Int. J. Miner. Process.

81 (2006) 15 – 26
www.elsevier.com/locate/ijminpro

The selective flotation of enargite from other copper minerals — a

single mineral study in relation to beneficiation of the
Tampakan deposit in the Philippines
G.D. Senior a , P.J. Guy b , W.J. Bruckard c,⁎
a
BHP Billiton, GPO Box S1431, Perth, WA, 6845, Australia
b
Lucia Street, Blackburn, Vic, 3130, Australia
c
CSIRO Minerals, Box 312, Clayton South, Vic, 3169, Australia

Received 12 April 2006; received in revised form 13 June 2006; accepted 13 June 2006
Available online 31 July 2006

Abstract

The floatability of enargite (3Cu2S.As2S5) has been determined as a function of pulp potential to establish whether the flotation
behaviour of the mineral differs sufficiently from that of other copper minerals thus offering the prospect of rejecting arsenic from
the Tampakan ore by potential control during flotation.
The results of a single mineral flotation study reveal that a threshold potential exists above which enargite floats and below
which it does not. On the standard hydrogen electrode (SHE) scale this potential is about −75 mV SHE at pH 8 and about −25 mV
SHE at pH 11. By contrast, chalcopyrite (CuFeS2) has a threshold potential of about + 160 mV at pH 8 and chalcocite (Cu2S) has a
threshold potential of about −155 mV SHE at pH 11. In addition, chalcocite and cuprite (Cu2O), but not enargite and chalcopyrite,
have an upper limiting potential at pH 11 (> +270 mV SHE) above which their floatabilities are depressed.
On the basis of these results it was concluded that the selective separation of enargite from other copper minerals would be
enabled by controlling the flotation pulp potential. Specific flotation separations are as follows.

• Copper sulphides such as chalcocite and copper oxides such as cuprite could be floated from enargite at pH 11 after setting the
potential to about − 125 mV SHE.
• Enargite could be floated from copper–iron sulphides such as chalcopyrite at pH 8 or pH 11 after setting the potential to about
0 mV SHE.
• Enargite could be floated from copper sulphides such as chalcocite and from copper oxides such as cuprite at pH 11 after setting
the potential to about +290 mV SHE.
A conceptual flow sheet for arsenic rejection at Tampakan, based on these findings, is presented and discussed in this paper.
Crown Copyright © 2006 Published by Elsevier B.V. All rights reserved.

