This paper is looking at DETA will depress Cu sulfides, just as We could easily test this with Los

pyrite single mineral, not ore it does Cu-activated pyrite Bronces Cu ore.
flotation
Minerals Engineering 57 (2014) 36–42

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Diethylenetriamine depression of Cu-activated pyrite hydrophobised

by xanthate
Eric A. Agorhom ⇑, W. Skinner, M. Zanin
Ian Wark Research Institute, The ARC Special Research Centre for Particle and Interfaces, University of South Australia, Mawson Lakes Campus, Adelaide, SA 5095, Australia

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

Article history: In copper sulphide flotation, copper adsorbs on pyrite through superficial oxidation of the copper miner-
Received 24 August 2013 als (e.g. chalcopyrite) which promotes pyrite flotation in the presence of xanthate. This ‘‘inadvertent’’ xanthate
Accepted 6 December 2013 activation of pyrite by copper ions is undesirable in copper sulphide flotation. In order to minimise this again. C
Available online 28 December 2013
effect, depressants are used to suppress the effect of the activating ions. The effect of diethylenetriamine plants d
(DETA) in different combinations (under aerated and non-aerated conditions) on Cu-activated pyrite use
Keywords: hydrophobised by xanthate was examined using flotation, spectroscopic and solution analyses, at pH
Flotation
oxidation of xanthate
secondary Cu 10. The results showed that DETA affects the flotation behaviour and surface chemistry of pyrite. How-
Depression
Diethylenetriamine sulfides is more ever, high dosages are required. The depression action of DETA on Cu-activated pyrite was attributed
to both the removal of surface copper to form soluble Cu–DETA complex in solution and competition What
Surface analysis likely. Plus Cu
Pyrite for Cu sites on the activated pyrite surface. The significant depression of pyrite in the presence of DETA depres
from nonsulfide
under the aerated condition was due to increased amount of iron oxy–hydroxides (Fe–O/OH), copper
Cu minerals
oxides and Cu(I)–DETA hydrophilic species.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction species, decomposition of xanthate and consumption of oxygen

(reduction in Eh) (Misra et al., 1985; Yamamoto, 1980; Miller,
Chalcopyrite and gold are the main valuable mineral phases in 1970). Despite numerous studies on the mechanism of sulphite
most polymetallic sulphide ores, with pyrite being the main ions in pyrite depression, little effort has been made to understand
sulphide gangue mineral. Chalcopyrite and gold are mostly associ- the effect of diethylenetriamine (DETA) in selective depression of
ated with pyrite in these ores; therefore, their economical extrac- pyrite in sulphide minerals.
tion requires a selective depression of pyrite. DETA is a polyamine and soluble in water and alcohol (Weast,
The major problem associated with chalcopyrite and pyrite 1985). Generally, polyamines are excellent complexing or chelat-
selectivity is due to accidental activation of pyrite by dissolved ing agents. The application of DETA in flotation is to depress sul-
Cu2+ or Pb2+ ions from complex sulphide minerals through oxida- phide minerals and has been used extensively in pyrrhotite
tion/dissolution reactions, which may be enhanced by galvanic rejection in Ni–Cu ore flotation. It has been observed by Falcon-
interactions. This enhances pyrite interaction with thiol collectors bridge Ltd., that DETA was only effective in rejecting pyrrhotite
and hence promotes its floatability. In most processing plants, so- in the presence of SO2 (Kelebek et al., 1995). The mechanism of
dium cyanide is employed to depress pyrite (by removing Cu2+ ions DETA in the rejection of pyrrhotite was linked to the removal of
from its surfaces) under alkaline conditions. The environmental activating ions (e.g. Cu2+ and Ni2+). The removal of activating ions
and health hazards associated with cyanide usage make it an un- from pyrrhotite surfaces in the presence of DETA resulted in a de-
safe approach to depress sulphides in selective flotation. As an creased xanthate adsorption and hence reduced its floatability
alternative to cyanide, sulphur–oxy depressants, in the form of sul- (Yoon et al., 1995). In another related operation (Inco operations),
phite (SO2 2 2
3 ), bisulphite (HSO3 ), metabisulphite (S2 O5 ) or sulphur it was observed that DETA was only effective when pyrrhotite was
dioxide (SO2
2 ) have been used in depressing pyrite, sphalerite and extensively oxidised. This is because the activation product on the
galena (Grano et al., 1997a, 1997b; Khmeleva et al., 2002, 2003; pyrrhotite surface (CuS species) is insoluble in the reducing condi-
Shen et al., 2001; Chander and Khan, 2000; Bulut et al., 2011). tion which is not soluble in DETA (Yoon et al., 1995). However,
The general mechanism of sulphide mineral depression using sul- when pyrrhotite is oxidised, the activation product is converted
phite ions involves the formation of metal sulphite hydrophilic to oxide/hydroxides of copper and nickel, which are more soluble
in DETA. The effective role of DETA in depressing pyrrhotite has
led to an investigation into its applicability in depressing other sul-
⇑ Corresponding author. Tel.: +61 883023692. phide minerals like pyrite. Sui et al. (1998) have shown that DETA
E-mail address: [email protected] (E.A. Agorhom).

