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Chemical Engineering Science 56 (2001) 63296336

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Gas bubble induced mixing in electrowinning baths


G. D. Rigbya; , P. E. Graziera , A. D. Stuarta , E. P. Smithsonb
a BHP

b Minera

Minerals Technology, P.O. Box 188, Wallsend NSW 2087, Australia


Escondida Ltd., Avda. Americo Vespucio 100 Piso 9, Las Condes, Santiago, Chile

Abstract
A method is proposed for assisting the commercial electrowinning of copper at current densities up to 600 A m2 . The method
utilises modi.cations to existing electrode feed manifolds to produce an air-electrolyte jet that mixes the cell contents and improves
the copper mass transfer by shrinking the Cu2+ concentration boundary layer around the cathode. A series of design criteria
for the modi.ed manifolds are proposed and utilised to select an appropriate ori.ce diameter (di = 2 mm). Experimental 4ow
modelling studies showed that acceptable mixing performance was possible for current densities in the range 400 600 A m2 ,
with appropriate air and electrolyte pressure operating parameters also provided. Pilot-scale electrowinning trials indicated that for
no air sparging, industrially unacceptable copper cathode was produced at current densities of 600 A m2 . However, the proposed
air-electrolyte system could produce high quality cathode at these conditions with little apparent evidence of unwanted dendrites
or nodules. ? 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Jetting; Bubble generation; High current density electrowinning

1. Introduction
The production of copper in electrowinning reactors
constitutes a major worldwide industry with hydrometallurgical plants generating product annually valued in
excess of US$ 7.5 billion. A signi.cant impediment to
productivity and e?ciency improvements in these electrowinning reactors is the presence of a boundary layer
of diminished Cu2+ ion concentration in the electrolyte
at the plating electrode surface. This boundary layer promotes unwanted dendritic growth, decreases the quality
of the deposited .nal metal surface, and ultimately prevents cell operation at more productive higher current
densities.
The use of gas sparging in electrowinning as an aid to
4uid mixing has been trialed by researchers for over one
century (e.g. see Farmer, 1885, for an original patent).
Subsequent to this patent, signi.cant investigations into
air enhanced copper electrore.ning were conducted by
various researchers, including those associated with Kennecott Copper (e.g. Harvey, Miguel, Larson, & Servi,
1975; Harvey, Randlett, & Bangerskis, 1978). In these
Corresponding author. Tel.: +61-2-4979-2465; fax: +61-24979-2465.
E-mail address: rigby.greg.gd@bhp.com (G. D. Rigby).

studies, air bubbles were introduced into the cell


using simple air-only pipe spargers (typical ori.ce diameter, di = 150 m, centre spacing = 10 mm apart), with
reported improvements in current density (and subsequent process e?ciency) of up to 10 times that obtained
during normal operation. Other fundamental studies
(Cooper & Mishra, 1987; Ettel, Gendron, & Tilik, 1975;
Janssen & Hoogland, 1970; Uceda & OKeefe, 1990)
investigated the eJect of rising gas bubbles on the thickness of the developed concentration boundary layer, and
found that the level of measured reduction in boundary
layer thickness and increase in mass transfer coe?cient
could be up to 10-fold. Some enhancements in operation
have also been attributed to the mixing eJect from gas
evolution at the counter electrode; however, these eJects
are generally restricted to the upper region of the plating
electrode (Ahmed & Sedahmed, 1988; Cooper, 1985).
Other agitation options, including high velocity jetting of
the electrolyte, mechanical wiping and the application of
ultrasonic energy may also be eJective, but suJer from
excessive energy demand, mechanical complexity, or
increased noise levels (SkarbH & Harvey, 1974; Uceda
& OKeefe, 1990).
In the described studies, it is clear that the most
eJective strategies for disturbance and minimisation of