Keywords: Flotation; Enargite; Copper; Potential-controlled flotation

1. Introduction

⁎ Corresponding author. Tel.: +61 3 9545 8500; fax: +61 3 9562 The Tampakan copper–gold deposit, located on the
8919. south eastern part of Mindanao in the Philippines, is the
E-mail address: Warren.Bruckard@csiro.au (W.J. Bruckard). largest known undeveloped copper deposit in Southeast
0301-7516/$ - see front matter. Crown Copyright © 2006 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2006.06.001
16 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26
Asia. The resource is currently estimated to be 1340
million tonnes at 0.66% Cu and 0.27 g/t Au. It is
understood that a pre-feasibility study to consider
options for beneficiating the resource is currently
being undertaken by Indophil Resources NL. In
developing a flow sheet to recover the copper from the
ore, it will likely be necessary to reject arsenic that
occurs at significant levels in the deposit, primarily as
the mineral enargite (3Cu2S.As2S5). Enargite nominally
contains 19.1% As and 48.3% Cu. Arsenic is a penalty
element for copper smelters where it can cause
environmental problems when volatile arsenic com-
pounds are emitted during smelting. Consequently, high
financial penalties are imposed by smelters to treat
copper concentrates containing higher than 0.2% As
(Wilson and Chanroux, 1993).
The separation by flotation of enargite from other non-
arsenic sulphide copper minerals is difficult as enargite is
strongly floatable with thiol-type collectors and difficult
to selectively depress with standard depressants such as
lime, cyanide, sulphide, and permanganate in conven-
tional copper circuits (Tajadod and Yen, 1997). There
have been, however, a number of approaches explored
recently with regard to this separation. One possible
method relies on selectively oxidising one or more of the
sulphide minerals present prior to flotation to provide
subsequent selectivity (Fornasiero et al., 2001). Castro
and Honores (2000) reported that enargite displays a
strong resistance to be depressed by the action of strong
oxidizing agents in alkaline conditions. This property
seems to have been exploited by Huch (1993), who
patented a method for the selective flotation of enargite
from chalcocite by using hydrogen peroxide and other
oxidizing agents to selectively oxidise and depress the
chalcocite. Another similar or related approach, which is
more subtle, involves the exploitation of pulp potential
effects to promote the separation of enargite from non-
arsenic sulphides (Menacho et al., 1993; Jaime and
Cifuentes, 1995; Yen and Tajadod, 2000; Guo and Yen,
2005), and some prospective results have been reported.
A third approach relates to the use of an enargite-selective
depressant. Yen and Tajadod (2000) report that MAA (a
mixture of magnesium chloride, ammonium chloride, and
ammonium hydroxide) depresses enargite but not chal-
copyrite under certain flotation conditions allowing a
separation of these two minerals to be made.
None of the above approaches, however, have proved
selective or robust enough to be implemented at a
commercial scale, and it appears that a further advance in
selectivity is needed before the separation of enargite by
flotation in sulphide copper circuits becomes a commer-
cial reality. Furthermore, much of the reported work on
possible enargite separation based on pulp potential
effects, which seems to be the most prospective treatment
option cited, has been conducted using synthetic mineral
samples in microflotation cells and Hallimond tubes.
Clearly, while the effects of pulp potential on the flotation
of most copper minerals are well established, there is a
need to define more clearly the effects for enargite in
larger scale batch flotation tests using a full size
distribution of natural enargite.
The aims of the present study were, firstly, to
determine the pulp potential dependence of enargite
flotation at selected pH values, and, secondly, to use this
information to identify conditions where pulp potential
effects might be exploited to separate enargite from other
copper minerals present in the Tampakan deposit. The
outcome sought was the identification of options for the
inclusion of an enargite (arsenic) rejection circuit in the
Tampakan flotation flow sheet. The results of this study
are presented in this paper.
2. Experimental details
Experimental work conducted included preparation of
high-grade enargite mineral, single mineral flotation tests at
various Eh and pH values, and chemical and mineralogical
analysis of flotation feed and product samples.
2.1. Mineral preparation
The enargite used in this study was concentrated from
high-grade arsenic ore obtained from the LePanto mine in
the Philippines (Tveter and McQuiston, 1962). Enargite-
rich samples were separated by hand picking and then
crushed to pass 1700 μm using a laboratory jaw crusher in
closed circuit with a screen. The crushed material was dry-
screened into seven size fractions: −1700+ 1180 μm,
−1180 + 850 μm, −850 + 600 μm, −600+ 425 μm, −425 +
300 μm, −300+ 212 μm, and −212 μm. The −212 μm
fraction, which was low grade, was discarded. The other
six size fractions were upgraded individually in a labora-
tory hindered settling cone classifier. The method used was
similar in principle to that described by Taggart (1945).
The objective here was to reject non-sulphide gangue of
lower specific gravity than the enargite (SG 4.4). The six
upgraded size fractions were then combined and blended
to make a −1700 + 212 μm enargite composite. Using a
sample of this size range in the single mineral tests ensured
that after grinding only a minimum quantity of the original
surface remained.
Charges of 50 g were riffled from the composite for
flotation testing together with sub-samples for chemical
and mineralogical analysis.
 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26
High quality white quartz, obtained and prepared
locally, was used as the diluent mineral in all the single
mineral flotation tests. The amount used in each
flotation test was 450 g of − 1700 + 212 μm quartz.
The combined weight of the individual flotation charges
(enargite composite plus quartz) was thus 500 g.
2.2. Grinding
Enargite is a brittle mineral and is readily ground so
that precautions are needed to avoid over-grinding it in
mixtures with quartz. The procedure adopted in all tests
was to grind the 450 g of quartz (and distilled water)
separately for 15 min and then to add the 50 g of enargite
and grind the mixture for a further 5 min.
For each grind 250 ml of either distilled water or
deoxygenated distilled water was used giving a final pulp
density of 67% solids. The grinding mill was a closed iron
mill (23 cm diameter by 20 cm long) with a 4 kg charge of
25 mm mild steel balls. Before each grind the mill and ball
charge were cleaned by grinding with quartz and distilled
water for 10 min followed by rinsing with distilled water.
For flotation tests conducted below the air-set
potential the grinding mill was purged with nitrogen
for 2 min prior to the addition of the minerals, and the
water added to the mill was deoxygenated distilled water.
2.3. Flotation
Single mineral flotation tests were conducted over a
range of pulp potentials at two selected pH values, to
determine the flotation response of enargite over this
range of conditions.
2.3.1. Flotation reagents
The flotation collector used in all tests was potassium
ethyl xanthate (KEX) that was synthesized from high
purity chemicals and recrystallised from ethanol. A
fresh batch of xanthate was prepared each day as a 0.1%
w/v solution in distilled water. The frother was a
commercial quality polypropylene glycol (Cyanamid
Aerofroth 65) prepared as a 0.25% w/v solution in
distilled water. The flotation gas was either high purity
bottled nitrogen or high purity bottled synthetic air (a
synthetic mixture of O2 and N2). Either distilled water or
deoxygenated distilled water was used to maintain the
