long, 2 cm wide and 0.

3 cm thick, which were attached to The geometric dimensions of RCE-PP were determined
the reactor on the
wall and connected to each other, were used as anodes. basis of RCE-LC geometric dimensions employed in the
The previous
experimental study on macro-electrolysis of Cu(II) works [1,6]; the dominant similarities were obtained using
recovery was dimensionless geometric correlations that involved the
performed in a pilot plant RCE reactor (RCE-PP) of 10 L new volume
capacity, operation, as well as length and area characteristics of
built using the methodology proposed here (Fig. 1). The the
RCE-PP electrodes (Eqs. (2)–(5)).
is equipped with: (a) rotating cylinder of S316 stainless VR =
steel as
cathode with a 12 cm diameter and 21.12 cm effective _L(r2
2
height, (b)
−
six plates of DSA (dimensional stable anodes) made of
RuO2/TiO2, r2
1 ) (2)
whose width and thickness were 4 cm and 0.3 cm,
respectively; r2 −
anode plates were connected to power supply by means r1
of screws. r1
The cathode was rotated with a (c) variable revolution =
engine
controller (Yaskawa J1000TM). The sulfate saturated 1.33 (3)
electrode, Lef
SSE (Hg/HgSO4/K2SO4(sat)) was used as reference 2r1
electrode. The =
model solution mimicking a rinsing electroplating solution
1.76 (4)
was
prepared with analytical grade reactants and deionized Aef =
water Milli- 2_r1Lef (5)
QTM. The Cu(II) concentration was 18.8 mM in 1 M 264 F.J. Almazán-Ruiz et al. / Electrochimica Acta 77 (2012) 262– 271
H2SO4. The Fig. 1. Rotating cylinder electrode electrochemical reactor pilot plant
macro-electrolysis was carried out under galvanostatic (RCE-PP). (a) Schema of RCE-PP, (b) schema of RCE-PP top view
and (c) RCE-PP photography.
control: where VR is the reactor volume, r1 is the internal radius or
48.71, 56.08 and 70.54 mA cm−2. These values were cathode
evaluated from radius (cm), r2 is the external radius or reactor shell (cm),
the correlation JL = Lef
(ziFDC/d)0.014Re0.91Sc0.356 reported by Rivera and Aef are the effective longitude and area of the
et al. [6,12] (see Section 3.5), using three rotating electrodes (cm).
velocities (600, The RCE-PP reactor volume was fixed at 10 L; the other
700 and 900 rpm). The power supply used was variables
DynaPowerTM connected are unknown and they are found by solving equation set
to midi LOGGER GL200ATM interface, whereas the data (2)–(5).
acquisition was carried out by means of GL200-800-APS In the present work the counter-electrode thicknesses
Ver 1.01. were not
The Cu(II) concentration depletion in the liquid bulk as a taken into account in order to save costs in the
function construction of the
of time was followed by atomic absorption new RCE-PP. Therefore, the thicknesses of counter-
spectrophotometer electrodes were
(VarianTM Model 220 FS). similar to those used in RCE-LC.
3. Scale-up method for a RCE bench scale 3.2. Hydrodynamic similitude
electrochemical The hydrodynamic study under turbulent flow on the
reactor liquid
The strategy used to scale-up RCE-LC to RCE-PP bulk within RCE reactor was approximated using the
consisted of four Reynoldsaveraged
issues that were considered the “dominant criteria” in Navier–Stokes (RANS) equation (Eq. (6)), where the
RCE reactor: so-called Reynolds stresses are expressed in terms of
(a) the new geometric dimensions of RCE-PP; (b) the turbulent
similitude viscosity (_T) and the gradient of mean velocity. The
of hydrodynamic study with computational fluid dynamics turbulent
(Comsol viscosity is specified by Eq. (7) according to the standard
Multiphysics 3.5a) and dimensionless numbers, i.e. k–ε turbulence
Reynolds model.
and Taylor numbers; (c) the similitude of mass transport (_u
study
·
with computational fluid dynamics, and (d) validation of
scale-up ∇)u
methodology with experimental data.
3.1. Geometric dimensions of the pilot scale reactor =
 To establish the hydrodynamic similitude between the
−∇P
RCELC
+ and RCE-PP, the dimensionless velocity profile
calculated
∇ in this study and the corresponding Taylor numbers are
· compared
as a function of radius ratio ((r
(_
−
+ r1)/(r2 −
_T )(∇u r1)) in both
scales.