0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 1 ) 0 0 2 3 3 - 0

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G. D. Rigby et al. / Chemical Engineering Science 56 (2001) 63296336

the concentration boundary layer rely upon enhanced


4uid mixing from rising and recirculating gas bubbles
that are purposefully introduced into the cell reactor in the
region around the base of the electrodes. Despite the potential shown by these methods for operational improvements in electrowinning of copper, the application of gas
sparging for improved mixing has been limited by clogging of the sparger ori.ces from precipitates formed in
the electrowinning baths, and maldistribution in the generated bubbles sizes (Tailoka & Fray, 1993). Moreover,
there still is little published information relating to the
successful practical implementation of the gas sparging
principles to current commercial electrowinning infrastructure.
In this study, a system is described that allows high
current density electrowinning based on modi.cation
of existing equipment and industrial practice. This system provides for the delivery of jets of fresh electrolyte
in conjunction with evenly sized air bubbles (bubble
diameter, db 0:51 mm) from a modi.ed version of
current operational equipment, thereby allowing the
implementation of high current density copper electrowinning. Initially, the design methodology for the
jetting system (based on three selection criteria for the
single-phase electrolyte 4ow) is described, highlighting
the modi.cations to the current cell 4uid distribution
manifold. Following this, the novel system for the simultaneous delivery of gas bubbles and electrolyte in
the form of two-phase jets from the existing manifold
into the reaction region around the cell electrodes is
described, and the suitability of the single-phase design
methodology is observed. Details of experiments are
given for the system, including optimal gas bubble and
jet penetration into the reactor as a function of nozzle
size, and applied pressure and 4ow rate of the gas and
liquid phasesand are summarised in terms of 4ow
maps indicating expected industrial operating windows.
Finally, a description is also given of pilot plant scale
electrowinning work that has demonstrated the use of this
gas bubble delivery for stable electrowinning operation
at signi.cantly increased current densities.
2. Theory
2.1. Design criteria for manifold system
The conventional design of the manifold system for
distribution of electrolyte into the cell is shown in
Fig. 1. The feed electrolyte is transported down through
the vertical feed pipe before splitting into the two horizontal arms of the distribution manifold. Along the length
( 6 m) of both arms of the manifold, outlet ori.ces may
be located at spacings corresponding to the positions for
the generation of jets on each side of the electrode (i.e.
120 jets for each manifold arm for a 60-cathode cell).

Fig. 1. Schematic representation of electrowinning cell showing feed


manifold.

Assuming 100% current e?ciency, the total 4ow of fresh


electrolyte into each cell, QT , is related to the mass 4ux
of copper MM , and the required strip of copper ions,
CS , depleted from the electrolyte during residence in the
cell, and is determined by the current density applied to
each cell, ID ; the number of cathodes, nC , and the surface
area per cathode available for plating, AC . Thus,
MM nC AC ID WM
=
;
(1)
QT =
CS
cI FCS
where cI is the ionic charge of the metal plating ion;
CS = Ci Co , and Ci; o are the inlet and outlet concentrations, respectively, of Cu2+ ; F is Faradays constant; and
WM is the molecular weight of copper.
The possible variables available for manipulation during the design of manifold ori.ces include the total electrolyte 4ow rate into each cell, and the ori.ce diameter, di .
However, examination of Eq. (1) shows that for a given
cell con.guration, plating ion species, current density rate
and electrolyte strip, QT for each cell is .xed. Therefore,
only di is available to modify the mixing intensity around
the cathodes. For this study, it is proposed that three
simpli.ed single-phase (electrolyte-only) criteria can be
identi.ed for the selection of optimal 4ow through the
manifold. These criteria are described as follows
Criterion 1. Minimisation of energy requirements for
electrolyte pumpingprimarily related to
the pressure drop across each manifold ori.ce.
Criterion 2. Maximisation of mixing across electrode
facecharacterised by the predicted jet centreline velocity, UM , at a penetration distance equivalent to half the total width of
the electrode, and is also important for the
subsequent generation and dispersion of gas
bubbles.

