Activation of Sphalerite by Cu Ions Produced by… 1

Activation of Sphalerite by Cu Ions Produced by Cyanide

Action on Chalcopyrite
S.R. Rao, J.E. Nesset and J.A. Finch
McGill University, Montreal, Canada

ABSTRACT: Cyanide used as a depressant for pyrite in the flotation of chalcopyrite from a complex ore was
found to result in the flotation of sphalerite. This was thought to be due to the leaching of cupric ions from
chalcopyrite by cyanide. A series of measurements were conducted to determine the extent of Cu ion production
from chalcopyrite treated with cyanide and the effect of pulp potential. The reaction is influenced by pulp
potential, a large cathodic potential suppressing the apparent activation. It was found, the activation, measured by
the uptake of Cu ions by sphalerite is suppressed when the potential is made cathodic by a reducing agent, and
enhanced by aeration, which makes the potential more anodic. It is suggested, this is related to the oxidation of
cuprocyanide to cupric cyanide, which supplies Cu ions.

1. INTRODUCTION to -200+325 mesh was sent from Laronde mines

In the selective flotation of chalcopyrite from a
complex ore, cyanide is used to depress pyrite. In
a plant in Quebec, Canada, it was observed that
this practice often led to the deportment of
sphalerite in the chalcopyrite concentrate. Further,
the extent of such inadvertent flotation of
sphalerite depended upon the pulp potential. The
deportment is reduced at lower pulp potential.
Somewhat similar observations were reported 40
years ago by Plaksin et al. (1964), but details of
that work are not available. As cyanide is a
common depressant for sulphide minerals, this
apparent activation of sphalerite in cyanide
treated ore led to the present investigations to
determine the causes and possible corrective
measure to reduce the non-selective flotation of
sphalerite, apparently caused by the action of
cyanide. It was suspected that as cyanide leaches
copper compounds forming cuprocyanide or
cupricyanide complex that could be a source of
cupric ions, which inadvertently activate sphalerite
leading to its non-selective flotation.
2. EXPERIMENTAL
2.1 Materials
High grade chalcopyrite and sphalerite from Ward’s
establishment were used for basic measurements.
The chalcopyrite analyzed 31% Cu and 28% Fe.
Sphalerite contained 65% Zn. Natural ore ground
of Agnico-Eagle (Quebec, Canada). Chemical
analysis showed 0.33% Cu, 4.1% Zn and 26.3%
Fe, besides several trace elements. Mineralogical
examination showed copper present as chalco-
pyrite. Some portion of it was found to have been
oxidized. Grinding balls for cementation studies
were sent by Laronde. Mild steel balls were
truncated cone shape and chrome steel balls were
spherical. Sodium cyanide, sodium dithionite
(Na2S2O4, used to lower the pulp potential) and
zinc sulphate were Fisher products. A 5% stock
solution of the cyanide was prepared. Dithionite
was mixed as powdered solid.
2.2 Procedure
An exact weight of chalcopyrite was mixed with
the chosen amount of cyanide in 100 mL in a
stoppered container and mechanically mixed for
30 min. The pH was measured by a portable pH
meter (Laval Labs) and pulp potential by an ORP
gold electrode (Cole Parmer). The chalcopyrite
was separated by centrifuging and the solution
analyzed for Cu by atomic absorption
spectroscopy (AA).
Effects of particle size, pulp potential and
sphalerite mixing were determined. The pulp
potential was made more anodic by bubbling
in air and more cathodic by mixing measured
quantities of sodium dithionite. In another set of
measurements, 0.5 g sphalerite was mixed with
2  Mineral Processing Technology (MPT 2007)
the chalcopyrite and cyanide pulp to determine
the possible uptake of Cu ions by sphalerite. In
the experiments with sphalerite, both Cu and Zn
ion concentrations were determined by AA.
A set of experiments was conducted to
determine the effect of zinc sulphate on leaching
of chalcopyrite by cyanide as zinc sulphate is
commonly used with cyanide as depressant, in
the weight ratio, 3 ZnSO4.7H2O to 1 NaCN.
Measurement of Cu Uptake by Sphalerite in
Cyanide Medium. In order to determine the effect
of pulp potential and the role of cupro- and
cupricyanide species on Cu uptake by sphalerite,
measurements were conducted by mixing cupric
sulphate with stoichiometric amount of sodium
cyanide to form cuprocyanide, –[Cu(CN)4]-3.
