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Corresponding author. 1460 East 135 S, Room412, Salt Lake city, UT 84012.
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E-mail address: michael.free@utah.edu (M.L. Free).
Conventional chalcopyriteprocessingbegins withcomminution
using crushing and grinding. 100 to 500 tons of ore are crushed and
ground at an energy cost of 10 to 20 kWhr per ton for every ton
of copper produced. Thus, energy consumption for comminution
can range from1,000 to 10,000 kWhr per ton of copper. After crus-
hing and grinding, the resulting ne particles of chalcopyrite are
separated from gangue minerals by otation. Flotation results in
a concentrate of chalcopyrite containing nearly 30% copper that
is smelted and converted into blister copper, which is further
processed into copper anodes that are around 99.5% copper. The
anodes are electrorened to produce 99.99% copper cathodes.
An alternative method of producing copper fromcopper oxides
and secondary suldes utilizes heap leaching, solvent extraction,
and electrowinning. This process circumvents most or all of the
crushing and grinding as well as all of the otation, smelting and
electrorening. This approach has increased in use over the past 30
years because it is cost effective. This process is performed using
sulfuric acid media for copper oxide and secondary copper sulde
ores. However, leaching chalcopyrite by conventional sulfuric acid
heap leaching is difcult and generally results in low recoveries.
Thus, there are opportunities to adapt some of the chemistry devel-
opedfor chalcopyrite concentrate leaching tochalcopyrite ore heap
leaching to create more sustainable practices.
http://dx.doi.org/10.1016/j.electacta.2014.07.015
0013-4686/ 2014 Elsevier Ltd. All rights reserved.
448 A. Rodchanarowan et al. / Electrochimica Acta 140 (2014) 447456
Table 1
Comparison of leaching and electrowinning reactions for various processes.
Process Anticipated Leaching Reaction Electrowinning Reaction
Arbiter[2] CuFeS
2
+4.25O
2
+4NH
3
+H
2
O=Cu(NH
3
)
4
2+
+0.5Fe
2
O
3
+2SO
4
2
+2H
+
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
BacTech/Mintek[3] CuFeS
2
+4Fe
3+
=Cu
2+
+5Fe
2+
+2S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
BHAS[4] 3Cu
2+
+CuFeS
2
=4Cu
+
+2S
o
+Fe
2+
CuFeS
2
+3Fe
3+
=Cu
+
+4Fe
2+
+2S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
BioCOP[3] CuFeS
2
+4Fe
3+
=Cu
2+
+5Fe
2+
+2S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
BRISA[3] CuFeS
2
+4Fe
3+
=Cu
2+
+5Fe
2+
+2S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
Bromide[5] 3Cu
2+
+CuFeS
2
=4Cu
+
+2S
o
+Fe
2+
2Cu
+
=Cu+Cu
2+
CANMET[6] 2H
+
+(calcined conc.) =CuCl
2
+2S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
CENIM-LINETI[7] 2CuFeS
2
+4O
2
+2NH
4
+
=2Cu
2+
+2NH
3
+Fe
2
O
3
H
2
O+SO
4
2
+3S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
CLEAR[8] CuFeS
2
+3Fe
3+
=Cu
+
+4Fe
2+
+2S
o
3Cu
2+
+CuFeS
2
=4Cu
+
+2S
o
+Fe
2+
2Cu
+
