Pyrite-Gold Recovery in Copper Rougher Flotation

Tailings
Eic Aminartey Agorhom1, William Skinner and Massimiliano Zanin
1
Ian Wark Research Institute
Ian Wark Research Institute, The ARC Special Research Centre for Particle and Interfaces, University of South
Australia, Mawson Lakes Campus, Adelaide, SA 5095, Australia
Email: Aminartey.Agorhom@mymail.unisa.edu.au
OK Tedi, Freeport Indonesia, etc.), in order to increase Cu and
Au grades, regrinding and depression strategies are used to
maximise pyrite rejection in the cleaner stage. Although these
depression strategies improve recovery and grade of copper,
gold recovery is very often affected due to its fine-inclusions
(~1-3 m) in pyrite and non-sulphide gangue minerals [1].

Abstract The present study investigates the effect of

regrinding and aeration on the separation of pyrite from
gold in copper rougher flotation tailings (0.07% Cu,
0.61g/t Au, tail grades). An aeration stage was applied both
at the head of copper flotation (copper rougher feed) and
after regrinding of the copper rougher tailings, before
gold/pyrite selective flotation. Also, different collector
regimes, involving sodium iso-butyl xanthate (SIBX) and
N-butoxycarbonyl-nbutyl thionocarbamate (XD5002),
have been tested. It was found that aeration of the copper
rougher feed produced lower gold (71%) and copper
(95%) recoveries than the non-aeration of the copper
rougher feed (73% Au and 98% Cu recoveries). Fine
regrinding of the copper rougher tails increased both gold
and copper recoveries in the subsequent flotation stage,
due to improved liberation. The highest gold recovery
from the rougher tailings (45%) was achieved without
aeration of the reground product. However, in these
conditions poor rejection of pyrite was achieved, and the
concentrate gold grade was low (1.3 g/t, versus 2.3 g/t
obtained after aerating the pulp). With respect to the
collector scheme, increased gold and copper recoveries
were achieved blending the two collectors (SIBX and
XD5002) compared to XD5002 alone. However, higher
gold (3.0 g/t) and copper (1.0%) grades were observed with
XD5002 alone, due to better pyrite rejection. This is
believed to be due to the high affinity of xanthates (e.g.,
SIBX) for the copper activated pyrite.

Also, selectivity between chalcopyrite and pyrite in Cu-Au

ores is a challenge due to unintentional activation of pyrite as a
result of the dissolution of Cu2+ or Pb2+ ion from complex
sulphides (i.e. Cp and galena, respectively) and its association
with pyrite as fine complex intergrowths. It has been proposed
that activation of pyrite occurs as an ion exchange process,
where Fe(II) is replaced by Cu(II) on the pyrite surface [2-4].
The presence of Cu on pyrite promotes its interaction with
generic sulphide collectors such as xanthate. It was observed
that in the presence of xanthate, dixanthogen is the main
xanthate species responsible for the flotation of Cu-activated in
alkaline medium. Dixanthogen form as a result of anodic
oxidation of xanthate at the surface of pyrite coupled with
cathodic reduction of oxygen [5-6]. Consequently, the
unintentional pyrite flotation is undesirable in a Cu-Au ore
flotation circuit due to the detrimental effect on Cu final grade.
Therefore, in order to improve final concentrate grade, pyrite
depression strategies (e.g. aeration, sulphite, cyanide addition,
etc.) have been used over the years to minimise pyrite
recovery.
In our previous study [7], the influence of Au mineralogy
on its flotation was studied in a typical copper ore. A two-stage
(Cu and pyrite) rougher flotation indicated that maximum Au
recovery (95%) can only be achieved with pyrite flotation
(recovery, 93%). A decrease in grind size of the flotation feed
from 70 m to 38 m and without pyrite flotation stage
resulted in a decreased Au recovery (73%) due to depression of
pyrite/gold composites (pH 11.5). Therefore, it is crucial to
study how regrinding of Cu tails at finer grind (p80 = 15 m)
and aeration can be used to maximise Au recovery and grade
while still rejecting significant pyrite. Regrinding in the stirred
mill (IsaMill) does not only reduce particle size, but also
liberate Au and Cu from the pyrite mineral, and expose new
surfaces for enhanced collector adsorption.