Sphalerite (0.5 g) was mixed with this solution
and Cu concentration measured. The measure-
ment was repeated after aerating cuprocyanide
(to oxidize to cupricyanide). Similar measurements
were conducted with an extract obtained by
treating chalcopyrite with cyanide following the
procedure described before. In another set of
measurements, the quantity of zinc ions from
sphalerite treated with cyanide-chalcopyrite
extract was measured to determine the exchange
of Cu and Zn ions. Microflotation tests were
conducted using a Siwek cell (Siwek et al.,
1981), capacity 50 mL, constructed at McGill
University’s glass blowing shop.) An exact
amount (0.5 g) of sphalerite (34-63 µm) in a
dilute (1%) slurry was mixed with sodium
isopropyl xanthate (1 mg). Dowfroth 250C, 0.05
mL of 10% solution, was added as frother. The
concentrate was collected, dried and weighed.
Cementation experiments were conducted with
mild steel balls and chrome steel balls. In one set
they were immersed in cupric sulphate solution,
50 mg/L Cu++, pH 7.5. In the second set, they
were immersed in the cyanide extract produced
by mixing with chalcopyrite. The change in
cupric ion concentrations were measured by AA.
3. RESULTS
The results obtained with different experimental
variables are summarized as follows:
Effect of Cyanide Concentration on Cu Ion
Produced from a Constant Weight (10 g of -200
+325 mesh mineral) of Chalcopyrite. 0.10-0.11
mg Cu was produced per unit weight of
chalcopyrite. There was no significant change in
the cyanide concentration range 250-750 mg/L.
Effect of Varying Weight of Chalcopyrite
(-200+325 mesh) at a Constant Quantity (25 mg
in 100 mL) of Cyanide. The quantity of Cu
produced per unit weight of the mineral was
unchanged at 0.10-0.11 mg per unit weight of
chalcopyrite.
Effect of Particle Size. With 5 g -325 mesh
chalcopyrite in 25 mg cyanide in 100 mL, the
quantity of Cu produced rose to 0.83 mg per unit
weight of the mineral
Effect of Aeration. By aeration, the ORP of
the slurry became more anodic, rising from -450
mV to -330 mV, but the quantity of Cu produced
per unit weight of chalcopyrite did not show
singnificant change (0.12 mg per unit weight of
thye mineral).
Effect of ZnSO4. In presence of ZnSO4, the
Cu ions produced per unit weitht of the mineral
dropped from 0.12 mg to 0.08 mg.
Effect of Lowering Pulp Potential (ORP).
When ORP is lowered by mixing sodium
dithionite, the quantity of Cu ions produced was
lowered significantly. Lowering the ORP from -
475 mV to -700 mV (adding 100 mg sodium
dithionite per i00 mL) resulted in a drop of Cu
ion produced to 0.08 mg (from 0.11 mg) per g
mineral. Further lowering of ORP to -750 mV
(adding 200 mg sodium dithionite per 100 mL)
resulted in a further drop of Cu ion produced to
0.06 mg per g mineral.
Cu Ion Measurement with Natural Ore. The
results recorded in Table 1 show, the Cu++ ions
released per g chalcopyrite in the natural ore is
almost 100 times greater than that found with
single mineral chalcopyrite. In part, this is
accounted for by the Cu++ ions produced by the
ore in water. When the slurry is aerated, the
potential becomes more anodic and the Cu++
produced increases six-fold.
Measurements of Cu Uptake by Sphalerite in
Cyanide Solution. The results of Cu uptake by
sphalerite from cuprocyanide and cupricyanide
solutions are shown in Tables 2 and 3 for a
synthetic cuprocyanide solution and cyanide-
chalcopyrite leach extract respectively.