G. D. Rigby et al. / Chemical Engineering Science 56 (2001) 63296336

Criterion 3. Minimisation of the di;erence in individual


ori<ce =owrates, Qi , through each ori<ce
on the manifold legrelated interconnected
pressure drop between the 4ow in the main
manifold and the pressure drop through each
outlet ori.ce.
A description of the theory related to Criteria 13 is presented in the following section.
2.2. Minimisation of energy requirements for
electrolyte pumpingCriterion 1
The scale of operation in many industrial electrowinning plants means that energy required for the pumping of
electrolyte through the manifold can be a signi.cant component of total operating cost, since a single tankhouse
may comprise over 500 cells, each of which contains two
manifold arms, often around 60 cathodes, and potentially
four ori.ces per cathode (120 ori.ces per manifold arm
in this study). For design purposes the electrolyte 4ow
through each ori.ce can be expressed in terms of a standard ori.ce equation,


2OP d2i CC 2OP
=
;
(2)
Qorif = AO CC
e
4
e
where Qorif is the electrolyte 4owrate through the ori.ce,
CC is the ori.ce coe?cient; d2i =4 = AO is the area of the
ori.ce; OP is the pressure drop across the ori.ce; and e
is the electrolyte density, assumed constant. Rearrangement of Eq. (2) gives
 
2 
K1
e 4Qorif
1
= 4:
(3)
OPi =
4
2
Co
di
di
In Eq. (3), if K1 is a constant parameter for a .xed Qorif
and cell geometry, then the pressure drop is inversely
proportional to d4i .
2.3. Maximisation of mixing across electrode
faceCriterion 2
Design modelling of the extent of mixing across the
cathode face that results from the electrolyte jet issuing
from the ori.ce is assumed to be directly related to a jet
centreline velocity as predicted at the centre of the cathode. Detailed modelling of transient velocity pro.les in
the cells are possible through the use of modern CFD techniques; however, for the design purposes in this study,
a semi-analytical Tollmien solution for a round, uncon.ned jet (Abramovich, 1963) is thought to provide su?cient detail, and has been utilised. A number of diJerent
values of the empirically determined constants within the
Tollmien solution can be found in the literature; however,
Rajaratnam (1976) recommends the following for 4ow

outside the jet potential core.



di
Um Um d2i
=
= 6:3
for
UO
4Qorif
xm

6331


xm
5:8 ;
di

(4)

where Um is the jet centreline velocity; UO = Qorif =AO


is the electrolyte velocity at the ori.ce; and xm is the
horizontal distance from the ori.ce. This equation can be
rearranged to yield a relation between Um and di , i.e.


4Qorif K2
xm
Um = 6:3
=
for
5:8 ;
(5)
di xm di
di
where K2 is a parameter maintained constant for a .xed
Qorif ; cell geometry, and speci.cally set position for xm .
For these conditions, the velocity can be seen to be inversely proportional to di .
2.4. Flow through multiple ori<ces in a
manifoldCriterion 3
Perry and Green (1984) provide general design rules
for obtaining even 4ow distribution through manifolds
by balancing the ratio of inlet stream kinetic energy with
pressure losses through the pipe and ori.ce. However,
a mathematical model of the distribution 4ow of electrolyte from feed pipes in electrowinning cells can also
be de.ned by application of Bernoullis equation along
streamlines connecting the distribution pipe inlet to the
outlet distribution ori.ces on the pipe surface.
In the model, a number of assumptions are made
regarding the electrolyte 4ow through the system.
These assumptions are: (i) that the 4ow in the pipe
is one-dimensional, implying plug 4ow conditions and
negligible variation in pressure across any cross-section
of the pipe (i.e. no change in axial direction momentum
in the bulk pipe 4ow); and (ii) the friction losses along
the pipe between each of the holes are small in comparison with other pressure losses in the system, and can be
neglected. This condition can be justi.ed for situations
where the diameter of the pipe is large in comparison
with the diameters of each of the holes.
Application of Bernoullis equation to a pipe containing n ori.ces gives
OP Ui2
= K3 ;
+
(6)
e
2
where Qi and Ui are the volumetric 4ow rate and velocity,
respectively, in the pipe approaching ori.ce i, and K3 is
a constant.
The ori.ce 4ow can also be expressed as
Qorif = Qi Qi1 :