Keywords: Depression; Aeration; Regrinding, Pyrite,

Gold; Flotation
I. INTRODUCTION
Froth flotation is a widely used separating technique for the
recovery of Cu and Au in porphyry copper-gold ores. In these
ores, chalcopyrite and gold are the main valuable mineral/metal
phases, with pyrite being the key sulphide gangue mineral.
However, in these ores gold is mostly associated with pyrite
rather than the copper minerals. Gold-pyrite and chalcopyritepyrite associations are problematic in porphyry copper-gold
flotation due to the requirement to minimise sulphur content
(improve concentrate grade) in the final Cu concentrate. For
example, in most Cu-Au flotation plants (i.e. Telfer gold mine,

In this study, the effect of aeration (both at the head of Cu

flotation and after regrinding of copper rougher tailings) on the
flotation behaviour of Au and Cu in a porphyry copper-gold is
examined in detail. Copper rougher and scavenger flotation

tests were performed by collector (SIBX/XD5002) addition in

stages. Consequently, the flotation behaviour of Cu, Au and
pyrite was examined on the basis of recovery and grade as well
as the mechanisms responsible for pyrite depression/rejection
using EDTA extraction techniques.
II.

TABLE I. FLOTATION TEST CONDITIONS OF THE

Cu ROUGHER AND SCAVENGER STAGES
Cu rougher stage
Pulp density (30 wt.% solids)
Pulp volume (4.5L)
Agitator speed (1200 rpm)
pH (11.5)
Total flotation time, 15 min ( 2.5 min
for each stage)

EXPERIMENTALS

Cu scavenger stage
Regrinding (for 35 min in IsaMill)
Pulp density (20 wt.% solids)
Pulp volume (2.0L)
Agitator speed (1000 rpm)
Total flotation time (8 min)

A. Materials
All tests were carried out in duplicates. At the end of each
test, concentrate and tail samples were filtered, dried at 60 0C
and assayed for Cu, Au, S and Fe. The flotation strategies
employed to optimise gold recovery whiles rejecting
significant pyrite in the copper tail are shown in Table 2.

A.I. Ore
Mineralogical characterisation of the ore revealed that
chalcopyrite and covellite were the major copper-bearing
minerals. Pyrite and silicates were identified as the main gold
host minerals in the ore. Gold occurred as either liberated or
locked in pyrite, sphalerite or biotite. Chemical analysis
showed that the ore contained 1.7 g/t Au, 1.0% Cu, 12.6% S
and 18.4% Fe.

60 min

A.II. Reagents
The collectors used were sodium iso-butyl xanthate
(C4H9OCSSNa, abbreviated SIBX) and N-butoxycarbonyl-n
butyl thionocarbamate (RHN-(C=S)-OR, abbreviated XD5002), supplied by Cytec Chemicals. The frother used was
methyl-iso-butyl carbinol (MIBC), also supplied by Cytec
Chemicals. All the reagents were freshly prepared for each
experiment as 1% w/w solutions. Lime was used as pH
modifier and compressed air as flotation gas (2 L/min).