+ 3.3. Mass transport similitude
∇uT ) Once the hydrodynamics in the RCE has been
established, its
+ effect on the mass transport rate has to be determined in
F (6) order
to evaluate the similitude between both scales of RCE
_T =
and finally
_C_ Fig. 2. Schema of the RCE reactor showing the geometry of the 2D
k simulation
domain and the conditions near the RCE and counter-electrode walls.
ε For the sake
(7) of clarity only one of the six counter electrodes is depicted.
In these equations, u is the average of velocity vector, P F.J. Almazán-Ruiz et al. / Electrochimica Acta 77 (2012) 262– 271 265
is the the comparison against experimental data. Therefore, the
average pressure, _ is the viscosity, _T is the turbulent study of
viscosity, F the mass transport of Cu(II) from the bulk to the RCE
is any external force, _ is the density, C_ is a turbulence electrode
model constant, surface was carried out using the approach reported
previously [1],
k is the turbulent kinetic energy and ε is the turbulent
as follows.
energy
In electrochemical system with no chemical reaction in
dissipation rate. Principles and development of RANS
the bulk
equations as
solution and under turbulent flow, the material balance of
well as the k and ε transport equations are given charged
elsewhere [30]. species i is given by Eq. (9), where the concentration and
The model is applicable under turbulent and isotropic velocity
flow conditions, fluctuation terms have been grouped into the so-called
for that reason the near-wall region is inaccessible for the turbulent
model due to the decrease in velocity when approaching
a solid diffusion term (_·Di,T_Ci) of a Reynolds-averaged mass
surface. One way of solving this problem is by using wall transport
functions equation, analogous to RANS equation.
[30–32], which circumvents the need to solve the ∂Ci
transport ∂t
equations in this region. The wall function based on the =
universal
velocity distribution, given by Eq. (8), is used instead of −u ·
no-slip
boundary condition at the wall for solving Eq. (6).
∇Ci +
u+ = ziF∇
5.5 ·
+1
(umiCi∇˚)
_
ln y+ (8) +
where u+ is a dimensionless velocity (=(u ∇
−
·
uw)/(_w/_)1/2), u the
velocity, uw the velocity of the wall, _w the wall shear (Di +
stress, _ the Di,T )∇Ci (9)
density, y+ the dimensionless distance to the wall
where Ci is the average concentration of electroactive
(=y_(_w/_)1/2/_),
species i, t is
y the distance to the wall and _ the von Karman the temporal variable, zi is the charge number of the ion,
constant. A schema F is the
of the RCE reactor is shown in the Fig. 2, where is
Faraday constant, umi is the ionic mobility, ˚ is the
represented the
electric potential,
geometry of the 2D simulation domain and the regions
Di is the diffusion coefficient and Di,T is the turbulent
near to walls
diffusion
of RCE and counter-electrode.
coefficient. The first term in the right-hand side of Eq. (9) −_Di
represents 0.3_T
the ion transport by convection due to the motion of the
fluid with
_
the average velocity u. The second term corresponds to ScT∞
migration ___−1
of charged species i due to the electric field. The last (11)
term describes where ScT∞ = 0.85.
the movement of specie i by molecular and turbulent In the model here proposed, Eqs. (10) and (11) might be
diffusion. applied
Eq. (9) must be solved simultaneously with charge only to the bulk fluid region. In the region close to the
balance wall, a
and electroneutrality equation in order to determine the dimensionless concentration distribution C+ can be
potential. considered. The
The problem is simplified, assuming that electroactive following distribution was adapted to the mass transport,
species are where
present in small amounts and a supporting electrolyte is Eq. (12) corresponds to the laminar sublayer and Eq.
added to (13) to the
electrolytic solution diminishing the effect of electric field. turbulent layer.