pulp level in the cell at a preset level. Dilute solutions
(2.5% w/v) of laboratory grade sodium hypochlorite
(NaClO) and sodium dithionite (Na2S2O4) were used to
control the pulp potential during flotation. AnalaR grade
sodium hydroxide (2.5% w/v) and nitric acid (2.5% w/v)
were added to set and maintain the pulp pH.
17
2.3.2. Flotation equipment
Samples were floated in a 3 dm3 modified stainless steel
Denver cell (Guy, 1992) in which the impeller was fitted
with a variable speed drive and was driven from below, to
allow the whole surface of the froth to be scraped with a
paddle at a constant depth and rate. The cell was fitted with
a rubber diaphragm, sight tube, and electronic sensor for
automatic detection and control of the pulp level.
For both conditioning and flotation the impeller
speed was 1200 rev/min. Air was delivered to the cell at
8 dm3/min. Frother was added continually during
flotation via a motorised variable speed dispenser
commencing 1 min before flotation. The addition rate
was 2 ml/min for this minute and the first 3 min of
flotation and then 1 ml/min thereafter. For a flotation
charge of 500 g the addition of 1 ml of frother was
equivalent to 5 g/t. This frother addition rate maintained
a high active froth column that would not limit flotation
rates and is similar to rougher flotation in practice.
The pulp potential was measured continuously
during testing using a high-impedance, differential
voltmeter with a polished platinum flag electrode and
a calomel reference electrode. The performance of the
electrode system was checked using standard ferric-
ferrous ion solution (Light, 1972). Measured potential
values were converted to the standard hydrogen
electrode (SHE) scale by the addition of 245 mV and
these values are referred to in this paper as Eh values, in
units of mV SHE.
A radiometer glass/saturated calomel electrode was
used to measure the pH continuously during testing.
Before each test the pH of the system was calibrated
using standard pH 7 and pH 11 buffer solutions.
Radiometer TTT80 titrators and ABU80 burettes were
used to add oxidant/reductant and acid/base to set and
maintain the Eh and the pH respectively.
2.3.3. Flotation procedures
The flotation response for enargite was determined at
various Eh values between − 500 and + 500 mV SHE at
pH values of 8 and 11. The natural pH of the ground
pulp varied between pH 7.2 and 7.7. The air-set
potential of the pulp at pH 8 was +255 mV SHE and
at pH 11 it was +175 mV SHE. The flotation procedures
used for the mineral mixtures followed a standard
procedure but there were differences for tests conducted
below and above the air-set potential. These modifica-
tions were necessary to ensure the reducing or oxidising
conditions required during flotation were not compro-
mised during any prior steps such as slurry transfer from
mill to cell, when setting the pulp Eh or pH, or when
conditioning the pulp.
18 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26
After the ground pulp was transferred to the flotation
cell the pH and Eh were set to their tests values using the
automatic titrators, with the potential being set upscale, that
is, from reducing to oxidising. Following this a standard
addition of 20 g/t KEX was made and the pulp conditioned
for 5 min. Flotation concentrates were then collected at 0.5,
1, 2, 4, 8, and 10 min by hand scraping at a constant depth.
A scraping rate of once every 2 s in the first min and once
every 5 s thereafter was maintained for all tests.
For tests below the air-set potential the ground slurry
was transferred from the mill to the cell under nitrogen and
a blanket of nitrogen was maintained above the pulp when
the Eh and pH were being set and also during reagent
conditioning. This helped minimise exposure to air before
flotation commenced. In these tests nitrogen was the
flotation gas and the makeup water used during flotation
was deoxygenated distilled water. For tests above the air-set
potential the flotation feed was prepared in the same way as
for tests below the air-set potential except that none of the
above precautions to avoid exposure of the pulp to oxygen
were taken, and the flotation gas was synthetic air rather
than nitrogen. The order of addition of reagents and the
conditioning times remained unchanged.
All flotation products were weighed wet, to allow
calculation of water recoveries, washed with alcohol,
dried, and prepared for analysis in a standard manner.
2.4. Chemical analysis of products
Sub-samples of the enargite composite and solid flotation
products were assayed for arsenic, copper, sulphur, and iron
by inductively coupled plasma-atomic emission spectrosco-
py (ICP-AES) using a standard method.
Filtrates of selected flotation pulps were analysed for
selected cations and anions. Cations were determined by
ICP-AES and anions were determined by high perfor-
mance liquid chromatography (HPLC).
2.5. Sizing analyses
Sizing analyses was conducted on a sub-sample of the
ground flotation feed using standard laboratory wet and
dry screening methods. Where sub-sieve sizing was
required the modified CSIRO Cyclosizing technique was
used (Kelsall et al., 1974). With this method two further
size fractions (CS6 and CS7), below those obtained by
conventional Cyclosizing (CS1-CS5), are collected
using a continuous centrifuge and a multiple decantation
procedure. All size fractions were analysed by ICP-AES.
In calculating elemental distributions in the sub-sieve
size range a SG (specific gravity) of 4.4 was used for
enargite to determine the appropriate Cyclosizer cut points.
2.6. X-ray diffraction (XRD) analyses
An X-ray diffraction pattern of the enargite compos-
ite was recorded on a Philips PW 1050 goniometer with
a PW 1710 diffraction controller using CuKα radiation.
Phases present were identified by comparison of the
peak positions and intensities with data published by the
International Centre for Diffraction Data (ICDD).
2.7. QEMSCAN analysis
A sub-sample of the enargite composite was
processed using QEMSCAN. Briefly the QEMSCAN
analysis involves preparing a polished section of the
sample and scanning the mount systematically with an
electron beam such that an image of each particle is
created. The minerals present at each point in these
images are identified by rapidly collecting an energy
dispersive X-ray spectrum (EDS) that is analysed to give
the chemical composition. By reference to an extensive
mineralogical database the chemical composition infor-
mation is converted to quantitative mineralogical data.
2.8. Single mineral flotation databank search
Heyes and Trahar (1977, 1979) have investigated
pulp potential effects in copper flotation systems over a
number of years and as a result CSIRO Minerals has
accumulated a significant databank of information on
the pulp potential dependence of flotation for a range of
copper minerals. Detailed information exists for chal-
cocite (Cu2S), chalcopyrite (CuFeS2) and cuprite
(Cu2O) together with some limited information on
digenite (Cu9S5), bornite (Cu5FeS4), and covellite
(CuS). This information was coupled with the flotation
experimental data obtained with the present enargite
composite sample to help identify conditions where pulp
potential effects might be exploited to separate enargite
from other copper minerals present in the Tampakan ore.
In the analysis that follows it has been assumed that
the flotation behaviour of chalcocite provides a guide to
that of copper sulphide minerals in general, including
digenite, and that the flotation behaviour of chalcopyrite
provides a guide to that of copper–iron sulphide
minerals in general, including bornite.
3. Results and discussion
The flotation response for enargite was determined at
various Eh values between − 500 and +500 mV SHE at
both pH 8 and pH 11 using the standard flotation
procedures detailed earlier. The results are discussed in
 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26 19