Air (5 L/min)
25 min

Rougher
block
Cu rougher
concentrate

Feed

d80=38 m
Regrind
Circuit

B. Methods
B.I. Grinding, aeration and flotation
The schematic representation of the experimental
procedure is shown in Fig. 1. The ore (2 kg crushed to -2 mm)
was ground for 60 min in a closed stainless steel Galigher
mill, in 1000 ml of demineralised water, adding 2.5 g/t
XD5002 and 1.0 g of dry lime. This resulted in a flotation feed
with 80 wt.% of the particles passing through 38 m screen
(p80=38 m) and a mill discharge at pH 9.0. After grinding,
the pulp was transferred to a 4.5 L Denver flotation cell. Two
conditions, aeration and non-aeration were applied to the pulp
before reagent conditioning.
In the first set, the pulp was aerated for 25 min before
SIBX and XD5002 were added in six stages. The total
flotation time was 15 min and the pulp pH was kept constant
at 11.5. After Cu rougher flotation, the tails were reground
with batch stirred mill (IsaMill) to produce a flotation feed of
p80=15 m. Copper scavenger tests were conducted with 15
g/t SIBX, 10 g/t XD5002 and 7.5 g/t MIBC. Two minutes time
(2 min) was allowed for each conditioning. Four concentrates
were collected at 1, 2, 4 and 8 min cumulatively. The detailed
test conditions for the Cu rougher and scavenger stages are
shown in Table 1.

d80 = 15 m
No
aeration

Air (5 L/min)
25 min

Final Tails

Scavenger blocks

Figure 1. Simplified Flowsheet showing flotation with and without aeration of

Cu rougher feed.

TABLE II. TEST CONDITIONS FOR Au REOVERY OPTIMISATION IN

THE COPPER ROUGHER TAILS
Cu feed non-aerated (IsaMill
regrinding, p80=15 m)

Test1: Aerated for 25 min and

floated for 8 min using
SIBX/XD5002

Test 2: Non-aerated and floated for

8 min using SIBX/XD5002

Cu rougher feed aerated

Cu feed non-aerated

80

Cum. Gold Recovery (%)

Cu feed aerated (IsaMill

regrinding, p80=15 m)

85

(b)

75

70

65

60

Error bar

55

Test 3: Aerated for 25 min and

floated for 8 min using
SIBX/XD5002

Test1-1: Aerated for 50 min and

floated using SIBX/XD5002

50
5

10

11

12

13

Cum. Gold Grade (%)

Figure 2. Effect of aeration condition on (a) gold flotation rates and (b)
gold flotation behaviour in different test conditions (Cu rougher feed aerated
and non-aerated) using SIBX/XD5002 as collector, p80=38 m.

Test 3-1: Aerated for 50 min and

floated using SIBX/XD5002
Test 3-2: Aerated for 25 min and
floated for 8 min using XD5002

However, when the copper rougher tails (Test 1, Test 2 and

Test 3) were reground, only 25% of the total gold lost was
recovered in Test 1. Test 2 showed the highest gold recovery
(45%), due to higher pyrite recovery (45%) (Table 3). When
the reground product of Test 3 was pre-aerated before flotation,
about 33% of gold was recovered at an improved grade (2.3
g/t). Also, the highest gold (86%) and copper (98%) recoveries
in the combined copper rougher and scavenger stage was
achieved when aeration was not applied both at the head of
copper flotation and after regrinding of the copper rougher
tailings.

A.III. EDTA extraction technique

Ethylene diaminetetraacetic acid (EDTA) was used to
extract metal oxidation products (e.g. oxide/hydroxide,
sulphate, carbonate, etc.) from the mineral surfaces [8-10]. A
pulp volume of 0.1dm3 was mixed with a 3% AR grade of
EDTA solution and conditioned for 5 min while purging with
nitrogen to prevent further oxidation of the mineral surface.
The EDTA solution was purged with nitrogen for 10 min
before extraction to remove residual oxygen. The amount of
surface oxidation products extracted by EDTA was measured
in solution by inductively coupled plasma mass spectroscopy
(ICP-MS).

TABLE III. FLOTATION DATA FOR Au, Cu AND Py AFTER

REGRIND TO p80=15m UNDER DIFFERENT TEST CONDITIONS (Au,
Rec 2%, Cu, Rec 1% and Py, Rec 4%)
Total Recoveries,
Gold

III.