Activation of Sphalerite by Cu Ions Produced by… 3
The results of Tables 2 and 3 show that there would activate the mineral, promoting its
is no uptake of Cu by sphalerite from cupro- flotation).
cyanide solution. When aerated, cuprocyanide is 10 g –200 mesh chalcopyrite + 100 mL solution
partially oxidized to cupricyanide (with corres- with 10 mg NaCN.
ponding increase in the pulp potential to anodic
The extract mixed with 1.0 g sphalerite (-325
region) when Cu uptake by sphalerite is
mesh) for 30 min. Centrifuged.
observed. The Cu uptake is significantly greater
from cyanide extract produced with chalcopyrite. Cu ion produced from chalcopyrite with NaCN
0.026 mmole (a)
Table 1: Cyanide Treatment of Natural Ore 20 g
ore + 10 mg cyanide in 100 mL water. Zn ion produced from sphalerite with NaCN
0.012 mmole (b)
Expt. Cu Cu ORP,
produced, produced, mV Cu ion in chalcopyrite cyanide extract
mg per g mg per g mixed with sphalerite 0.019 mmole (c)
ore chalcopyrite
Blank (in Zn ion in chalcopyrite cyanide extract
0.06 6.0 -365
water, pH 9.8)
Cyanide only 0.11 11.0 -450
mixed with sphalerite 0.0197 mmole (d)
Cyanide + Zn ions released from sphalerite byactivation
ZnSO4 0.10 10.0 -454 with cupric ions: (d) – (b) 0.0077 mmole
(30 mg)
Cyanide + Cu ion consumed by sphalerite:
dithionite 0.06 6.0 -598 (a) – (c) 0.007 mmole
(200 mg)
Cyanide + air 0.68 68.0 -256 There is fair agreement between the Cu ions
taken by sphalerite and the Zn ions produced
Table 2: Uptake of Cu by Sphalerite from from sphalerite, indicating exchange of Cu ions
Cuprocyanide Solutions, without and with for Zn ions, the mechanism of activation of
Aeration sphalerite.
Conditions Quantity of ORP,
Cu(II) ions mV
Cementation. Table 4 shows the results of
in 50 mL (SCE) cementation studies.
Cuprocyanide solution 16.1 -310 Table 4. Cementation Studies to Determine
Cuprocyanide solution + any Possible Effect of Grinding Medium on
16.1 -336
Sphalerite Copper Uptake by Chalcopyrite Treated with
Cuprocyanide solution + Cyanide.
20.6 -266
air
Cuprocyanide solution + 1. With Mild Steel (Truncated Cones)
14.0 -255
air + Sphalerite a. 4 cones + 10 mg Cu++ in 200 mL (50 mg/L)
Table 3: Uptake of Cu by Sphalerite from b. 4 cones + 10 mg Cu++ + 40 mg Cyanide
Cyanide-Chalcopyrite Leach Extract c. 20 g Chalcopyrite (-325 mesh) + 20 mg
Conditions Quantity of ORP, mV Cyanide in 200 mL. Aeration
Cu(II) ions (SCE)
in 50 mL
d. 4 cones + 20 g Chalcopyrite (-325 mesh) + 20
Leach solution 28.0 -390 mg Cyanide in 200 mL. Aeration.
Leach solution e. 4 cones + 20 g Chalcopyrite (-325 mesh) + 2
27.1 -385
+ Sphalerite
g Sphalerite + 20 mg Cyanide in 200 mL.
Leach solution
+ air
54.6 -288 Aeration.
Leach solution
21.5 -146 2. With Chrome Steel (Spheres)
+ air + Sphalerite
Repeat a, b, c, d, e with 2 Spheres (to get almost
Uptake of Cu Ions by Sphalerite. The cyanide equal surface area)
extract produced by mixing chalcopyrite with
cyanide was mixed with sphalerite to determine Expt. 1a 1b 1c 1d 1e
the uptake of Cu++ ions by sphalerite (which ORP, -170 -291 -266 -244 -210
4  Mineral Processing Technology (MPT 2007)
mV some leaching of Cu from chalcopyrite by
Cu++, 34.0 50.6 28.8 26.3 20.2 cyanide. The results of the leaching, in the first
mg/L stage is cuprocyanide ions:
Expt. 2a 2b 2c 2d 2e Cu+ + 4 CN- ⇔ Cu(CN)4 3-
ORP, -165 -296 -266 -264 -212
mV
As long as ORP is sufficiently cathodic, the
cuprocyanide will be in equilibrium with cyanide
Cu++, 35.0 50.1 28.8 28.4 20.1
mg/L and there will be no further Cu leached from the
mineral; that is, the quantity of Cu produced will
The results show, Cu++ ions displace Fe from be limited and as Cu is in +1 oxidation state, it
steel balls, as shown by the drop in Cu will not be exchanged for divalent Zn ions.