0892-6875/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.12.010
 E.A. Agorhom et al. / Minerals Engineering 57 (2014) 36–42 37

can be a good depressant for pyrite. The depression mechanism of was examined, at pH 10. The experimental procedure is shown
DETA on pyrite involves the removal of activating ions (in this case, schematically in Fig. 1.
Pb2+) and the formation of a hydrophilic Pb–DETA complex which
adsorbs back onto the pyrite surface to compete with xanthate for 2.4. Rest potential measurement
adsorption sites. Although the use of DETA for depressing pyrite is
as good as sulphur–oxy depressants, limited work has been con- The rest potential for the pyrite in the pulp during conditioning
ducted on this depressant (Sui et al., 1998; Zanin and Farrokhpay, and flotation was measured using a TPS 90-FLMV pH/Eh/DO com-
2011). bined meter. The pH and Eh probes were calibrated using pH buffer
In this study, the effect of DETA in combination with aeration of solutions of 7 and 10 and Light’s solution (Light, 1972).
Cu-activated pyrite in flotation was investigated. Surface (X-ray
spectroscopic, XPS and EDTA extraction technique) and solution 2.5. X-ray photoelectron spectroscopy (XPS)
(Ultraviolet visible spectroscopic, UV–visible and inductively cou-
pled mass spectroscopy, ICP-MS) analytical techniques were used The X-ray spectroscopy (XPS) measurements were performed
to understand the mechanisms of DETA on Cu-activated pyrite using a Kratos Axis-Ultra X-ray photoelectron spectrometer
depression. equipped with a delay-line detector. A monochromatised Al Ka
X-ray source was used, operating at 300 W and the spectrometer
analysis area was 0.3  0.7 mm dimensions. The broad scan sur-
2. Materials and methods
vey and high-resolution spectral data were processed using Casa-
XPS version 2.3.5. The Cu-activated pyrite samples were taken
2.1. Chemical composition
from the flotation experiments (Fig. 1) and the following sample
This streams (Py + Cu + X, Py + Cu + X + 500 g/t DETA, Py + Cu + X + Air
A high grade pyrite sample was obtained from a copper mine in
paper is Peru. The chemical/elemental compositions of the pyrite sample and Py + Cu + X + Air + 500 g/t DETA) were analysed. For the XPS
lookind at analysed by inductively coupled plasma mass spectroscopy (ICP- analysis, each sample was analysed for Cu, Fe, S, O, C and N in
pyrite terms of their surface atomic concentration (.%). High resolution
MS) is shown in Table 1.
single scans were also collected of the C 1s, O 1s, Fe 2p, Cu 2p and S 2p
mineral photoemission lines.
2.2. Reagents
2.6. EDTA extraction technique
All the chemical reagents were of analytical grade. Potassium
amyl xanthate (CH3CH2OCS2K, abbreviated PAX) and methyl iso- Ethylene diaminetetraacetic acid (EDTA) was used to extract
butyl carbinol (MIBC) were used as collector and frother, respec- metal oxidation products (e.g. oxide/hydroxide, sulphate, carbon-