RESULTS AND DISCUSSION

A.I. Effect of aeration and liberation

The effect of aeration on gold flotation in the copper
rougher stage is shown in Fig.2. It can be seen that the highest
recovery (82%) was achieved at the expense of grade (5.7 g/t)
when the copper rougher feed was not pre-aerated before
flotation. This is because such condition promotes pyrite
flotation which invariably leads to higher gold recovery since
the majority of the unliberated gold particles were associated
with pyrite as fine inclusions (~1-3m) [1, 7]. Although higher
gold grade (7.6 g/t) was achieved when the copper rougher
feed was pre-aerated before flotation, the gold flotation
recovery (71%) and kinetics were low.

(a)

Goldrecovery(%)

60

Aerated Cu rougher feed

Non-aerated Cu rougher feed

20

0
0

10

12

% (Cu Ro+Sc
stage)

Recovery

Grade

Recovery

Grade

Recovery

Grade

Au

Cu

(%)

(g/t)

(%)

(%)

(%)

(%)

Test 1

25

2.2

43

0.6

10

24.5

73

96

36

Test 2

45

1.7

54

0.3

45

54.3

86

98

62

Test 3

33

2.3

56

0.8

16

32.4

82

97

49

In case of copper flotation, there was no significant change

in copper recovery for the two different test conditions (Fig.3).
The best copper grade (7.3%) was achieved when the copper
rougher feed was pre-aerated before flotation. It has been
demonstrated by a number of researchers that flotation of
copper minerals such as chalcopyrite improved at higher pulp
potential, ~300 mV [11-12]. This is evident in the flotation of
the reground product of Test 3, where maximum copper grade
(0.8%) was achieved as a result of significant reduction in
pyrite recovery (16%) as compared to Test 2 (Table 3).
Although copper recoveries were not significantly affected
compared to the baseline flotation studies [7], copper flotation
rate was slower when copper rougher feed was pre-aerated
before flotation (Fig.3). This condition promotes the formation
of metal hydroxide species on the surface of chalcopyrite
which makes the formation of metal xanthate on the
chalcopyrite surface difficult resulting in slower flotation rates

100

40

Pyrite

Test #

A. Results

80

Copper

14

Flotation time (min)

Py

in flotation [13]. Higher pyrite rejection (about 64%) was

observed when both copper rougher feed and reground product
were aerated before flotation, but this caused a significant
reduction in gold recovery. The significant pyrite
rejection/depression correlate with higher oxygen consumption
rate (kla = 0.131 min-1) of the reground product determined
from oxygen demand test (not shown here). The pulp potential
(Eh) increase steadily from 269 to 342 mV SHE after aeration,
which may be responsible for the effective pyrite depression
under this test condition (Table 4).

TABLE IV. PULP CHEMISTRY PARAMETERS (DO & Eh) AND

OXYGEN CONSUMPTION RATE, kla AFTER AERATION OF
REGROUND PRODUCT (TEST 1), p80 = 15 m.
Pulp parameters

Initial

Final

DO (ppm)

2.72

7.76

Eh (mV SHE)

269

342

Kla (min-1)

0.131

0.029

100

(a)
Gold recovery (%)

80

A.II. Effect of aeration time and collector suite

Increase in aeration time from 25 min to 50 min for the
reground products of Test 1 and Test 3 resulted in decreased
gold, copper and pyrite recoveries. When the aeration time for
Test 1 was increased, total gold recovery decreased from 73%
to 70% with an improved overall gold concentrate grade (8.5
g/t) (Table 5). A similar reduction in copper and pyrite
recoveries were observed in Test 1-1. However, copper grade
(7.2%) improved significantly as a result of drastic reduction in
mass recovery. Also, increase in aeration time for the reground
product for Test 3 showed a decreased gold recovery (81%) but
did not impact on gold grade (5.4 g/t) (Test 3-1). There was no
significant change in copper recovery but copper grade
increased by 0.2%. Pyrite and mass recoveries reduced
significantly.

