Electrochemical Hydrodynamics Modeling Approach For A Copper Electrowinning Cell
Electrochemical Hydrodynamics Modeling Approach For A Copper Electrowinning Cell
Electrochemical Hydrodynamics Modeling Approach For A Copper Electrowinning Cell
\
|
|
|
.
|
\
|
=
C
bulk
s
C
C
i i
|
q
exp
0
(4)
where, q is the overpotential at the electrode,
C
is the Tafel slope, i
0
is the exchange current
density, and superscripts s and bulk are the locations at the electrode surface and bulk electrolyte,
respectively.
For electrolyte salt in the interior of an electrolytic cell, there are no free electrical charges. The
potential drop across the bulk electrolyte is governed by the Laplace equation [15, 16]:
0
2
= V | (5)
where, | represents the local electrical potential. In addition, the current density distribution is
obtained by solving the following equation (k= electrical conductivity):
| kV = i (6)
Assuming that we impose a specific voltage drop (
Cell
E ) across the electrodes, the overall
voltage balance may be written as:
c a ohm Cell
E q q | + + = (7)
where
ohm
| is the ohmic voltage drop, q
a
and q
c
are the voltage drops owing to activation
polarization (i.e., kinetic effects) and concentration polarization (owing to concentration gradients
between the electrode surface and bulk electrolyte), respectively.
2.3. Electrowinning cell geometry and boundary conditions for simulation
Copper electrowinning is the process of winning copper from an electrolyte to solid form on a
cathode by passing an electric current through the electrolyte to attract copper ions to the cathode. In
this demonstration approach, a simple channel cell was selected. Its geometry is rectangular and the
distance between the electrodes is a bit large compared to their width. Copper electrowinning takes
place in a rectangular channel geometry, with two protruded planar electrodes opposing each other,
and the current moves between the electrodes and depletes the copper ions at the cathode.
Int. J. Electrochem. Sci., Vol. 8, 2013
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It may then be assumed that the flow is in a steady state and is turbulent, and incompressible
and is between two planar and parallel electrodes. The geometry and generated mesh for this cell is
shown in Figure 1.
Outlet
Cathode
Anode
Inlet
Cathode
plane
20 m
Figure 1. Schematic view of volume-discretized electrowinning cell geometry.
The electrolyte volume was meshed with the tetrahedral elements within the Ansys Workbench
platform. In the simulation, the fluid domains of the electrolyte were divided into a diffusion-dominant
region near the cathode and a stationary region for the outside, which were connected together with a
domain interface. In particular, the fine meshes (~1 m) were applied to the cathode surface to obtain
the velocity distribution behaviors and concentration gradient.
Zero gradient boundary conditions for the ion concentration were imposed along the walls
except the inlet, outlet and cathode surface. No-slip velocity boundary conditions were applied on all
walls. Calculations were initialized with the ion concentration equal to the bulk concentration
throughout.
3. RESULTS AND DISCUSSION
3.1 Model parameters and hydrodynamically coupled electro-transport
The relation between electro-transport and mass transport with electrolyte flow during
electrolysis was modeled using computational fluid dynamics. In this modeling approach, the
electrolyte flow may be considered to be steady, and the fluid is supposed to have a constant chemical
composition and physical properties. It was assumed that the aqueous acid electrolyte containing
approximately 50 mol/m
3
of cupric ion (Cu
2+
) was fed into the channel cell at various inlet velocities.
Table 1 is the properties of the acid sulfate electrolyte and electrode reaction kinetics used in this
simulation [12].
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12338
Table 1. Properties and parameters used in the simulation [12]
Electrolyte properties values
Inlet electrolyte velocity, u (m/s) 0.1-0.5
Initial and inlet concentration of cupric ions, C
bulk
(mol/m
3
) 50
Diffusion coefficient of cupric ions, D
C
(m
2
/s) 4.210
-10
Electrolyte density (kg/m
3
) 998
Electrolytic conductivity (S/m) 35
Kinematic viscosity, v (m
2
/s) 1.0910
-6
Kinetic parameters for copper deposition
Tafel slope, b
C
(V) 0.0525
Exchange current density, i
0
(A/m
2
)
-0.537
Cathode
Anode
Inlet
Outlet
Figure 2. Velocity distribution between the anode and cathode (inlet velocity =0.2 m/s).