terms of the characterisation of the enargite composite, Table 2

effects of collector addition and soluble species in the QEMSCAN analysis of enargite composite
pulp, and possible flotation windows for separating Component Mineral Nominal formula Abundance (%)
enargite from other copper minerals. Major sulphides Enargite 3Cu2S.As2S5 44
Pyrite FeS2 22
3.1. Analysis of enargite composite Minor sulphides Bornite Cu4FeS4 0.1
Chalcopyrite CuFeS2 <0.1
Covellite CuS <0.1
The chemical analysis of the enargite composite, as Chalcocite Cu2S <0.1
determined by ICP-AES, is given in Table 1. The data show Digenite Cu9S5 <0.1
that the composite contained 22.3% Cu and 8.2% As. Non-sulphides Various Various 33
Using this arsenic value together with the nominal arsenic
Total >99.1
content of enargite (19.1% As) and assuming that all the
arsenic present is associated with enargite, the calculated
enargite content of the composite is 43%. The average representing the enargite, was calculated to be 106 μm.
calculated head assay from the 14 flotation tests conducted This was within the targeted range of 100–110 μm.
is also given. These results are in excellent agreement with
the assay head results for all elements analysed. 3.3. Effect of collector addition
Mineralogical data on the enargite composite
obtained from QEMSCAN analysis are presented in A standard addition of 20 g/t of KEX was used in
Table 2. These results indicate that the composite testing the enargite–quartz mixture. This value pro-
contained 44% enargite with pyrite (22%) being the duced an adequate response from enargite with
major sulphide contaminant. Pyrite was expected to be recoveries remaining in a region that was sensitive to
concentrated with the enargite in the mineral preparation changes in pulp potential. Pyrite present in the
upgrading process because of its relatively high specific composite was expected to float with the enargite
gravity. Non-arsenic sulphide copper minerals using the xanthate collector and no reagents were added
accounted for less than 1% of the composite. The to depress the flotation of the pyrite. A typical recovery-
enargite level (44%) is consistent with the calculated time response is shown in Fig. 1 for flotation at pH 11
value obtained from the chemical analysis data (43%). and a potential of + 95 mV SHE. In this graph and
X-ray diffraction analysis confirmed that the predom- subsequent graphs the pyrite recoveries are calculated
inant minerals in the composite were enargite, pyrite, and based on iron assays and enargite recoveries calculated
quartz. Small amounts of arsenosulvanite, Cu3(As,V)S4, based on arsenic assays. Enargite recoveries can also be
and luzonite, Cu3AsS4 (dimorphous with enargite), were calculated based on copper assays and in all flotation
also identified. tests these calculated recoveries were virtually identical
to those calculated based on the arsenic assays. This is
3.2. Flotation feed size distribution consistent with the composite sample containing only
trace amounts of other copper-bearing minerals.
Elemental distributions by size for the ground Note that in Fig. 1 and subsequent graphs different
flotation feed are listed in Table 3. These results show symbols have been used to represent the data points for
that after milling the bulk of the arsenic lies in a floatable the different minerals. Enargite is represented by the
size range and that the enargite has not been overground
Table 3
(the amount of arsenic in the finest size range, − CS6 Elemental distribution by size for ground enargite composite
which is approximately − 4.6 μm, is 8.0%). The P80 (size
Size range Weight Distribution (%)
at which 80% of the component passes) for arsenic, (μm) (%)
As Cu S Fe
− 300 + 106 18.5 20.8 21.0 24.2 24.4
Table 1 − 106 + 53 33.4 31.4 31.2 27.9 24.1
Chemical analysis of enargite composite − 53 + 24⁎ 13.7 20.9 20.7 21.1 17.7
Head sample Element − 24⁎ + 11⁎ 16.7 11.6 11.7 11.8 10.7
− 11⁎ + 4.6⁎ 10.0 7.3 7.5 7.2 10.1
As (%) Cu (%) S (%) Fe (%)
− 4.6⁎ 7.7 8.0 7.9 7.8 13.0
Assay head 8.2 22.3 25.0 14.2
Calculated head⁎ 8.2 22.3 24.8 14.3 Total 100.0 100.0 100.0 100.0 100.0
⁎Average of 14 single mineral flotation tests. ⁎ Nominal Cyclosizer cut points for a mineral of SG 4.4.
20 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26