=Cu+Cu
2+
Cuprex[4] CuFeS
2
+4Fe
3+
=Cu
2+
+5Fe
2+
+2S
o
Cu
2+
+2Cl
=Cl
2
+Cu
Cymet[9] CuFeS
2
+3Fe
3+
=Cu
+
+4Fe
2+
+2S
o
3Cu
2+
+CuFeS
2
=4Cu
+
+2S
o
+Fe
2+
Cu
+
+4Fe
2+
=3Fe
3+
+Cu+Fe
Dextec[10] Cu
2+
+CuFeS
2
+0.75O
2
+0.5H
2
O=2Cu
+
+2S
o
+FeOOH Cu
2+
+2Fe
2+
=2Fe
3+
+Cu
Ecochem[11] 3Cu
2+
+CuFeS
2
=4Cu
+
+2S
o
+Fe
2+
+ some CuFeS
2
+3Fe
3+
=Cu
+
+4Fe
2+
+2S
o
2Cu
+
=Cu+Cu
2+
some Cu
+
+Fe
2+
=Fe
3+
+Cu
some Cu
2+
+2Fe
2+
=2Fe
3+
+Cu
Electroreduction [22] 2CuFeS
2
+ 2H + 4H
+
= Cu
2
S + 3H
2
S + 2Fe
2+
Cu2S(s) +2H (surf) =2 Cu(s) +H2S
H
+
+ e
= H
H
2
S = S
+ 2H
+
+ 2e
Electroslurry[12] CuFeS
2
+4Fe
3+
=Cu
2+
+5Fe
2+
+2S
o
Cu
2+
+2Fe
2+
=2Fe
3+
+Cu
Elkem[13] 3Cu
2+
+CuFeS
2
=4Cu
+
+2S
o
+Fe
2+
CuFeS
2
+3Fe
3+
=Cu
+
+4Fe
2+
+2S
o
2Cu
+
=Cu+Cu
2+
Galvanox[14] CuFeS
2
+4Fe
3+
=Cu
2+
+5Fe
2+
+2S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
HydroCopper[3] CuFeS
2
+CuCl
2
+0.75O
2
=2CuCl +0.5Fe
2
O
3
+2S
o
NA (precip. CuO, hydrogen reduction to Cu)
Intec[15] Cu
2+
+CuFeS
2
+0.75 O
2
+0.5H
2
O=
2Cu
+
+2S
o
+FeOOH
2Cu
+
=Cu+Cu
2+
Leach/SX/EW(ore) CuS +2O
2
=Cu
2+
+SO
4
2
(for comparison to CuFeS
2
leaching)
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
(for comparison only)
Minemet[16,17] 3Cu
2+
+CuFeS
2
=4Cu
+
+2S
o
+Fe
2+
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
Nenatech[18,19] CuFeS
2
+4Fe
3+
=Cu
2+
+5Fe
2+
+2S
o
Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
Nitric Acid[20] 3CuFeS
2
+5HNO
3
+15H
+
=3Cu
2+
+3Fe
3+
+10H
2
0+6S
o
+5NO Cu
2+
+H
2
O=0.5O
2
+Cu +2H
+
USBM[21] CuFeS
2
+3Fe
3+
=Cu
+
+4Fe
2+
+2S
o
Cu
+
+Fe
2+
=Fe
3+
+Cu
Considerable research has been performed to replace smelting
and converting with hydrometallurgical processing of chalcopyrite
ores [222]. A list of many of the processing methods that do not
involve pressurizedvessels are presentedinTable 1. Other methods
have been developed for elevated pressure applications that will
not be discussed here.
1.1. Halide based leaching and electrowinning
Note that of the processes shown in Table 1, those with halide
are generally performed at lower temperature (near ambient con-
ditions) than those with sulfate. Halide based leaching is generally
muchfaster thansulfate leaching at ambient temperature. Chloride
salts such as sodiumchloride are readily available and inexpensive,
and in some locations seawater brines are used out of necessity in
arid coastal areas. In addition, halides can in some cases be directly
integrated with gold leaching. Thus, the halide based methods are
among those most likely to be used in a heap leaching scenario
for chalcopyrite ore. Metal recovery experiments using integrated
leaching-electrowinning [23,24], have also been performed for
recovery of metals such as Cu, Ag, Pd, Sn, and Pb from electronic
scrap in halide media. Copper recovery from IPC (Inco Pressure
Carbonyl) process has been reported, where multistage leaching
was utilized in order to produce copper without solvent extraction.