The electrolyte solution generally flows between two planar and parallel electrodes.
Considering the order of magnitude of the electrolyte velocities, the flows are generally turbulent. It is
considered that the cathode is a sink of ion transport as the deposit parallel to the anode. Under these
conditions, the modeling for the electrochemical and mass transport phenomena occurring in the cell
can be coupled in the CFD platform.
In the model, forced convection by inlet electrolyte is considered. The velocity contours that
are flowing at an inlet velocity of 0.2 m/s are shown in Figure 2. From this, the localized velocity
values are predicted between the electrodes. The electrolyte velocity profile in a rectangular channel
cell under a pressure-driven hydrodynamic flow shows parabolic patterns with a wide plateau. The
maximum velocity was found at the region between the electrode and center of the channel, because of
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12339
the electrodes projecting out over the channel. The velocity was almost zero at all of the channel walls.
However, the fully developed parabolic profile patterns were not found at the inlet or outlet region
within the channel.
In this study, we modeled the stationary flow-assisted mass transport that controls the electrode
reaction rates in an electrochemical system using a CFD based electrochemical simulation approach.
Hence, it is necessary to know the concentration distribution of electrolyte ions in the vicinity of the
electrode surface at various flow velocities, which preludes using the coupled transport equation for
convective diffusion. To develop a comprehensive modeling approach, we focused our attention on the
deposition of copper at the cathode in this simulation. A concentration sink flux equivalent to the
current density was applied at the cathode.
0.00000 0.00025 0.00050 0.00075 0.00100
0
10
20
30
40
50
60
0.0000
0.0002
0.0004
0.0006
0.0008
0.0010
C
o
2
+
c
o
n
c
e
n
t
r
a
t
i
o
n
(
m
o
l
/
m
3
)
Distance from cathode (m)
Inlet velocity (m/s)
0.1
0.3
0.5
Concentration
Convection
F
l
u
x
(
m
o
l
/
m
2
s
)
Diffusion
Figure 3. Concentration and mass transport (convection and diffusion) profiles close to the cathode
with three electrolyte flow conditions (0.1, 0.2 and 0.3 m/s).
During electrolysis, cations (Cu
2+
) have to be transported from bulk electrolyte to the cathode
surface. In general, this mass transport occurs by diffusion, convection, and migration. Close to the
electrode surface, the primary mass transport process is diffusion. At an electrolyte region near the
cathode, the diffusion flux is the dominating transport mechanism, while the convection is the
dominant flux in the bulk electrolyte, as shown in Figure 3. The copper ion concentration decreases
with a decreasing distance from the cathode owing to its ion consumption with the electrode reaction.
An increasing flow velocity results in an increase in surface concentration.
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12340
Cathode
Anode
Inlet
Outlet
Figure 4. Diffusion boundary layer thickness at the cathode (i
app
=100 A/m
2
, inlet velocity =0.2 m/s).
Cathode
Anode
Inlet
Outlet
Figure 5. Surface concentration distribution at the cathode and side channel wall (i
app
=100 A/m
2
,
inlet velocity =0.2 m/s).
The distribution of the diffusion boundary layer thickness was simulated at the cathode surface,
as depicted in Figure 4. A higher thickness value of the diffusion boundary layer gives rise to a
decreased surface concentration as shown in Figure 5.
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12341
3.2 Mass transport-coupled electric field analysis
Cathode
Anode
Inlet
Outlet
Figure 6. Electric potential distribution between the anode and cathode (i
app
=100 A/m
2
, inlet velocity
=0.2 m/s).