60
Aerated Cu rougher feed
Non-aerated Cu rougher feed

40

20

0
0

10

12

14

Flotation time (min)

100

(b)

Cum. Copper Recovery (%)

98
96
94
92

A change in collector suite, from a combination of SIBX

and XD5002 to only XD5002 (a more Cu-sulphide selective
collector) for Test 3 reground product (Test 3-2) resulted in a
reduction in gold recovery from 83% to 76% at an improved
grade (7.4%). Copper recovery also dropped marginally, by
1%. However, copper grade increased significantly (6.8%).
The change in collector suite has more significant impact on
pyrite rejection than increasing the aeration time of the
reground product (Test 3-1) (Table 5).

90
Cu rougher feed aerated
Cu rougher feed non-aerated

88
86
84

Error bar

82
80
4

10

12

14

Cum. Copper Grade (%)

100

Aerated Cu rougher feed

Non-aerated Cu rougher feed

Pyrite recovery (%)

80

60

TABLE V. FLOTATION RECOVERY AND GRADE DATA FOR Au,

Cu AND Py IN THE COMBINED ROUGHER AND SCAVENGER STAGES
(Au, Rec 2%, Grade 0.08g/t; Cu, Rec 1%, Grade 0.05% and Py, Rec
4%, Grade 3%)

(c)

Gold

40

Test #

Copper

Pyrite

Mass
Yield

Recovery

Grade

Recovery

Grade

Recovery

Grade

(%)

(g/t)

(%)

(%)

(%)

(%)

Test 3

82

5.4

97

5.7

49

41.9

312

Test 3-1

81

5.4

97

5.9

28

38.4

292

Test 3-2

76

7.6

96

6.8

29

37.7

182

Test 1

73

96

5.2

36

36.9

242

Test 1-1

70

94

7.2

24

37.7

152

(%)

20

0
0

10

12

14

Flotation time (min)

Figure 3. Effect of aeration on (a) copper flotation rates; (b) copper

flotation behaviour and (c) pyrite flotation rates in different test conditions
using SIBX/XD5002 as collector, p80=38 m.

5.7

8.5

aerated and non-aerated feed) improved gold recovery.

Aeration of the reground products of the aerated/non-aerated
copper feed further decreased pyrite recovery and consequently
decreased gold recovery. Under the aerative condition, higher
oxidizing medium (higher Eh value, ~342 mV SHE) is created,
which easily oxidized S22- to various surface oxidation species
such as S, SO42-, SO32- and S2O32-. Some of these surface
oxidation species (e.g. S, polysulphides, etc.) are hydrophobic,
but the majority is hydrophilic (SO42-, SO32-, S2O32-, Fe(OH)3)
and reduce pyrite floatability. These surface contaminants
passivate pyrite surface, prevent Cu and collector adsorption
and hence decreased pyrite flotation. This is in agreement with
other studies in the literature, which show that passivation of
pyrite surface by iron oxidation products reduce its flotation
[14-15]. Also, when the tails of the non-aerated Cu rougher
feed were reground and floated with XD5002 alone after
aeration (Test 3-2) lower gold recovery was produced
compared to when floated with a combination of SIBX and
XD5002 (Test 3). This can be attributed to better performance
of collector mixture, synergism and improved adsorption
characteristics of collector blend than the single collector [1618]. Also, the lower recovery of gold in the presence of
XD5002 alone may be attributed to its selectivity against iron
sulphide minerals (e.g. pyrite).