tively. PAX and MIBC were supplied by Orica Mining and Cytec ate, etc.) from the pyrite surface (Kant et al., 1994; Rumball and
Chemicals, respectively. Copper sulphate (CuSO4) was used as an Richmond, 1996; He, 2003), in the following: Py + Cu + X, Py +
activator for pyrite during the conditioning time. Diethylenetria- Cu + X + 500 g/t DETA, Py + Cu + X + Air and Py + Cu + X +
mine (NH2–CH2–CH2–NH–CH2–CH2–NH2, abbreviated DETA, 99% Air + 500 g/t DETA sample streams. A pulp volume of 0.1 dm3
pure) supplied by Sigma–Aldrich, and air were used as depressants. was mixed with a 3% AR grade EDTA solution and conditioned
The pulp pH was kept constant at 10 by means of lime and hydro- for 5 min while purging with nitrogen to prevent further oxidation
All chloric acid additions. Ethylene diaminetetraacetic acid di-sodium of the pyrite surface. The EDTA solution was purged with nitrogen
dosages salt (abbreviated EDTA, 99% pure), supplied by AJAX CHEMICALS. for 10 min before extraction to remove residual oxygen. The
are very The reagents concentrations used were; CuSO4 (200 g/t), PAX amount of surface oxidation products extracted by EDTA was mea-
high (100 g/t), MIBC (40 g/t), DETA (200 and 500 g/t) and air (2 dm3/ sured in solution by inductively coupled plasma mass spectroscopy
min for 5 min). Each reagent was prepared as 1% solution strength (ICP-MS).
before used in the flotation process.
2.7. UV–visible spectroscopy
2.3. Sample preparation and flotation
An Evolution 201 UV–visible spectrophotometer was used to
3 determine the concentration of xanthate remaining in solution be-
The experiment was carried out in a 0.5 dm Gliwice mechani-
fore and after treatment with DETA. Identifying the peaks (for
cally agitated flotation cell. Ceramic agate mortar and pestle were
xanthate and DETA) in the process water was difficult due to the
used to grind the pyrite sample to produce particles of d80 = 38 lm.
presence of other mobile ions, hence demineralised water at neu-
The particle size distribution of the feed pyrite was determined by
tral pH was used for all the experiments. A 0.1 dm3 beaker contain-
Malvern MasterSizer (Malvern Instrument Ltd., UK). The ground
ing demineralised water was maintained at neutral pH 7 prior to
products were divided into 50 g each, kept under a desiccator to re-
potassium amyl xanthate addition. All spectra were recorded over
move all moisture content before storing in a freezer below 4 °C
the range 200–400 nm. In addition to xanthate in solution, adsorp-
to minimise surface oxidation. After grinding, 50 g of the sample
tion spectrum was recorded for Cu-activated pyrite induced by
was pulped in the flotation cell and agitated for 5 min before re-
xanthate in the presence of DETA.
agent conditioning. In these tests, the effect of depressant, DETA
(at different dosages) under aerated and non-aerated conditions
3. Results