Cathode
Anode
Inlet
Outlet
Figure 7. Electric field distribution between the anode and cathode (i
app
=100 A/m
2
, inlet velocity
=0.2 m/s).
Metal ion reduction at the cathode yields a decrease in the ion concentration, which reduces the
electrode reaction rate. Although the current distribution at the anode as a counter electrode will be
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12342
non-uniform under a real situation, this is found to have a negligible effect on the rate of the cathode.
Accordingly, the simulation approach using a fixed anode potential shows that (for the same current)
the cathodic current distribution is negligibly affected [12]. This approach allows the average current
density to be fixed. Based on the conservation of charge, the numerically simulated average current on
the cathode should be equal to the total current on the anode.
If the deposition rates at the cathode side are focused on the modeling approach, the rate of the
anodic reaction can be assumed reversible under a constant applied current condition. This assumption
is the ideal case of no surface overpotential at the anode. Figure 6 shows the electric potential
distribution patterns (cross section view) coupled with the cathode overpotential through the
electrolyte region between the anode and cathode. Since herein it is the assumed that the anode is
grounded as 0 V, the potential at the cathode can be calculated from the given flux-out (current density
from Tafel kinetics) using mixed boundary conditions. Owing to the electric conductivity of the
electrolyte, there is a potential increase toward the grounded anode. This is the ohmic potential drop,
which is the loss associated with resistance to the electron transport in the electrolyte region. A
simulation of the electric field between the electrodes is also shown in Figure 7. Spatial current
densities are locally proportional to theses gradients of potential. These results show the case of a
coupled computation with the concentration gradient and surface overpotential.
3.3 Local current density and overpotential
Cathode
Anode
Inlet
Outlet
(a)
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Cathode
Anode
Inlet
Outlet
(b)
Figure 8. Local overpotential (a) and current density (b) at the cathode surface (i
app
=100 A/m
2
, inlet
velocity =0.2 m/s).
In addition, the model can provide many more details on the mass transport controlled
electrochemical characteristics occurring in an electrowinning cell. An increased diffusion boundary
layer leads to a higher overpotential in this electrode region. Accordingly, an increased inlet velocity
condition results the decreased overpotential owing to a smaller diffusion boundary layer thickness. In
Figure 8, the distribution of overpotential (a) and local current density (b) throughout the cathode
surface are provided for the case of a current density of 100 A/m
2
and an inlet velocity condition of
0.2 m/s. The effects of electrolyte concentration are taken into account in this simulation. It was found
that a higher local overpotential arises from a lower ionic concentration at the electrode surface. Under
this condition, there is not a large potential drop in the electrolyte bulk. Thus the diffusion transport
has a dominant control factor at the electrode surface. It is shown that the increased inlet velocity
condition gives a decreased surface overpotential and has less of an effect on the ohmic drop. This is
evident from the modified Tafel kinetics, which is a function of the overpotential and surface
concentration, as in Equation (4). Accordingly, to maintain the given current density, a higher
overpotential is necessary for the compensation of the ionic reactant depletion.
The diffusion boundary layer () is defined in the literature [17]. Once we know the local
diffusion boundary layer, the current density can be locally estimated according to Ficks law, as in
Equation (8):
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12344
o
s bulk
C
x
C
C C
zFD
x
C
zFD i
~ |
.
|
\
|
c
c
=
=0
(8)
Since Equation (8) serves to define the diffusion boundary layer thickness, it can be obtained
from the local concentration gradients in the direction normal to the electrode surface. Close to the
cathode surface, the primary mass transport for an electro-transport process is diffusion control. Local
current density can be approximated according to Ficks law as expressed in Equation (8). Once a
concentration gradient in the direction normal to the cathode is obtained from the mass transport
simulation, the diffusion boundary layer thickness () is able to be estimated from the definition as the
intersection between the tangent at the concentration distribution and concentration of the bulk
electrolyte.