(18 ppm) of sulphate. These changes suggest that the

sulphides started to oxidise when air was introduced into
the pulp but that the extent of oxidation in the 10 min of
flotation was minor and hence their effect on flotation
was considered to be negligible.

3.5. Effect of pulp potential on enargite flotation

3.5.1. Flotation of enargite and pyrite at pH 8

Fig. 1. Cumulative mineral recovery as a function of flotation time for
enargite and pyrite (20 g/t KEX, pH 11, iron mill, Eh 95 mV SHE).
symbol ⋄, pyrite by the symbol ▵, chalcocite by the
symbol □, chalcopyrite by the symbol ○, and cuprite by
the symbol ⁎. In addition, the open symbols (e.g. ▵) are
used for results obtained at pH 8 and the closed symbols
(e.g. ▴) for data obtained at pH 11.
The relationship between enargite flotation and pulp
potential at pH 8 is shown in Fig. 2 as a plot of mineral
recovery in the first minute against pulp potential.
Between about −150 mV and −50 mV SHE the mineral
goes from being non-floatable to being strongly floatable.
The threshold potential for the transition, which we define
as the potential at which recovery after 1 min is 50%, is
about −75 mV SHE. As far as it was tested (up to
+400 mV SHE), no upper limiting potential was found.
Fig. 2 also shows the flotation response of the pyrite in
the enargite composite. Like enargite, this mineral starts to
float at potentials above about −150 mV SHE although its
response in this sample is never as strong as that of enargite.
By contrast with enargite, the pyrite tends to become less
floatable as conditions are made more strongly oxidising,
that is, as pulp potentials are made more positive.

3.4. Formation of soluble species 3.5.2. Flotation of enargite and pyrite at pH 11

Recovery data for enargite flotation as a function of
Filtrates from two flotation pulps were analysed for pulp potential at pH 11 are shown in Fig. 3 where a clear
selected cations and anions. One pulp related to boundary or edge for enargite flotation is again evident.
reducing conditions, and was sampled immediately The data here suggest a threshold potential at about
after grinding, while the other pulp related to oxidising −25 mV SHE, which is 50 mV SHE more positive or
conditions and was collected at the end of a flotation test
(after 10 min) conducted above the air-set potential. The
results shown in Table 4 indicate the levels of anions and
cations in both flotation pulps were low. Under the
strongly reducing conditions initially produced by
grinding, all species analysed for were below detection
level. When the pulp potential was raised, by aerating
the pulp, only very low levels of iron and copper were
detected together with a somewhat higher level

Table 4
Typical analyses of filtrates from flotation pulps under reducing and
oxidising conditions
Pulp Cations (ppm) Anions (ppm)
conditions⁎
Cu As Fe S2O32− SO42−
Reducing <0.1 <0.1 <1 <1 <1
Oxidising 0.2 <0.1 1.5 <1 18
⁎Reducing conditions immediately after grinding, oxidising conditions
at the end of a flotation test (after 10 min) conducted above the air-set Fig. 2. Mineral recovery at 1 min as a function of pulp potential for
potential. enargite and pyrite at pH 8 (20 g/t KEX, iron mill).
 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26 21

similar to that at pH 8 (Fig. 2), the only real difference

being that the lower flotation edge occurs at more
positive potentials at pH 11.

3.6. Effect of pulp potential on flotation of other copper

minerals

The data presented in the following section has been

drawn from the CSIRO Minerals databank of information
on the pulp potential dependence of flotation for a diversity
of copper minerals. Data are presented for chalcocite
(Cu2S), chalcopyrite (CuFeS2), and cuprite (Cu2O).