Table 1 3.1. Flotation

Chemical composition of the pyrite sample.

Elements (wt.%) 3.1.1. Effect of DETA and aeration

Fe S Cu Ca Si Pb Mg Zn Mn Py The effect of DETA on pyrite rejection was studied under two
Pyrite 44.9 53.5 0.13 0.44 0.69 0.02 0.08 0.18 0.02 >98
different test conditions; (1) non-oxidising (or non-aerated) and
(2) oxidising, (or aerated) condition. The experimental results
38 E.A. Agorhom et al. / Minerals Engineering 57 (2014) 36–42

DETA (200 g/t, 500 g/t)

3 min
Air, 2 dm 3/min (5 min)

PAX (100 g/t) MIBC (40 g/t)

CuSO4 (200 g/t)
2 min 1 min
3 min

Feed
Tail

d80 = 38 µm

Fig. 1. Schematic representation of the experimental procedure for studying the effect of DETA in single mineral pyrite flotation.

under non-aerated condition are presented in Fig. 2a. The results The depression of pyrite in the presence of DETA is also de-
showed that pyrite recovery without air and DETA was high scribed by the initial rate constants, k0, under the experimental
(92 wt.%) in the presence of xanthate. However, under aerated con- conditions (Table 2). In the absence of air and DETA, the initial flo-
dition, pyrite recovery decreased from 92 wt.% to 65 wt.% (Fig. 2b). tation rate constant of pyrite was high (1.06 min1). However, in
This can be attributed to the formation of ferric hydroxide species the presence of air, 200 g/t DETA and 500 g/t DETA, the initial pyr-
which passivate pyrite surface and prevent adsorption of both Cu ite flotation rate constants decreased to 0.61 min1, 0.29 min1
and xanthate (Owusu et al., 2013). Addition of 200 g/t DETA with- and 0.20 min1, respectively. Similar lower flotation rate constant
out aeration also decreased pyrite recovery substantially (from 92 of pyrite (0.02 min1) was observed when DETA was added before
to 44 wt.%). Increased DETA concentration (500 g/t) further de- xanthate conditioning. Also, lower pyrite flotation initial rate con-
creased pyrite recovery, from 92 to 33 wt.% (Fig. 2a). The effect is stants were observed when DETA was applied after aeration of the
enhanced when aeration and DETA are used in combination pulp and this could be responsible for the significant depression of
(Fig. 2b). This shows that DETA can depress Cu-activated pyrite flo- pyrite (Table 2). The results indicate that DETA addition and aera-
tation induced by xanthate. However, high dosages are required, tion decreased pyrite recovery significantly than either DETA or air
which is consistent with other studies in the literature (Sui et al., alone.
1998). DETA addition prior to collector (PAX) resulted in drastic
reduction in pyrite recovery, from 92 to 13 wt.% (Fig. 2a). This 3.1.2. Rest potentials
can be attributed to both the removal of activated copper and The open-circuit or rest potential measured during the flotation
adsorption of DETA onto the active sites of pyrite to compete with involving DETA is shown in Fig. 3. Addition of DETA decreased the
xanthate. The latter can lead to the formation of Cu–DETA hydro- rest potential by 35 mV (from 257 to 222 mV). The decreased rest
philic species on pyrite surface and thus hinder the formation of potential may be due to the ability of DETA to form chelates
Cu–xanthate (hydrophobic entity) for improved pyrite flotation. with Fe2+ ions resulting in their stability. This may slow down

100 100

(a) Py+Cu+X+Air (b)

Py+Cu+X+Air+200 g/t DETA
80 80
Py+CU+X+Air+500 g/t DETA
Pyrite recovery (%)
Pyrite recovery (%)

Py+Cu+X
60 Py+Cu+X+200 g/t DETA 60
Py+Cu+X+500 g/t DETA
Py+Cu+500 g/t DETA+X

40 40

20 20

0 0
0 2 4 6 8 10 0 2 4 6 8 10
Flotation time (min) Flotation time (min)

Fig. 2. Effect of DETA on depression of Cu-activated pyrite induced by xanthate (PAX) at pH 10 under (a) non-aerated condition and (b) aerated condition. [CuSO4] = 200 g/t,
[PAX] = 100 g/t, [DETA] = 200 g/t and 500 g/t and aeration rate was 2 dm3/min for 5 min.

Table 2

The initial rate constants of Cu-activated pyrite after conditioning and flotation with DETA at different dosages and conditions (aerated and non-aerated), k0 ¼ k Rmax .

Rate constant Xanthate X + 200 g/t DETA X + 500 g/t DETA 500 g/t DETA + X X + Air X + Air + 200 g/t DETA X + Air + 500 g/t DETA
k0 1.06 ± 0.03 0.29 ± 0.01 0.20 ± 0.01 0.02 ± 0.01 0.61 ± 0.02 0.18 ± 0.01 0.06 ± 0.01
k 1.16 ± 0.03 0.69 ± 0.01 0.64 ± 0.01 0.14 ± 0.01 0.95 ± 0.02 0.67 ± 0.01 0.48 ± 0.01
 E.A. Agorhom et al. / Minerals Engineering 57 (2014) 36–42 39

260 passivation (masking) of surface Fe by increased amount of C and

Open circuit potential (mV SHE)