0.00 0.01 0.02 0.03 0.04
-200
-150
-100
-50
0
0
100
200
300
400
500
0
10
20
30
40
50
Local current density
Diffusion boundary layer thickness
Surface concentration
Cathode current density: 100 A/m
2
Inlet velocity: 0.2 m/s
L
o
c
a
l
c
u
r
r
e
n
t
d
e
n
s
i
t
y
(
A
/
m
2
)
Distance along the cathode center line (m)
Simulation
Approximation
D
i
f
f
u
s
i
o
n
b
o
u
n
d
a
r
y
l
a
y
e
r
t
h
i
c
k
n
e
s
s
(
m
)
S
u
r
f
a
c
e
c
o
n
c
e
n
t
r
a
t
i
o
n
(
m
o
l
/
m
3
)
Figure 9. Simulation and approximated local current density along the center line of cathode (i
app
=100
A/m
2
, inlet velocity =0.2 m/s).
Figure 9 shows a comparison of the local current density between the simulation and
approximation from the diffusion boundary layer thickness for an applied current density of 100 A/m
2
and inlet velocity condition of 0.2 m/s. In this figure, the local current densities were drawn on the
center line along the cathode surface. The approximated local current density indicates a fairly good
agreement with the simulation results along most of the cathode surface. However, as an
approximation was considered on the concentration gradient along the normal direction to the cathode,
a slight difference was found in the vortex region of the electrolyte facing the protruded cathode.
Figure 10 shows a variation of current density as a function of overpotential based on the
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12345
average values of the diffusion boundary layer thickness throughout the cathode. The curves were
obtained by the relationship between the current density and overpotential with the values of the
diffusion boundary layer thickness estimated from the concentration profile for various inlet velocities.
The simulated polarization curves clearly show the charge transfer, mixed (charge transfer and mass
transport) and mass transport controlled region.
-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0
-100
-75
-50
-25
0
Charge transfer control region
Mass transport control region
0.5 m/s
0.4 m/s
0.3 m/s
0.2 m/s
Inlet velocity
L
o
c
a
l
c
u
r
r
e
n
t
d
e
n
s
i
t
y
(
A
/
m
2
)
Overpotential (V)
0.1 m/s
Figure 10. Local current density as a function of overpotential at various inlet velocities (0.1-0.5 m/s).
In the charge transfer controlled region, the electrolyte turbulence has little effect on the
voltage drop. In this simulation condition, the polarizations with a lower exchange current density
would play a significant role in the total losses causing a potential drop from the ideal voltage. It was
simulated that the overpotential contributed to most of the cell potential under this demonstration
condition.
The above simulations provide a good illustration of the capabilities of the present modeling
approach. The proposed CFD model was shown to be able to predict not only the convective diffusion
behavior of the ionic reactants but also the mass-transport limited electrochemical polarizations. It was
found that the flow characteristics of the electrolyte influenced the diffusion-limited current density
and electrowinning deposit. To evaluate these influences, a coupled approach of the multiphysics
simulation for the flow and ion transport is necessary. In addition, more detailed analyses and
benchmarking tests are desirable to fully investigate a validation study.
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4. CONCLUSIONS
This study demonstrated a modeling approach based on the full coupling of electrochemical
reactions with a mass transport of ionic species using a commercially available CFD platform. An
analysis was carried out for the case of copper electrowinning from a flowing cupric acid electrolyte
through the simplified channel cell with planar and parallel electrodes. The demonstrations presented
here have focused only on copper deposition during steady-state electrolysis. A finite volume
numerical scheme based the CFD technique was successfully adapted to simulate 3-dimensional
behaviors of the electrochemical cell. The CFD model was shown to be able to predict not only the
convective diffusion behavior of the ionic reactants but also the mass-transport limited electrochemical
polarizations. This comprehensive model provides valuable information on the transport phenomena
inside an electrolytic cell such as the ion concentration, electric potential and local current density
distribution under a given current driven condition. Future work will focus on the benchmarking of this
model to validate with a proven electroplating system that controls the fluid dynamics and mass
transport conditions.
ACKNOWLEDGMENTS
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the
Korea government (MSIP).
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