Then, C+ =
the migration term of Eq. (9) can be neglected and the
following Sc y+ (12)
equation is obtained. C+ =
∂Ci ScT
∂t _1
= _
−u · ln y+ +
∇Ci + 5.5
+
∇
Pc
· _
(Di + (13)
where C+ is defined as:
Di,T )∇Ci (10)
C+ =
Eddy diffusivity or turbulent diffusivity can be evaluated
(Ci,w −
considering
analogy between transport phenomena. If eddy Ci)C1/4
diffusivities of _ k1/2
heat and mass are assumed to be equivalent to each Ji,w
other (˛T = Di,T), (14)
the respective dimensionless turbulent numbers, PrT and Ci,w is the fluid concentration on the solid surface, Ci is
ScT, are the concentration
equal and Kays–Crawford model [34] can be used in at a distance y+ from the wall and Ji,w is the diffusion flux
terms of ScT in the near-wall region. The term Pc takes into account
according to Eq. (11). the change of
mass transfer resistance from the viscous sublayer to the
ScT =
turbulent
_ layer and can be calculated with the following empirical
1 equation
2ScT∞ that has provided good results in mass transfer
simulation [1,33].
+ 0.3 _
Pc
ScT∞
=
_T
_Di A
− __
_ Sc
0.3 ScT
_T _3/4
_Di −
_ 1
_ _
1 (15)
where A is a constant whose value (A = 9.24) has been
−
determined
exp
from experimental data of heat transfer on smooth pipes.
_ In the case
of copper recovery in a RCE-LC the value of A has been Taylor number in both scales. The Taylor number was
determined obtained by
(A = 2.9) [1]. This value of the constant A takes into means of Eq. (16)
account the Ta
enhanced mass transport as compared to smooth pipes
=
caused by
the dendritic metal deposit. Re1/2
The boundary conditions used for solving Eq. (10) are: (i) _
wall r
functions (Eq. (13)) on the surface of the RCE and (ii) −
impermeable r1
boundary in all other walls (n·(−Di_Ci + uCi) = 0), where n r2 −
is the r1
vector normal to the surface of the RCE (see Fig. 2). _
3.4. Computational strategy for process simulation (16)
Transport equations were solved numerically by finite where the Re number is defined by (Eq. (17))
elements
Re
using commercial software (Comsol Multiphysics 3.5a).
Due = u_d
to higher computer resources demanded by turbulent _
flow simulations (17)
as the reactor size increases, the transport phenomena where u is the angular velocity of the rotating electrode,
of process simulation of Cu(II) recovery were carried out cylinder
in 2D diameter d = 2r1, _ and _ are the density and viscosity of
instead of a 3D simulation domain, since the movement the liquid
of the fluid phase, respectively. The next step was to determine limit
is mainly in the azimuthal direction with no important current
dependence density applied to RCE-PP in order to carry out macro-
of velocity profile on axial direction (z) [1]. electrolysis
The hydrodynamic model was solved in steady state and for mass transport similitude validation. The limit current
the density
results obtained were stored through the option available 266 F.J. Almazán-Ruiz et al. / Electrochimica Acta 77 (2012) 262– 271
in the Table 1
program, in order to be used in the mass transfer model. Characteristic dimensions used in RCE bench scale and RCE-PP.
Dimension characteristics RCE bench scale RCE-PP
Afterwards, Internal diameter (2r1)/cm 3.8 12
the transient diffusion-convection equation (Eq. (10)) External diameter (2r2)/cm 8.8 28
along Effective high (Lef)/cm 6.7 21.12
with Kays Crawford model (Eq. (11)) and mass transport Effective area (Aef) 80 796.2
Anode thickness/cm 0.3 Hypothetic/actual
wall functions
3.3/0.3
given by Eqs. (13)–(15), were solved using the results of [(r2 −
the r1)/r1] 1.33 1.33
hydrodynamic calculation: (i) the time-averaged velocity Lef/2r1 1.76 1.76
to evaluate was calculated using the following correlation reported in
the convection term in Eq. (10), (ii) the turbulent viscosity [12] for
to a RCE bench scale reactor.