However, most of these experiments were performed for metal
rich residue leaching. Other methods, such as many of those in
Table 1, can be effective in concentrate leaching scenarios, but are
not likelytobeutilizedincommercial heapleachenvironments due
to reagent costs, heating costs, capital costs, and a variety of other
reasons.
Cupric chloride and ferric chloride solutions are very efcient
oxidizing agents for sulde mineral leaching [9,10]. Leaching of
chalcopyrite in chloride media can be represented by [4,6].
CuFeS
2
+4FeCl
3
CuCl
2
+5FeCl
2
+2S
0
CuFeS
2
+3CuCl
2
+4Cl
4CuCl
2
+FeCl
2
+2S
0
These reactions suggest that chloride based leaching of chal-
copyrite using cupric chloride and ferric chloride as leachants,
produces cuprous as well as ferrous ions. The associated elec-
trowinning reactions can be expressed as:
CuCl
2
+e
Cu + 2Cl
(cathode)
CuCl
2
CuCl
2
+e
; FeCl
2
FeCl
2
+
+e
(anode)
Some supplemental oxidation is needed to meet the stoichio-
metric requirements drive the chalcopyrite leaching reactions. The
additional oxidation can be provided by air injection. Also, oxida-
tion of remaining ferrous ions after the electrowinning step helps
to facilitate FeO(OH) precipitation prior to leaching.
Producing quality copper in chloride media often requires
smooth deposits to avoid entrapped impurities as well as short-
circuiting. Appropriate additives and mass transport control are
generally required to achieve smooth deposits in industrial elec-
trowinning. Thus, this study will present research in this area that
is applied to copper chloride media.
A. Rodchanarowan et al. / Electrochimica Acta 140 (2014) 447456 449
Fig. 1. Schematic diagramof leaching and electrowinning experimental set up.
2. Experimental Procedures
2.1. Leaching Tests
Inorder to examine the viability of halide leaching [25], factorial
designs of experiments (two levels, three factors) were established.
Factors chosen in this case are acid concentration, ratio of concen-
trationof ferric andferrous ions, andratioof concentrationof cupric
and cuprous ions. The amount of copper extracted (gm/gmof ore)
was chosen as the response variable. Laser induced breakdown
spectroscopy analysis of ore samples was performed for elemen-
tal characterization. Line identications were done using PLASUS
Specline software. Chalcopyrite ore (5 grams) of size (-35 +100)
was taken and wet screened properly for removal of nes. Ore
was then dried for further use. A small 50ml burette was used for
leaching. Leaching solution from the reservoir was pumped into
the burette where it uidized ore particles. This uid was sent back
to the reservoir. This operation was carried out for a period of two
days.
The experimental matrix for leaching test conditions is pre-
sented in Table 2. Eight different experiments were conducted.
After completion of leaching, solids were ltered out from the
column and dried. Leaching residue was completely ground and
digested in aqua regia. Inductively coupled plasma mass spec-
troscopy was conducted, in order to determine the amount of
leached copper.
2.2. Electrowinning with combined leaching
Inorder toevaluateelectrowinningperformance, thesamesolu-
tions were used for both electrowinning and leaching as indicated
inTable2. Theseexperiments areessential for exploringthevalidity
and performance evaluation of an overall integrated process.
Table 2
Factorial design test matrix for leaching and electrowinning.
Test ID Cu
++
(M) Cu
+
(M) Fe
+++
(M) Fe
++
(M) HCl(M)
Cu01-09Fe01-09H05 0.01 0.09 0.01 0.09 0.05
Cu09-01Fe01-09H05 0.09 0.01 0.01 0.09 0.05
Cu01-09Fe09-01H05 0.01 0.09 0.09 0.01 0.05
Cu09-01Fe09-01H05 0.09 0.01 0.09 0.01 0.05
Cu01-09Fe01-09H15 0.01 0.09 0.01 0.09 0.15
Cu09-01Fe01-09H15 0.09 0.01 0.01 0.09 0.15
Cu01-09Fe09-01H15 0.01 0.09 0.09 0.01 0.15
Cu09-01Fe09-01H15 0.09 0.01 0.09 0.01 0.15
Stainless steel cathodes (thickness =0.06mmand area 2-3 cm
2
)
were used. Cathodes and anodes were spaced 1cmapart. In order
to simulate an actual tank house environment, lead was used as
the anode. The volume of electrolyte for each test was 100ml. Elec-
trowinning operations were carried out at 40
C. The duration of
electrowinning (EW) was 20hours for each test.