N. The reduction in Fe could also be due to the formation of aque-

250
ous complex of DETA with oxidised ferrous iron (Kelebek, 1996).
240 This condition may slow down the rate of the oxidation of pyrite
resulting in the formation of ferric hydroxyl xanthate, which is
230
one of the species responsible for impacting hydrophobicity of
220 pyrite for improved flotation.
Under the aerated condition (Fig. 4b), DETA removes Cu from
210
Open-Circuit Potential (mV SHE)
the pyrite surface and, in the process, collector is removed. It is
suggested that DETA competes with collector-Cu, displacing the
200
collector (due to decrease in C concentration) and increase in both
190 Fe and S. It is also observed that some of the DETA binds with Cu on
0 CuSO4 Xanthate Aeration DETA st DETA ed
the surface (appearance of significant N) oxidising it to Cu(II) in the
Condition
process. Consequently, the concentration of the surface copper
Fig. 3. Open-circuit or rest potential after DETA addition at pH 10. [DETA] = 500 g/t, responsible for collector adsorption decreased significantly (i.e.
[PAX] = 100 g/t, [CuSO4] = 200 g/t and [Air] = 2 dm3/min for 5 min. from 3.4 to 0.9 .%). After conditioning, the aerated Cu-activated
pyrite with DETA, the surface Fe exposure increases significantly,
and this may be due to the relative contribution of iron from oxi-
the oxidation process of xanthate to dixanthogen, which is the dised species (Fe–Ox) to the total surface Fe. Clearly, the use of
main xanthate product responsible for pyrite flotation. DETA after aeration has a greater effect on the surface chemistry
of pyrite particles compared to either DETA or air alone. In the
3.2. Surface/solution chemical effect presence of air and DETA, more iron oxide (Fe–Ox), copper oxide/
hydroxides and Cu–DETA species (increased amount of N) were
3.2.1. XPS study formed on the pyrite surface increasing the surface hydrophilicity
The results in Fig. 4a show the XPS analysis of Cu-activated pyr- and hence decreasing pyrite floatability (Fig. 2b). The Fe 2p and Cu
ite induced by xanthate before and after conditioning with DETA, 2p XPS spectra in Fig. 5a and b further confirm the presence of iron
under non-aerated condition. After contacting DETA with Cu-acti- oxy–hydroxide and copper oxide/hydroxide species on the surface
vated pyrite, it was observed that the amount of Cu on pyrite sur- of the Cu-activated pyrite in the presence of air and DETA.
face decreased considerably. About 75% of the Cu was removed
from pyrite surface in the presence of DETA. This suggests that
DETA is an effective Cu deactivator. The surface exposure of N on 3.2.2. EDTA extractable surface metal species
pyrite concomitantly increases after contacting with DETA. This To further understand the mechanism of DETA depression of
finding suggests that DETA does not only remove copper from Cu-activated pyrite under aerated and non-aerated conditions,
the activated pyrite but also adsorb onto the pyrite surface, per- EDTA extraction was performed on the aerated and non-aerated
haps displacing and/or preventing further interaction with collec- samples before and after DETA addition. Table 3 shows the amount
tor (xanthate). The surface Cu exposure was too low after DETA of Cu and Fe oxidation species extracted by EDTA solution. For the
treatment for the collection of a high resolution Cu 2p spectrum, non-aerated condition, the amount of EDTA extractable copper in-
however the Cu 2p3/2 component acquired in the survey spectrum creased (from 0.032 to 0.038 mg/g) while the amount of EDTA
appeared to have broadened somewhat on the high binding energy extractable iron decreased (from 0.086 to 0.074 mg/g) after DETA
side. No Cu(II) satellite contributions could be discerned, which addition, as shown in Table 3. A similar trend in terms of the con-
means that some DETA remains bound to Cu sites at the surface centrations of Cu and Fe oxide/hydroxide species was observed
in a Cu(I)–DETA form. This would seem quite plausible as a similar when DETA was added after aeration (Table 3). With respect to
broadening, to higher binding energy, of the Cu 2p3/2 has been copper oxide/hydroxide species, the EDTA extraction and XPS
observed for amine adsorption on fine Cu powders (Unwin et al., results correlate for both test conditions. This confirms the obser-
2008). The concentration of Fe in the presence of DETA decreased vation made under the aerated condition that adsorption of DETA
significantly for the Cu-activated pyrite. This may be due to on pyrite surface results in subsequent copper oxidation, from

50 50
Py+Cu+X
Py+Cu+X+Air
Py+Cu+X+500 g/t DETA
Py+Cu+X+Air+500 g/t DETA
40
Atomic Concentration (%)

40
Atomic Concentration (%)

(a) (b)
30 30

20 20

10 10

0 0
Cu Fe O C S N Cu Cu(I) Cu(II) Fe Fe-Ox O C S N
Surface Species Surface Species

Fig. 4. Surface species present on Cu-activated pyrite induced by xanthate in the presence of 500 g/t DETA under (a) non-aerated and (b) aerated conditions. ‘‘Py’’ and ‘‘X’’
denote pyrite and xanthate, respectively.
40 E.A. Agorhom et al. / Minerals Engineering 57 (2014) 36–42

Fe 2p
Fe(II)-S Cu 2p
Fe(II)/Fe(III)-O
Cu(I)-S

Py+Cu+X+Air

(a) (b)

Py+Cu+X+Air
Cu(II)-O

Py+Cu+X+Air+500 g/t DETA

Py+Cu+X+Air+500 g/t DETA

Fig. 5. Fe 2p (a) and Cu 2p (b) XPS spectra of Cu-activated pyrite in air and air plus DETA.