obtain the turbulent diffusivity through Eq. (11), and (iii) JL = ziFDiC
the eddy
d
kinetic energy required in Eq. (14) for evaluating Ji,w from
the wall 0.014Re0.91Sc0.356 (18)
function. Eq. (18) is useful because it incorporates geometry,
Upon verifying numerical solutions reached at different hydrodynamics,
values and mass transport coefficients in an implicit way, as well
of y+ and mesh size, the y+ value and mesh size were as the electrochemical reaction parameters, where, JL is
fixed for solving the hydrodynamics. The time dependent the limit
mass current density (A cm−2), z is the electron number
transport problem was solved using the same y+ value transfer in the
and electrochemical reaction, F is the Faraday constant
mesh size and a time step of 1 s. The following (95485 C mol−1),
properties were Di is the diffusion coefficient of the electroactive species,
used in the simulation: _ = 0.001 kg m−1 s−1, _ = 1059 kg C0 is the
m−3 and initial concentration of the electroactive species (mol cm−
3), d is the
Di = 7.2
diameter of the rotating electrode (cm); Re is the
× Reynolds number
10−10m2 s−1 [1]. (Eq. (17)) and Sc is the Schmidt number (_/_D). The
3.5. Validation of scale-up methodology constant
3.5.1. Limit current density for RCE-PP values a = 0.014, b = 0.91, and c = 0.356 are associated
To validate the scale-up it is necessary to keep constant with shape
the and cell dimensions, hydrodynamic and mass transport
regimens,
respectively. F.J. Almazán-Ruiz et al. / Electrochimica Acta 77 (2012) 262– 271 267
4. Results and discussion Fig. 5. Taylor number as a function of dimensionless radial position in
the RCE bench
4.1. Characteristic dimensions of both RCEs scale and RCE-PP with hypothetical counter-electrode thicknesses
The characteristic dimensions found for RCE-PP through (solid line), RCEPP
equation with actual counter-electrode (dashed line); (a) in front of the reactor
set (2)–(5) are shown in Table 1, together with the vessel wall
(between two plates) and (b) in front of the counter electrode.
geometric
of a nearly regular hexagon, while in the pilot plant
similitude in both scales. These similarities were the
reactor the
interelectrode
contour lines exhibit more complex pattern. A greater
gap ((r2 − spacing
r1)/r1) and length–diameter cathode ratio between cathode and counter electrode and small arc
(L/2r1) keeping the same values with a different length of the
magnitude of 10 L RCE-PP reactor give rise to the formation of a local
characteristic dimensions used in RCE bench scale and maximum in
RCE-PP. front of each counter electrode. This is because the
4.2. Velocity profile similitude thickness of the
Fig. 3 shows the velocity field obtained in the simulation counter-electrode was not scaled-up proportionally with
at two different scale reactors and the same Taylor respect
number to RCE bench scale dimensions. When the thickness
(Ta = 7.84 proportional to
× RCE bench scale dimensions is taken into account, as
105); Fig. 3a corresponds to the RCE bench scale was presented
in Fig. 3, the flow patterns are similar in both RCE
reactor (ω = 91 rpm) and Fig. 3b to RCE-PP with a
reactors.
hypothetical
In order to show more clearly how similar are the
counter-electrode thicknesses (3.3 cm) scaled-up
hydrodynamic
proportionally
behaviors in both scales, Fig. 5 shows the values of Ta
with respect to RCE bench scale dimensions (ω = 900 number as a
rpm). The function of the dimensionless radial position in the inter-
behavior of dimensionless velocity profile in both scales electrode
is very gap using the following expression (Eq. (16)).
similar; high velocity regions close to the rotating cylinder Ta
and
stagnant zones near the wall of the reactor vessel are =
clearly Re1/2
distinguished. It is important to consider that RANS _
equations
r
were solved from a distance ı of all walls (Fig. 2) so that
the −
velocity field within this small film is not shown in Fig. 3. r1
Fig. 4 shows the dimensionless velocity field simulation r2 −
results r1
of the RCE-PP with actual counter-electrode thickness _
(0.3 cm). As where “r” represents the radial position in the inter-
can be seen, the behavior of dimensionless velocity electrode gap.
profile is different Fig. 5a shows the Ta as a function of dimensionless
with respect to velocity profile obtained in both RCE radial position
bench scale in front of the counter electrode; meanwhile Fig. 5b
and RCE-PP with a hypothetical counter-electrode shows
thicknesses the Ta in front of the reactor vessel wall (between two
(Fig. 3). This demonstrates that despite both RCE plates). The
reactors operate solid line represents the Ta behavior of RCE bench scale
under the same Re and Ta number, the velocity field and RCE-PP
exhibits non with hypothetical counter-electrode thicknesses
identical behavior. On the other hand, the contour lines (overlapped), and
included in the dashed line represents the Ta behavior of RCE-PP
Fig. 4 show a deformation of the concentric circles with actual
pattern caused counter-electrode. In the first case, the velocity
by the presence of the six plate counter electrode. In the decreases continuously
bench along the r direction and in the second, a plateau
scale reactor the velocity field contour lines show the between
formation 0.3 and 0.85 of the dimensionless radius is formed. The
Fig. 3. Simulation of the velocity field in the RCE with 6 counter
electrodes at Taylor
profiles of
number of 7.84 the Ta number of the RCE-PP with hypothetical counter-
×105. (a) RCE bench scale and (b) RCE-PP with hypothetical electrode
thicknesses of the counter-electrode (3.3 cm). thicknesses follow the same trend of the profiles of the
Fig. 4. Simulation of the velocity profile in the RCE-PP with actual RCE bench
counter electrodes scale (overlapped). On the other hand, the profiles of the
(0.3 cm) at Taylor number of 7.84 Ta number
×105.