3.6.1. Chalcocite
The flotation response of chalcocite as a function of
pulp potential is shown in Fig. 4 for flotation at pH 8 and
in Fig. 5 for flotation at pH 11. The response at these two
Fig. 3. Mineral recovery at 1 min as a function of pulp potential for pH values for reducing and mildly oxidising conditions
enargite and pyrite at pH 11 (20 g/t KEX, iron mill).
(< + 200 mV SHE) is similar with the threshold potential
being about − 155 mV SHE. At higher potentials,
oxidising than that in Fig. 2 for enargite flotation at pH 8. however, an additional upper limiting potential at about
Whether the shift in threshold potential between pH 8 and + 270 mV SHE is apparent at pH 11 but not at pH 8.
11 is real is difficult to decide from Figs. 2 and 3 because The cessation of chalcocite flotation at pH 11 under
of the scatter of results that inevitably occurs in conditions more oxidising than the air-set potential is
experiments of this type. More data points would need well documented and has been attributed (Heyes and
to be obtained to verify or otherwise any significant Trahar, 1979) to the decomposition of cuprous xanthate
difference. When both data sets (pH 8 and pH 11) are by a mechanism of the general type shown in Eq. (1).
plotted together, a single curve with a threshold potential
of −25 mV SHE can be fitted. The closeness of the fit is CuX þ H2 O→CuO þ X− þ 2Hþ þ e− ð1Þ
much the same as that in Figs. 2 and 3, which shows the This reaction is favoured at high pH where xanthate
difficulty of confirming any shift in potential. We have not is replaced by hydroxide or oxide on the mineral
investigated the issue further but note that theoretically the
threshold potential, which is related to the oxidation
potential of the mineral, should be dependent on pH.
For an industrial process a shift of 50 mV SHE for a
change in pH of 3 units is unlikely to be of any real
consequence. Even when holding the pH essentially
constant, it is unlikely that the potential in a plant could
be maintained near the threshold potential to better than
± 25 mV SHE. To separate enargite from another copper
mineral by potential control would probably require a
difference in their threshold potentials of at least 75 mV
SHE.
The data plotted in Fig. 3 for the pyrite at pH 11 also
show a clear potential dependence. The mineral is un-
floatable under strongly reducing conditions and only
starts to float when the potential is raised above about
− 100 mV SHE. In the oxidising region (positive
potentials) there is an upper potential limit near
+ 300 mV SHE above which the recovery decreases
sharply. Comparing the pyrite data for both pH values Fig. 4. Mineral recovery at 1 min as a function of pulp potential for
tested it is apparent that the response at pH 11 (Fig. 3) is chalcocite at pH 8 (40 g/t KEX, glass mill).
22 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26
Fig. 5. Mineral recovery at 1 min as a function of pulp potential for
enargite and chalcocite at pH 11 (enargite; 20 g/t KEX, iron mill,
chalcocite; 40 g/t KEX, glass mill).
surface. The released xanthate, or dixanthogen derived
from it, is presumably oxidised irreversibly in the
strongly oxidising environment.
3.6.2. Chalcopyrite
The influence of pulp potential on chalcopyrite
flotation behaviour at pH 8 is shown in Fig. 6. The
mineral exhibits a clear lower flotation threshold at
about +160 mV SHE, which is significantly higher than
that for either enargite or chalcocite. Over the range of
Fig. 6. Mineral recovery at 1 min as a function of pulp potential for
enargite and chalcopyrite at pH 8 (enargite; 20 g/t KEX, iron mill,
chalcopyrite; 40 g/t KEX, stainless steel mill).
Fig. 7. Mineral recovery at 1 min as a function of pulp potential for
enargite and cuprite at pH 11 (enargite; 20 g/t KEX, iron mill, cuprite;
40 g/t KEX, glass mill).
potentials studied (up to + 360 mV SHE), no upper
limiting potential was found.
3.6.3. Cuprite
The relationship between floatability and pulp
potential for cuprite in the presence of collector at pH
11 is presented in Fig. 7. By contrast with enargite,
chalcocite and chalcopyrite, cuprite does not exhibit a
lower limiting potential and floats strongly at potentials
as reducing as − 400 mV SHE. An upper limiting
potential occurs at about + 290 mV SHE. This upper
limit has also been attributed to the decomposition of
xanthate according to the general reactions shown in Eq.
(1) (Heyes and Trahar, 1979).
4. Possible separations between enargite and other
copper minerals
The data obtained have been examined to identify
differences in flotation responses that could be exploited
to separate enargite selectively from other copper
minerals on the basis of pulp potential effects. Three
promising options have been identified. These are
discussed below.
4.1. Separation of enargite from copper–iron sulphides
such as chalcopyrite
A clear region or window of separation between
enargite and chalcopyrite exists at pH 8 in the potential
range between − 25 and + 50 mV SHE as shown by the
 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26 23