Table 3 ted Cu-activated pyrite, the effect of DETA is to form a soluble prod-
Surface Cu, S and Fe oxidation species present on the pyrite surface as extracted by uct (at peak 250 nm) suspected to be a Cu(DETA)2+ complex (Fig. 6b).
EDTA for Cu-activated pyrite in the presence of DETA under non-aerated and aerated
conditions.
Kelebek (1996) showed, for the Cu–Fe–S–DETA system at pH 7, that
the most dominant solution species was Cu(DETA)2+ (Fig. 7). In order
Test condition Metal oxidation species extracted by EDTA (mg/g of pyrite) to confirm the presence of Cu(DETA)2+, a mixture of Cu and DETA in
Cu Fe 1:2 M ratio was prepared and analysed by UV–visible spectroscopy.
Xanthate 0.033 ± 0.002 0.086 ± 0.002 The identified peak correlates with the peak obtained when Py +
X + DETA 0.038 ± 0.002 0.074 ± 0.002 Cu + X was treated with DETA (Fig. 6a). This finding supports the
X + Air 0.029 ± 0.002 0.098 ± 0.002 observations of earlier workers that DETA can desorb Cu from pyr-
X + Air + DETA 0.036 ± 0.002 0.069 ± 0.002
rhotite surfaces (Xu et al., 1997). Also, conditioning of Cu-activated
pyrite with DETA before xanthate addition shows little or no loss
of xanthate from solution (Fig. 6b). This observation, together with
Cu(I) to Cu(II) (Fig. 4b). Also, the reduction in the oxidised Fe the XPS surface analysis, shows adsorption of DETA onto the active
concentration in the presence of DETA suggests a possible com- sites of pyrite through complex formation with copper with a much
plexation of Fe(II) with DETA. Thus, we therefore propose that higher affinity than xanthate. This is consistent with similar obser-
adsorption of DETA onto pyrite surface through Cu–DETA complex vation made on Pb-contaminated pyrite interaction with DETA
formation promotes surface copper oxidation. (Sui et al., 1998). Therefore, this result indicates that DETA can both
desorb Cu and adsorb on more ‘‘robust’’ Cu sites on pyrite surface.
This correlates well with the flotation depression of pyrite in the
3.2.3. UV–visible study
presence of DETA (Figs. 2, 4 and 5).
The adsorption spectra for potassium amyl xanthate (PAX) in
solution, in the absence and in the presence of DETA, have been re-
corded at pH 7 as shown in Fig. 6a. In solution, the xanthate peak 4. Discussion
at 301 nm (Hao et al., 2000, 2008; Khmeleva et al., 2002; Montalti
et al., 1991) was identified but disappeared from solution in the 4.1. DETA and aeration
presence of Cu-activated pyrite. This shows a complete adsorption
of xanthate onto the pyrite surface. The addition of DETA to PAX, In the present study, it has been demonstrated that DETA can
alone, did not consume xanthate. In the presence of xanthate-trea- depress the flotation of copper-activated pyrite induced by

5 5

(a) X (b)
4 Xanthate (301 nm) X+DETA 4 Xanthate (301 nm)
DETA
X+DETA
Cu+DETA
X
Cu+DETA+X
Absorbance

Absorbance

3 3 DETA+X

Cu-DETA (250 nm)

2 2 Cu-DETA (250 nm)

1 DETA (303 nm) 1

0 0
200 250 300 350 400 200 250 300 350 400
Wavelength, nm Wavelength, nm

Fig. 6. UV absorbance spectra of potassium amyl xanthate in solution (a) and Cu-activated pyrite hydrophobised by PAX (b) in the presence of DETA at pH 7. For the Cu–DETA
complex, Cu and DETA were mixed in 1:2 M ratios. [DETA] = [Cu] = 1% solution strength.
 E.A. Agorhom et al. / Minerals Engineering 57 (2014) 36–42 41