concentration from 50 mg/L to 35 mg/L (1a and When the slurry potential is raised by
2a), but Cu in cuprocyanide does not displace Fe aeration, the cuprocyanide is oxidized to cupric
from the steel balls, as Cu++ ion concentration cyanide:
remains unchanged at 50 mg/L (1b and 2b). With 2 Cu(CN)4 3- + ½ O2 + H2O→ 2 Cu(CN)2 + 2 OH-
cyanide- chalcopyrite extract, with aeration, the
Cu produced displaces some iron from the steel + 4 CN-
ball surface (comparing Cu concentrations in 1c This leads to more Cu being leached from
and 1d), but there is no action on chrome steel as chalcopyrite, and as part of the Cu is oxidized to
indicated by no change in Cu ion concentration +2 oxidation state, it can exchange for Zn ions in
(2c and 2d). Cu ions produced are still, however, sphalerite causing activation of the mineral. The
abstracted by sphalerite (1e and 2e). results also explain lower Cu concentration found
Microflotation. The results of microflotation in presence of dithionite, which makes the ORP
are shown in Table 5. more negative, thereby hinders the oxidation of
0.5 g sphalerite mixed with Cyanide Cu+ to Cu2+. The quantity of Cu2+ produced from
Chalcopyrite Extract (pH 9.8) natural ore is higher by a factor of ten as
+ 0.5 mg K isopropyl xanthate + 0.05 mL, compared to that from single chalcopyrite. Two
10 % Dowfroth 250. possible reasons for such high production of Cu2+
are suggested. Firstly, chalcopyrite is in contact
Flotation conducted in a Siwek
with pyrite. When the ore is ground, there would
microflotation cell.
be galvanic interaction between pyrite and
Flotation time, 3 min. chalcopyrite. Pyrite being nobler of the two,
The concentrate collected, dried, weighed. draws electrons from chalcopyrite. That will
produce elemental sulphur (by the oxidation of
Flotation conditions Percent Recovery
sulphide) and Cu2+ ions (by the oxidation of Cu).
Mineral in water + xanthate, pH 4-6 Secondly, it appears, chalcopyrite in the natural
9.8
ore appears to have been partly superficially
Mineral in cyanide, pH 9.8 + ~0
xanthate
oxidized by atmospheric weathering and it
produces Cu2+ in water, as was observed with
Mineral in cyanide-chalcopyrite 28-32
extract blank measurements in water at pH 9.8 (Table 1).
Mineral activated with Cu ions, + 70-76 Implications in Flotation. The results of
xanthate these measurements show that in industrial
The results show appreciable flotation of flotation of chalcopyrite ores, where cyanide is
sphalerite from the chalcopyrite-cyanide extract. used as depressant, it could have an inadvertent
effect causing the activation of sphalerite by the
Cu ions leached from chalcopyrite. The reaction,
4. DISCUSSION however, is sensitive to pulp potential. Under
conditions where the pulp potential is sufficiently
The results described show that the cause of
negative (< -400 mV vs SCE), the action is
observed activation of sphalerite in chalcopyrite
suppressed as the copper leached stays as
containing ores treated with cyanide is due to
Activation of Sphalerite by Cu Ions Produced by…
cuprocyanide with Cu in +1 oxidation state,
which has no activating action (as it cannot
exchange with divalent Zn ions). In semi-
autogenous grinding of polymetallic ores, where
the grinding media do not consume much
oxygen, the pulp potential could be sufficiently
anodic to oxidize Cu+ to Cu2+, thus inadvertently
promoting the activation of sphalerite. In addition
to chalcopyrite, such actions may also be found
with ores containing other Cu minerals like
chalcocite, bornite and covellite, which may be
leached by cyanide to a greater extent than
chalcopyrite.
5. ACKNOWLEDGEMENT
5
Work done under NSERC-CRD grant with
support from sponsoring companies. Authors
thank Agnico-Eagle Mines (Laronde operations)
for initiating the project, providing samples and
useful discussions.
REFERENCES
[1] Plaksin, I. N., Okolovich, A. M., Figurkova, L.
I., and Sidorenko, A. N., Activating effects of
small amounts of cyanide in size reduction of
copper ores. Dobycha I Obogashch Rud
Tsvetnye Metall., 8, 36-39 (1964).
[2] Siwek, R., Zembala, M., Pomianowski, A., A
method for the determination of fine particle
flotability. Int. J. Mineral Process., 8, 5-88
(1981).