data in Fig. 6. In this range it should be possible to float • In Stage 1, setting the pH to 11 and then generating a
enargite selectively from chalcopyrite. We would not reducing pulp condition that is above the lower
expect the threshold potential for chalcopyrite flotation threshold potential for the flotation of chalcocite but
to change much with pH and therefore a similar below that for the flotation of enargite and chalco-
separation might also be possible at pH 11. pyrite. At this pulp potential (about − 125 mV SHE)
chalcocite and any cuprite present should float while
4.2. Separation of enargite from copper sulphides such enargite and chalcopyrite should remain un-floated.
as chalcocite • In Stage 2, raising the pulp potential of the tailing
from Stage 1 to about 0 mV SHE, which is above the
At pH 8 the potential dependence of flotation of
enargite is too close to that of chalcocite to allow a clean
separation. At pH 11, however, two windows of
separation are possible, as shown in Fig. 5. The first is a
relatively narrow window between about −150 and
−75 mV SHE in which chalcocite floats ahead of enargite.
The second is in the range above about +270 mV SHE
where enargite floats but chalcocite is depressed.

4.3. Separation of enargite from copper oxides such as

cuprite

Fig. 7 shows the flotation response of enargite and

cuprite at pH 11. Two windows of separation are again
evident. The first is a broad window at potentials below
− 150 mV SHE in which cuprite floats and enargite does
not. The second is at potentials above about +290 mV
SHE where enargite floats but cuprite does not.
At oxidising conditions it is apparent that the window
for the separation of chalcocite from enargite is similar
to that for the separation of cuprite from enargite. It
should therefore be possible to separate both these
minerals from enargite in a single stage of flotation
rather than in two separate stages.

5. Conceptual flow sheet

Based on the combined results of the single mineral

studies a flow sheet showing one way in which the various
enargite separations could be linked to lower the arsenic
level of the Tampakan copper concentrate has been
conceptualised. The flow sheet is briefly discussed in
terms of its arrangement, including any implicit assump-
tions made in its design, and reagent considerations.