of the RCE-PP with actual counter-electrode closely represent the simulation results of the RCE bench scale
follow the and RCE-PP
profiles of the bench scale unit with a minor difference, with hypothetic counter-electrode thicknesses
despite the (overlapped lines);
lack of scale-up proportionality with regard to counter- dotted lines show the simulation results of the RCE-PP
electrode with actual
thickness. counter-electrode.
Although the proportionality of the counter-electrode All simulations were carried out using the same value of
thickness the
was not preserved during scale-up procedure, the A constant (A = 2.9) reported previously [1]. This value
present methodology takes into
considered that preserving the electro-active area in both account the increased surface roughness of the
scales was more important; such hypothesis is confirmed electrode, caused by
in the deposition of copper, compared with the value reported
next section. (A = 9.24)
4.3. Mass transport field similitude for heat transport in smooth pipes [1]. The simulation
Fig. 6 shows the simulation results of the hydrodynamic results
effect agree very well with experimental data in both reactors
on the dimensionless concentration field in the RCE until a
bench scale dimensionless concentration of C/C0 = 0.4, after which
(Fig. 6a), RCE-PP with hypothetical counter-electrode the simulated
thickness concentrations are greater than the experimental ones.
(Fig. 6b), and RCE-PP with actual counter-electrode (Fig. The
6c) at faster experimental copper depletion rate is expected
Ta = 7.84 considering
×105, C0 = 18.8 mM, and t = 1800 s. In all cases, contour that, under galvanostatic control, the current applied
becomes
lines near to RCE zone are concentric (Fig. 6) following
greater than the limiting current of copper reduction as
the same
the electroactive
hydrodynamic pattern as showed in Fig. 3a, b and 4.
species concentration decreases. The excess of current
In Fig. 6(a) and (b), the dimensionless concentration field
is
are
used by secondary side reactions, such as the reduction
practically similar, however, the dimensionless
of protons;
concentration field
gas bubbles produced a complete change in
in Fig. 6(c) shows minor deviations with respect to RCE
hydrodynamics and
bench scale.
mass transport, aspects not included in the model.
The main differences are observed near the counter-
The empirical constant A = 2.9, used previously to fit
electrode; in
experimental
this region, the counter line for RCE bench scale forms a
data of mass transfer in copper recovery in a RCE bench
hexagon,
scale
while in RCE-PP with a hypothetical counter-electrode
[1], in the present study shows to be able to predict the
thicknesses
copper
it presents a minor deformation (practically a concentric 268 F.J. Almazán-Ruiz et al. / Electrochimica Acta 77 (2012) 262– 271
circle), Fig. 6. Simulation of the dimensionless concentration in the RCE
which is due to minor counter-electrode thicknesses. On reactors with
the other 6 counter electrodes at Ta = 7.84
hand, near the RCE zone, the counter lines are the same ×
in both 105. (a) RCE bench scale, (b) RCE-PP with
hypothetical counter-electrode thicknesses (3.3 cm), and (c) RCE-PP
cases.
with actual
In order to show the similarity of mass transport behavior counter-electrode (0.3 cm).
in Fig. 7. Experimental evolution of the dimensionless concentration as a
both reactors, Fig. 7 exhibits the experimental evolution function of
of dimensionless electrolysis time ((a) Ta = 5.22
concentration as a function of electrolysis time compared ×
with simulation result at different Ta numbers ((a) Ta = 105, (b) Ta = 6.09
5.22 ×
105, (c) Ta = 7.84
×
×
105, 105). Symbols
(b) Ta = 6.09 represent the experimental data. _ RCE bench scale;
× _
RCE-PP. The lines represent
105, (c) Ta = 7.84
the simulation results. – RCE bench scale and RCE-PP with
× hypothetical counterelectrode
105). Full symbols and empty thickness (0.3 cm) (overlapped),··
symbols correspond to experimental data of copper ·
concentration ·
obtained from galvanostatic electrolysis in RCE bench RCE-PP with actual counter-electrode
scale and thickness (3.3 cm).