Deposition was carried out using galvanostatic current at
5mA/cm
2
. The ratio of cupric to cuprous ions, ferric to ferrous ions,
and HCl concentration were selected as factors. Current efciency
was the response variable.
Alabscale experimental setupwas establishedinorder toevalu-
atepreliminaryviabilityof simultaneous leachingandEWas shown
in Fig. 1. In this experiment, leaching solution was circulated from
the EWcell through the column, which is lled with ore, and then
returned to the EWcell. The recirculating solution was maintained
at a set pH by a pH controller. Eh and pH of the solution were con-
tinuously monitored. Electrowon copper was measured by weight
at regular intervals. Stainless steel electrodes were used as the
working electrodes. A platinummesh electrode was chosen as the
counter electrode. Scanning electron microscope (SEM) character-
ization of selected electroplated samples was performed using an
FEI Nova NanoSEM
TM
.
The general test conditions for ore leaching and electrowinning
were 1.9M CaCl
2
, 0.1M CuCl
2
, 500 grams of -14+35 Mesh ore, 1
liter of total solution, pH1.5, 2.8liters per hour of recirculating ow.
It shouldbe notedthat this integratedleaching-electrowinning test
was performed using cupric chloride in the leaching solution to
examine and validate the proof of concept. Calcium chloride has
been used to recovery of various heavy metals fromsoil [26,27] as
well as to recover copper fromarsenical Cu-Co sulde concentrate.
In this study CaCl
2
was added to enhance recovery and moderate
the free sulfate and iron concentrations.
2.3. Additive and Mass Transport Testing
A three component electrowinning cell was used in the exper-
imental deposition of copper to evaluate roughness. It consisted
of a platinumcounter electrode and a saturated calomel electrode
(SCE), against which the potentials are reported. The working elec-
trode was a copper disc (99.999% pure from Alfa Aesar) mounted
in a Teon holder with an area of 0.203 cm
2
exposed to the elec-
trolyte. It was polished with600-grit polishing paper to remove the
deposition products from the previous tests and then rinsed with
pure water. This electrode was further polished with Micropolish
alumina powder (0.05m) to obtain a smooth, clean, defect-free
450 A. Rodchanarowan et al. / Electrochimica Acta 140 (2014) 447456
Fig. 2. LIBS spectrumof chalcopyrite ore sample. Inset shows a portion of ore surface, chosen for elemental analysis.
surface. Finally the electrode was cleaned in an ultrasonic water
bath to remove any polishing particles from the surface. All solu-
tions were prepared using reagent grade chemicals and ASTMType
I water. Electrochemical tests were performed using an EG&G 273
potentiostat, operated using PowerSuite software made by Prince-
ton Applied Research, and PCI4/750 potentiostat operated using
Virtual Front Panel software, both made by Gamry Instruments,
connected to an IBM compatible PC and AFASR rotator from Pine
Instruments for potentiostatic andgalvanostatic current transients.
Surface roughness was characterized by a CCDIris camera by SONY
with the help of LEAD CAPTURE and LEAD CONVERT software (by
LEAD technologies) along with Microimage software (University
of Utah). Surface roughness calculations were performed by MAT-
LAB (Mathworks Inc.). Surface roughness was quantied as the
quadratic mean for the vertical deviations of the area prole of
electrodeposited surface. Selected samples were examined using
an SEMto examine electrodeposit quality.
