
permit an ongoing reaction and increase hydrophobicity and float-
ability of the pyrrhotite through the circuit. However, high dosages of
xanthate will not necessarily result in increased recoveries unless
there is sufficient contact time allowed for adequate surface coverage
to occur. At short contact times surface coverage can be enhanced
by prior addition of copper sulphate. Ultimately the slow reaction of
xanthate with pyrrhotite as a result of the presence of surface iron
hydroxide species will result in the pyrrhotite being slow floating
rather than non-floating and hence managing flotation cell residence
times and contact times with xanthate will be an important operating
variable. In the presence of other sulphides pyrrhotite would
experience lower xanthate coverage due to the preferential adsorp-
tion of xanthate on, for example, chalcopyrite or pentlandite.
Careful management of copper sulphate can lead to increased
recoveries but overdosing may result in the formation of excess
copper hydroxide in solution and that is likely to have a more serious
negative effect on pyrrhotite recovery than overdosing with xanthate
since the copper hydroxide will react with the collector before the
latter is able to react with the mineral surface. Recycled process
water may often contain significant amounts of copper ions but this
may, in certain circumstances, result in increased recoveries. Finally
the depressants will generally reduce recovery unless added after the
Cu2+ ions have had an opportunity to activate the surface.
207
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