RCE-PP with actual counter-electrode, respectively. The concentration decay in a larger reactor (32 times the
solid lines volume and
10 times the cathode area). the lines represent those determined by simulation: (–
These results mean that upon varying the reactor size RCE bench
and using scale;.–. RCE-PP).
three different rotation velocities, the changes in The mass transport coefficient in copper recovery follows
hydrodynamics the
are taken into account correctly and mass transfer same trends with a deviation of 0.34% for RCE bench
resistance is scale and
modified in accordance with the model proposed. In this RCE-PP (Fig. 8) confirming the similarity in mass
model, transport. The
the mechanism of Cu(II) transport towards RCE takes concordance between experimental mass transfer
place in different coefficient and
regions. In the bulk region for y+ greater than 22, the those obtained with simulation in both reactor scales
transfer (RCE bench
takes place principally by turbulent diffusion; and in the scale and RCE-PP) at three hydrodynamic conditions
near-wall (Taylor numbers)
region, turbulent contribution slowly decreases as the show that the model takes into proper account the effect
distance to of
F.J. Almazán-Ruiz et al. / Electrochimica Acta 77 (2012) 262– 271 269 the hydrodynamics in the mass transport.
Fig. 8. Experimental mass transfer coefficients (Km) and those 4.4. Current efficiency
determined by simulation
as a function of Taylor number. Experimental data: _ RCE bench scale Fig. 9 shows the current efficiency as a function of
and electrolysis
_ RCE-PP. Simulation results: – RCE bench scale;.–. RCE-PP with time at different Taylor numbers, 5.22
actual counterelectrode ×
thickness.
the electrode diminishes until the transfer takes place by 105, 6.09
molecular ×
diffusion in the viscous sublayer. The magnitude of 105, and
turbulent 7.84
diffusivity and thicknesses of different layers, which ×
determine
mass transfer rate, depend on the hydrodynamics 105. These curves were obtained by the following Eq.
prevailing in (20).
each region. Thus, the constant A operates as a fitting ϕ
parameter = zF_CVr
to amplify or diminish the local mass transfer flux for Qt
each hydrodynamic (20)
condition; for this reason, in the absence of additional Fig. 9. Variation of the current efficiency in the pilot scale reactor with
phenomena, such as hydrogen gas evolution from the electrolysis
cathode, for time at different Taylor numbers (a) Ta = 5.22
example, one single value of A can be sufficient to ×
represent the 105, (b) Ta = 6.09
decay of concentration at different hydrodynamic ×
conditions at the 105, (c)
Ta = 7.84
rotating cylinder.
×
Finally, to observe the similarities in the mass transport
105.
from
the experimental and simulated data to different Taylor where _C = (C0 −
numbers, Ct) is the concentration difference (mol cm −3) and
the mass transport coefficient (Km) was calculated using Qt is the total charge in the electrolysis defined as:
Eq. (19) Qt =
and considering that the deposition of copper follows a t
first-order 0
kinetics. I(t)d(t) (21)
∂Ci,av The current efficiency diminishes as electrolysis times
∂t increases
(Fig. 9a–c), this behavior is typical for electrolysis
= KmARCE performed in
VR a galvanostatic mode, since the current applied becomes
Ci,av (19) greater
where Ci,av is the average concentration of the than the limiting current of copper reduction as the
electroactive species electroactive
in the reactor at a determined time, Km the overall mass species concentration decreases. The excess of current
transfer is used by
coefficient, ARCE the surface area of the electrode and VR secondary side reactions, such as the reduction of
the protons; gas
reactor volume. In Fig. 8 the symbols represent the 270 F.J. Almazán-Ruiz et al. / Electrochimica Acta 77 (2012) 262– 271
experimental bubbles produced a complete change in hydrodynamics
and mass
mass transfer coefficients (_ transport. On the other hand, the electrolysis time where
RCE bench scale and _ RCE-PP), and the current
efficiency is near 100% raises as Taylor increases.