3. Results and Discussion
3.1. Application scenarios for chalcopyrite leaching in chloride
media
One approach to reducing energy in chalcopyrite ore leaching
is to utilize run-of-mine or crushed ore in heaps to reduce com-
minution costs. Elemental characterization of ore sample based
on LIBS spectrum suggests that it contains elements such as Cu,
Fe, S, Si and trace amount of other elements including Zn and Al
(See Fig. 2). Leaching can be performed using chloride media to
recover copper. The use of chloride media results in rapid leach-
ing of chalcopyrite and the production of cuprous chlorides that
require only half of the electrons (Cu
+
+e
Cu). In
addition, the cell voltage is reduced by approximately half due to
the use of cuprous andferrous ions oxidation(Cu
+
Cu
2+
+e
; Fe
2+
Fe
3+
+ e
[C
ba
(
C
sa
C
ba
)
a
exp(
a
F
RT
) C
bc
(
C
sc
C
bc
)
c
exp(
c
F
RT
)] (1)
Fig. 9. Scanning electron microscope image of copper electrodeposit (as deposited and slightly polished), Electrolyte contains 0.1MCuCl, 4MNaCl and 0.01MHCl.
454 A. Rodchanarowan et al. / Electrochimica Acta 140 (2014) 447456
Table 3
Comparison of surface roughness values fromrotating disc experiments for direct and pulsed electrodeposition condition.
Charge (C/cm
2
) DC Roughness (m) Time (min) Pulse Roughness (m) Time (min)
75 4.58 120 6.23 120.0
108 5.39 120 8.00 473.4
180 13.20 120 13.91 460.5
250 24.96 120 14.28 479.7
Fig. 10. Surface topography image of copper rotating disc electrode sample obtainedafter electrodepositionat a cathodic current density of 10mA/cm
2
for 30min at rotational
speed of 250 rot/min and 500 rot/min. Bath contain 0.1mol/L CuCl, 4.0mol/L NaCl and 0.01mol/L HCl.
where k is a constant that is directly related to the equilibrium
exchange current density, C
b(a or c)
is the bulk concentration for the
anodic (a) or cathodic (c) reactions, C
s(a or c)
is thesurfaceconcentra-
tion for the anodic (a) or cathodic (c) reactions, is overpotential,
R is the gas constant, T is absolute temperature, and is a factor
that depends upon reaction mechanisms and related factors and it
is usually between 0.25 and 1. In subsequent expressions, will be
assumed to be 1.
If the overpotential becomes very large, then a limit is reached
where the rate of mass transport reaches a maximum level. The
current density measured under these complete mass transport
control conditions is known as the mass transport limiting current
density (i
L
). This limiting current density is governed by the diffu-
sion rates of the dissolved metal ions in the solution and hence it
is also known as diffusion controlled current density. This can be
written:
i
L
=
nFD(C
ba
C
sa
)
(2)
where Dis the diffusivity of the dissolved species and is the thick-
ness of the diffusion layer.
If mass transport is controlling the current owin electrodepo-
sition, the limiting current density is an important parameter that
can be used to study this diffusion limited mass transfer. Therefore,
a series of experiments were carried out to study cathodic elec-
trodeposition of copper under direct current conditions. The effect
of mass transport on electrode surface of copper electrodeposit
morphology was studied by varying rotational speed of work-
ing electrode from 250 to 1000rpm. It has been observed that
surface roughness of electrodeposit decreases with increase in
rotational speed. Such an observation was for xed direct cur-
rent conditions (See Fig. 10). On the other hand an increase in i/i
L
ratio causes enhanced surface roughness. Pulsed potential results
in a short deposition period, during which the depositing ions
become depleted in solution near the electrode interface. A rest
period allows replenishing of depositing ions near the electrode-
electrolyte interface. Thus, the rest period allows for an increased
limiting current density for the short duration of the applied
pulsed voltage. For argon purged electrolyte containing 0.1mole/L
CuCl, 4mol/L NaCl, and 0.1mol/L HCl a 30% enhancement in
limiting current density was observed when the pulse-off time was
increased from10ms to 50ms. It can be understood that the longer
relaxation time allows greater replenishment of ions in the bound-
ary layer, resulting in a higher mass transport limiting current.