100 pyrite) or by deliberate activation of pyrite with copper sulphate in

porphyry copper–gold flotation. The latter is mostly done to in-
crease gold recovery as a result of enhanced pyrite flotation in
80 Cu2+ CuOHDETA+ the rougher stage. However, in the cleaner stage, where selectivity
CuDETA2+
Cu-species disrtibution (%)

between chalcopyrite, gold and pyrite is required to improve cop-

per and gold grades, pyrite liberation and depression becomes
60
crucial. The findings from this study suggest that DETA can be an
advantageous depressant to reject Cu-activated pyrite hydrophob-
ised by xanthate. Furthermore, not only will DETA be able to de-
40
press pyrite but may also clean chalcopyrite surface of oxidation
products (e.g. Cu(OH)2) due to its affinity for copper ions (Fig. 7).
20
This will enhance subsequent chalcopyrite interaction with collec-
CuHDETA3+
tor and thus improve copper recovery and grade, and selectivity
over pyrite (Kelebek, 1996).
Cu+
0
2 4 6 8 10 12
pH 5. Conclusions

Fig. 7. Species distribution of Cu in Cu–Fe–S–DETA system, [DETA] = 103M DETA depressed xanthate-induced Cu-activated pyrite at pH 10
(modified after Kelebek, 1996).
(d80 = 38 lm). The depression of pyrite was more pronounced in
the presence of DETA at higher dosage (500 g/t DETA). However, al-
xanthate at a pH 10. The flotation results in Fig. 2a and b indicate most complete depression of Cu-activated pyrite by DETA was ob-
that DETA is even more effective depressant for pyrite activated by served when the pyrite was oxidised by purging with air (2 dm3/
Cu and xanthate when used in aerated condition than in non-aer- min for 5 min) before DETA addition. Spectroscopic and solution
ative condition. However, higher dosages of DETA are required. studies revealed that the depression of pyrite in the presence of
Oxidation of Cu-activated pyrite before DETA addition proved to be DETA was due to complexation with Cu in solution or its adsorbed
the most effective mechanism of pyrite depression in the presence of state (whether copper hydroxide or xanthate). The XPS, UV–visible
DETA. Cu(II) is reduced, during the adsorption process, to Cu(I) via sul- and EDTA extraction results have demonstrated under the experi-
phur oxidation to form a Cu(I)S surface species (Voigt et al., 1994). Spe- mental conditions studied that the following mechanisms are
cifically at the surface of pyrite, and in the vicinity of the reaction, this responsible for pyrite depression:
may be represented by (von Oertzen et al., 2007):
(i) Copper removal/deactivation (whether copper sulphide or
FeS2 þ 3xCu2þ þ 4xH2 O ! Cu3x FeSð2xÞ þ xSO2
4 þ 8xH
þ
ð1Þ xanthate) from the pyrite surface.
This (Cu–S species) then interacts with the collector for im- (ii) Formation of Cu(I)–DETA complex on pyrite surface and con-
proved pyrite flotation. The Cu–S activation product is observed sequently increased the oxidation of surface copper (mainly
to be highly stable and insoluble in DETA, however oxidation/aer- copper oxide).
ation of the Cu-activated pyrite transforms this product to oxides/
hydroxides which are more soluble in the presence of DETA. A sim- The fundamental findings (DETA depression effect) can be ap-
ilar observation was made by Yoon et al. (1995), where depression plied to pyrite depression in pyritic copper–gold ore flotation
of pyrrhotite was more effective under aerated or oxidative condi- and, in particular, in the post-regrind depression of pyrite for gold
tions than non-aerated condition. This is further confirmed by the recovery.
XPS and EDTA extraction results (Fig. 4a and b and Table 3), which
show that the significant depression of pyrite by DETA and aeration Acknowledgements
may not only be due to the removal of copper ions but also to in-
creased oxidation products (such as Fe–Ox, Cu(OH)2) on the pyrite The financial support from AMIRA International and the indus-
surface. try sponsors of the P260F project is strongly acknowledged. The
The XPS results (Fig. 4a and b) have shown, under the experi- first author would like to acknowledge the scholarship he received
mental conditions studied, that DETA can desorb Cu from the pyr- from the University of South Australia, Ghana government, and the
ite surface and also adsorb strongly to Cu sites in competition with University of Mines and Technology, Ghana.
xanthate. Since the activating Cu (Cu–S species) is the main species
which enhances xanthate interaction and adsorption on pyrite sur-
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