5. Conclusions basis of the three similarities described in the
A strategy was developed to scale-up a RCE reactor methodology lead
used for to a reactor design that fulfills the desired operational
copper recovery from rinse water of electroplating characteristics.
industry. Three Acknowledgements
issues were taken into account in the strategy: (1) the Francisco J. Almazán-Ruiz acknowledges the financial
geometric support provided by ICyT-DF, México through
similitude between the laboratory unit and the pilot scale agreement:
of the RCE ICyTDF/013/2009.
reactor where relevant geometrical ratios (interelectrode Appendix A. Nomenclature
gap/RCE Description Symbol
diameter and RCE length/RCE radius) were kept; (2) the Dimensionless numbers
Taylor number Ta
hydrodynamic Reynolds number Re
similitude evaluated through CFD simulation where the Schmidt number = _/(_Di) Sc
velocity profile in the RCE-PP reactor was identical to Sherwood number Sh
that in the Turbulent Schmidt number = _T/(_Di,T) ScT
bench scale RCE reactor (although minor differences in Description Symbol Units
Internal diameter or diameter of the RCE 2r1,d m
the flow External diameter 2r2 m
pattern were revealed by velocity contour lines); and (3) Radial coordinate r m
the mass Effective high Lef m
transport similitude shown in the CFD simulation where Effective area Aef m2
Energy consumption Econ KW h m−3
the copper
Initial concentration of the electroactive species Ci,0 mol cm3
concentration decay curves exhibited the same behavior Dimensionless concentration
in =
both scales of the RCE reactor. The simulations were (Ci,w −
performed Ci)C1/4
with a widely used fluid flow model (RANS equations, k– _ k1/2/Ji,w
ε turbulence C+ –
model and proper wall functions) and a mass transport Mass transfer flux at the wall Ji,w mol cm−2 s−1
Concentration of electroactive species Ci/Cu2+
model consisting of the averaged convection-diffusion
t mol cm3
equation, Average concentration of electroactive species Ci,av mol cm3
the Kays–Crawford equation in terms of the turbulent Concentration of electroactive species at the wall Ci,w mol cm3
Schmidt Constant of the _–ε turbulence model C_ –
number and the Launder–Spalding wall functions Reactor volume VR m3
Mass transfer coefficient Km m s−1
adapted to mass Limit current density JL mA cm−2
transport, using the same value of a fitting parameter (A Charge number of the ion zi –
= 2.9) of Ionic mobility umi –
the mass transport wall function reported previously for Diffusion coefficient Di m2 s−1
the bench Turbulent diffusion coefficient Di,T m2 s−1
Constant of the Kays–Crawford model ScT∞ –
scale RCE reactor. The simulation results showed the Factor of integration of resistances in near-wall
ability of the layers
model to predict successfully the experimental copper Pc –
decay in the Empirical constant of equation for Pc A –
Faraday constant F C mol−1
pre-pilot scale RCE reactor (error < 8%) until 80% of
Tangential velocity of the cylinder u m s−1
copper recovery. Dimensionless velocity = u/(_w/_)1/2 u+ –
A unique value of parameter A for simulating both scales Cartesian coordinates x, y, z –
is Dimensionless distance to the
a worthy fact, since this opens the possibility to apply the wall = y_(_w/_)1/2/_
proposed y+ –
Vector normal to the wall n –
methodology for scaling-up the RCE reactor to a pilot or Velocity vector u –
fully industrial size. In addition, the 2D simulation External force in Navier–Stokes equation F –
analysis (instead Time t s
of 3D simulation), used in this work, saves time and Pressure P Pa
Greek letters
computational
Turbulent thermal diffusivity ˛T –
resources allowing the efficient scale-up and optimization Turbulent energy dissipation rate ε –
study of the reactor. On the other hand, the electrolytic Electric potential ˚ V
removal of Density _ kg m−3
Cu(II) using the RCE pre-pilot scale generated the Viscosity _ kg m−1 s−1
desired copper Current efficient _ –
powders at high angular velocities and high mass Turbulent viscosity _T kg m−1 s−1
transfer rates, Turbulent kinetic energy k m2 s−2
with current density (JL) between 48 and 70 mA cm−2. von Karman constant _ m2 s−3
Angular velocity ω rad s−1
Results presented
Wall shear stress _w –
in this study show the pre-pilot-scale RCE to produce Shear stress _ –
similar Thickness of the boundary layer near the wall ı –
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