It was observed that surface roughness of deposits obtained
under pulsed current is low compared to deposit obtained at dc
conditionwithhighi/i
L
value. Informationfromtopography exami-
nationsuggests that at i/i
L
=0.50, rms roughness was almost double
for pulsed plating condition compare to dc-electrodeposition. The
surface roughness of electrodeposits depends on nucleation and
growthrate. Growthwas monitoredfor trapezoidal anomaly, it was
observed that highest point on growing surface receive higher cur-
rent andhavegreater access of uxof incomingreactionions. Sucha
region which receive higher ux, higher growth of electrodeposit is
expected. Increase in rotational speed causes lowering of preferen-
tial growth of electrodeposits due to more uniformcurrent density
distribution. Increase in cathodic overpotential results in higher
current density. However such higher overpotential increases the
difference in current density at top and bottom region of trape-
zoidal anomaly, which results in different growth rate in these
regions. Table 3 shows the comparison of surface roughness values
fromrotating disc experiments for direct and pulsed electrodepo-
sition condition.
For a given rotational speed of a rotating copper disc, a limiting
current density was observed in the cathodic direction as seen in
Fig. 11. In Fig. 11, it is seen that changes in the applied potential
Table 4
Copper electrodeposition purity (samples were collected fromdifferent places).
Sample Copper purity
1 99.1%
2 99.0%
3 99.4%
A. Rodchanarowan et al. / Electrochimica Acta 140 (2014) 447456 455
Fig. 11. Potentiodynamic scans for argon purged electrolyte with 0.1mol/L CuCl,
4 mol/L NaCl and 0.01mol/L HCl as a function of rotational speed of electrode at a
scan rate of 5mV/s. A calomel electrode was used as a reference electrode against
which all the potentials were measured.
Fig. 12. Limiting current densities under direct current conditions in a bath con-
taining 0.1mol/L CuCl, 4.0mol/L NaCl and 0.01mol/L HCl.
Fig. 13. Effect of i/iL on rms surface roughness of copper electrodeposits obtained
fromabathcontaining0.1mol/LCuCl, 4.0mol/LNaCl and0.01mol/LHCl under direct
current conditions at various rotational speeds of copper working electrode.
result in very little change in the current in the regions where mass
transfer limitations dominate. In this region the electrochemical
reaction can only proceed as quickly as the reacting ions can be
transported to the electrode surface.
This region of nearly constant cathodic current density can be
viewed as the balance between the rate of electrochemical reaction
and the rate at which the reacting ions are transported to the elec-
trode. With increase in the rotational speed of the disc, this rate of
mass transport increases, thereby increasing the limiting current
density as seen in Fig. 12.
One way to characterize the extent to which the deposition is
mass transport controlled is to determine the ratio of the applied
current density to the limiting current density. As this ratio (i/i
L
)
approaches 1 the systemapproaches complete mass transport con-
trol. When i/i
L
is near zero the deposition process is controlled by
electron charge transfer kinetics. Therefore, the effect of i/i
L
on
root- mean-squared surface roughness of copper electrodeposits
was studied. It was foundthat the surface roughness increasedwith
increase in i/i
L
for direct current conditions as seen in Fig. 13.
4. Conclusions
In summary, potential of copper recovery using chloride media
was examined using coupled leaching-electrowinning approach.
The 2-day copper extraction was as high as 68%. Deposit qual-
ity, percentage recovery, and electrowinning efciency were also
examinedusing electrolytes containing different levels of dissolved
iron and copper. The copper electrodeposited per electron in chlo-
ride media was higher thanfor conventional sulfate electrowinning
systems. Analyses were done using statistical models and avail-
able theory for chloride media leaching. Electrodeposit quality
improvements were accomplished using proper choice additives
and mass transport conditions. A detailed investigation were per-
formed using more than 25 additives as well as different mass
transport conditions including rotational speed variation, different
limiting current density, pulse and dc electrodeposition.
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