A.III. Effect of surface species

To account for the differences in pyrite recovery for the
aerated and no-aerated Cu rougher feed, EDTA extraction was
performed on the feed, primary ground product and after
aeration. Table 6 shows the amount of Cu, S and Fe oxidation
species extracted. The results indicate that the concentration of
surface Cu and Fe oxidation species in the feed was relatively
low compared to the primary ground product. The EDTA
extractable Cu and Fe increased approximately from 19 and
2% (feed) to 23 and 4%, respectively, after primary grinding.
The observed increase in Cu and Fe concentration after
primary grinding at high pH suggests the formation of more
Cu(OH)2 and Fe(OH)3 on the Cp surface, which will hinder its
surface affinity for collector adsorption. On the other hand, the
presence of Cu(OH)2 in solution can cause copper activation
of pyrite which will increase its surface affinity for collector
adsorption. The latter may account for the high pyrite recovery
observed after primary grinding with without aeration (Fig.3c).
Aeration of the pulp prior to flotation subsequently
increased the surface Cu and Fe oxidation. The EDTA
extractable Cu and Fe increased by approximately 5 and 2%,
respectively, after aeration. These could be related to the
creation of a more oxidising environment where high Eh values
are reached. It is generally accepted that pyrite is more reactive
than chalcopyrite therefore, at this stage it can be assumed that
the pyrite surface is strongly oxidised and covered with
hydrophilic iron oxide/hydroxide species preventing or
minimising their surface interaction with the collector. This
may explain why lower pyrite recovery was observed for the
aerated Cu rougher feed than the non-aerated Cu rougher feed.

In the case of copper, aeration and regrind do not

significantly affect copper recoveries. However, the grade of
copper was higher when XD5002 alone was used due to its
lower affinity for pyrite. Better selectivity of thionocarbamate
collectors for copper sulphides against iron sulphide is
achieved due to their specific interaction with cupric ions and
not with ferric, ferrous or lead ions [19-21]. The flotation
recovery of copper was improved marginally under the aerative
conditions than the non-aerative conditions. It has been shown
that flotation performance of chalcopyrite improved in high
pulp potentials [11-12]. Aeration of the pulp increases the pulp
potential to more oxidising environment which enhances
oxidation of collectors on chalcopyrite surface, hence improved
copper flotation.

TABLE VI. SURFACE Cu, S AND Fe OXIDATION SPECIES

PRESENT ON THE PYRITE SURFACE AS DETECTED BY EDTA
EXTRACTION FOR THE FEED, PRIMARY GRIND PRODUCT AND
AERATED PRODUCT.
Cu

Survey/sample

Con.
EDTA
Ext.,
mg/l

Total

Total

weight,

metal,

Con.
EDTA
Ext.,
mg/l

Fe

Total

Total

weight,

metal,

Con.
EDTA
Ext.,
mg/l

Total

Total

weight,

metal,

Feed

29

0.25

19

1071.0

8.99

68.15

46.20

0.39

1.77

After grinding

38

0.29

22.87

1575.0

12.39

93.85

100.8

0.79

3.62

Aeration

48

0.36

27.87

1722.0

12.92

97.84

134.4

1.01

4.60

B. Discussion
The results in Fig. 3 indicate that aeration of the Cu rougher
feed decreased gold recovery due to decreased pyrite recovery.
The mineralogical analysis of the ore [1] showed that the
majority of the unliberated gold particles were associated with
pyrite. However, regrinding of the copper rougher tails (both

CONCLUSIONS
Regrinding and aeration improved Au recovery and grade
due to improve liberation and significant rejection of pyrite in
Cu rougher tails. The flotation strategies indicate that the best
approach to maximise Au recovery and grade was nonaeration of Cu rougher feed and aeration of the reground
product. The different flotation strategies do not have a
significant effect on Cu recovery. However, the use of
XD5002 alone together with aeration of the reground product
of the non-aerated Cu rougher feed gave the highest Au and
Cu grades with maximum pyrite rejection. The results
discussed here when combined with our previous studies [1, 7]
could provide a holistic approach of maximising Au flotation
in a typical porphyry copper-gold ore without detrimental
effect on Cu flotation.

FUTURE WORK

[12]

Surface analysis using X-ray spectroscopy (XPS) will be

conducted in the future to determine the surface species
responsible for the pyrite rejection.
[13]
ACKNOWLEDGEMENTS
The financial support from AMIRA International and the
industry sponsors of the P260F project is strongly
acknowledged.

[14]

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