5.1. Flow sheet design and arrangement

In the proposed flow sheet, presented in Fig. 8,

enargite is rejected in a three-stage process that yields
three products: a chalcopyrite/bornite-rich product, a
chalcocite/digenite-rich product and an enargite-rich
product. Briefly, the process involves the following Fig. 8. Conceptual flow sheet for a Tampakan arsenic rejection circuit,
stages. based on pulp potential effects.
24 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26
lower threshold potential for the flotation of enargite
but still below that for the flotation of chalcopyrite.
The pulp pH is kept at pH 11. At these conditions
enargite and any remaining chalcocite should float
selectively from the chalcopyrite to leave a chalco-
pyrite-rich flotation tail (Product 1).
• In Stage 3, combining the enargite-rich concentrate
(froth product) from Stage 2 with that portion, if any,
of the froth product from Stage 1 which is high in
enargite, and conditioning the combined stream
under oxidising conditions that are above the upper
limiting potential for the flotation of chalcocite and
cuprite (about + 290 mV SHE). The pulp pH is kept
at pH 11. These flotation conditions should yield an
enargite-rich froth product (Product 2), and any
chalcocite or cuprite present will remain un-floated.
The Stage 3 flotation tail is combined with the
copper-rich flotation concentrate from Stage 1 to give
a chalcocite/cuprite-rich product (Product 3).
The proposed flow sheet has been designed such that
the arrangement of the stages is coherent and the number
of changes of pulp potential is minimal. Further, the
flotation conditions suggested have been selected to
maximise the difference between the threshold potentials
of the minerals to be separated. It is proposed that this be
at least 50 mV SHE and preferably more than 100 mV
SHE. The flow sheet allows for the re-treatment of some
portion of the froth product from Stage 1 (chalcocite-rich
product) where the difference between the threshold
potentials of chalcocite and enargite is small and where
the separation might therefore not be all that clean.
The proposed feed to the arsenic rejection circuit, as
shown in Fig. 8, is the final bulk copper–arsenic
concentrate. This is a low flow stream and as such the
control of the pulp potential is likely to be easier and the
addition rate of potential-controlling reagents is likely to
be lower. A regrind mill is also shown in the flow sheet
up-front of the circuit to regrind the copper–arsenic
feed. It is not known at present whether further size
reduction or liberation of the feed (and hence the regrind
mill) is required, but it is noted that the use of a regrind
mill at this stage of the flow sheet may be useful in
generating the initial strongly reducing pulp conditions
required for the first stage of flotation.
5.2. Reagent considerations
Another major consideration in the flow sheet
development, for both cost and environmental reasons,
is the minimum use of chemical reagents in all three
flotation stages. As shown in Fig. 8 the use of different
flotation gases is proposed as the primary method of
pulp potential control. Initial reducing conditions would
be produced as a result of regrinding the feed and these
conditions maintained under nitrogen. The pulp poten-
tial could then be adjusted upscale as required by the
controlled addition of air. For secondary control of the
potential the recommendation in the first instance is
either sodium hydrosulphide or sodium sulphide as
reductant and either calcium peroxide or hydrogen
peroxide as oxidant. If significant amounts of cuprite or
tenorite are present sulphide may not be a suitable
reductant because it reacts with both minerals. In this
case ferrous sulphate might be a substitute. Sodium
hypochlorite would be a technical alternative to
peroxide as an oxidant but would probably be
unacceptable environmentally because of by-product
chlorine.
It is noted that flotation with nitrogen, as proposed in
stages 1 and 2, will probably necessitate the use of a
specialised flotation cell. Such equipment does exist but
selection decisions are beyond the scope of this work
suffice to say further technical and engineering studies are
required to confirm the most suitable and practical oxidants,
reductants and flotation carrier gases for such a circuit.
Finally, it is clear that the flow sheet in Fig. 8 is not the
only way in which the various enargite separations could
be linked. At this stage, however, it would seem the
simplest, the most cost effective and the cleanest
environmentally. Likewise, the final bulk copper–arsenic
concentrate is not the only stream that could be treated in
an arsenic rejection circuit such as that proposed. For
streams with greater flows, however, capital and operating
costs would almost certainly be higher.
5.3. Design assumptions
The results in this work have been obtained in
simplified single mineral flotation systems involving
mixtures of clean minerals. A number of assumptions
are therefore implicit in the formulation of the flow sheet
shown in Fig. 8 and these are now summarised.
Firstly, it is assumed that any interactions between
the minerals that might affect their threshold and upper
limiting potentials are minimal. This is not an
unreasonable assumption for systems of this type
where the oxidation products of all the minerals are
likely to be similar. Note that the tests conducted here
were all single mineral tests, using a particular mineral
mixed with a quartz diluent; no mixed mineral tests were
conducted.
Secondly, it is assumed that the grinding environ-
ment is without effect. The laboratory mill used, for
 G.D. Senior et al. / Int. J. Miner. Process. 81 (2006) 15–26
example, to prepare the chalcocite was a glass mill (non-
reducing) whereas that used to prepare the chalcopyrite
was a stainless steel mill.
Thirdly, it is assumed that pulp potential hysteresis
effects will not be pronounced. In some systems,
hysteresis in the threshold potential occurs depending
on whether the potential is being shifted upscale or
downscale.
Fourthly, it is assumed that the flotation behaviour of
chalcocite, with respect to pulp potential dependence, is
similar to that of copper sulphide minerals in general,
including digenite, and that the flotation behaviour of
chalcopyrite, with respect to pulp potential dependence,
is likewise similar to that of copper–iron sulphide
minerals in general, including bornite.
Finally, the pre-treatment stages to our proposed circuit
are not clear as yet. These include primary grinding and
flotation to produce the bulk copper–arsenic concentrate.
It is assumed at this stage that reagents added to float the
bulk concentrate do not fundamentally alter the pulp
chemistry of the proposed arsenic rejection circuit.
Similarly, the single mineral flotation tests conducted in
this work were carried out on well-liberated minerals and
our proposed flow sheet is based on the assumption that
liberation will not impose a major limitation on enargite
separation efficiency. In essence, general compatibility
between the bulk copper–arsenic and arsenic rejection
flotation circuits is assumed at present.
To validate these assumptions and to test the concepts
and flow sheet proposed in a real system, the work now
needs to be extended to laboratory batch testing on the
Tampakan drill core.
6. Conclusions
A single mineral flotation study was undertaken on
an enargite sample from the Philippines to determine the
floatability of enargite, the major arsenic-bearing
mineral present in the Tampakan ore, as a function of
pulp potential. This information was coupled with
previously obtained experimental data on the floatability
of other copper minerals as a function of pulp potential
to help identify conditions where pulp potential effects
might be exploited to separate the enargite from other
copper minerals present in the Tampakan ore, and hence
lower arsenic levels in final copper concentrates.
The results of the study have revealed that the pulp
potential dependence of enargite flotation is different
from that of chalcocite, chalcopyrite and cuprite. These
differences in pulp potential effects point the way to a
possible method for separating enargite efficiently from
other copper minerals.
25
On the basis of the results obtained it seems possible
that the following separations could be achieved:
• Floating copper sulphides such as chalcocite from
enargite at pH 11 after setting the pulp potential to
about − 125 mV SHE.
• Floating enargite from copper–iron sulphides such as
chalcopyrite at pH 8 or pH 11 after setting the
potential to about 0 mV SHE.
• Floating enargite from copper sulphides such as
chalcocite and from copper oxides such as cuprite at
pH 11 after setting the potential to about +290 mV SHE.
A conceptual flow sheet, linking these separations in
a coherent way that minimises the number of flotation
stages and the number of pulp potential changes, is
proposed. Reagents for possible use in a commercial
operation have been identified.
Acknowledgement
WMC Resources Ltd. (now part of BHP Billiton) is
thanked for supporting the work, providing the enargite
sample used in this study, and for conducting the
assaying of the flotation products at its laboratory at
Belmont, Western Australia.
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