(7)

It should be noted that in Eqs. (6) and (7) the ori.ces


are numbered from last to .rst. Using this structure a
series of equations can be written that account for the
4ow through each ori.ce and result in a system of n
non-linear, interconnected equations which can be solved
simultaneously using numerical techniques.

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G. D. Rigby et al. / Chemical Engineering Science 56 (2001) 63296336

For the situation where the pipe contains many holes,


all of similar size, the 4ow may also be modelled by
a continuous model (rather than one containing many
discrete holes). This diJerential system reduces to

2OP
dQorif
= CC Ai
i
e


= CC Ai

2OPK3
e



Q2
1 orif 2
2K3 A0

(8)

Eq. (8) can be integrated to give


 




CC Ai 2=e
OP
Qorif (i) = A0 2K3 sin i
:
2
A0
(9)


Note that Eq. (8) is valid for i A0 2=2CC Ai 2=e .


Larger values of i result in non-physical solutions. In
practice, the maximum variation in the individual values
of Qorif along the manifold, as described by Eq. (9) can
be minimised by the selection of di to ensure that the
relations described in Criteria 1 and 2 (that relate to the
4ow at a speci.c ori.ce) are valid for all ori.ces along
the length of the complete manifold arm.

3. Experimental
Two separate sets of apparatus were used for the experiments conducted in this study. These included: (i) a
model of the single leg of an electrolyte distribution manifold, where liquid and gasliquid 4ow through a novel
venturi bolt ori.ce (BHP Innovation, 2001) could be
observed along the manifold length; and (ii) a pilot-plant
scale copper electrowinning cell that allowed experiments to be conducted using a series of industrially sized
electrodes.
3.1. Manifold apparatus and venturi bolts
The experimental trials relating to the simulation of
the 4ow of electrolyte and gas bubbles out of a cell
manifold through the ori.ces, were conducted in a large
steel-framed tank of dimensions 6 m long by 0:8 m wide
by 1:2 m high. The tank contained clear acrylic viewing
windows along the length of the tank and was not acid
resistant, so an arti.cial electrolyte comprising 0:3 M
NaCl in water was usedthis is comparable to normal
plant electrolyte in density and viscosity, and has the
additional important similarity in that bubbles present in
either medium do not readily coalesce (Craig, Ninham,
& Pashley, 1993). Due to space limitations in the viewing tank, only one of the two arms of the manifold was
simulated, and the total manifold length was slightly

Fig. 2. Plan view of modi.ed manifold showing installed venturi


bolts.

truncated (equivalent to 52 cathodes instead of the


full-scale 60 cathodes of industrial EW cells); however,
this was still of su?cient scale to allow the 4ow visualization and modelling veri.cation to be conducted.
To allow the electrolyte jet from each ori.ce to be
mixed with air bubbles, a novel venturi bolt was installed
in each outlet ori.ce on the manifold. The operation of
these bolts relied on a concentric pipe modi.cation to
the standard manifold (see Fig. 2 for details). The .gure
shows that compressed air and electrolyte 4ow in separate lines into each arm of the manifold. Within each arm,
electrolyte 4ows in the inner of two concentric PVC pipes
and exits into the EW cell through the hollow central
tube of each venturi bolt. Compressed air 4ows through
the outer manifold pipe and is drawn into the electrolyte
stream through an entry hole in the bolt drilled perpendicular to the electrolyte tube where high kinetic energy
mixing of the two phases occurs, and .ne air bubbles are
generated. The venturi bolts are located at 50:8 mm intervals along the length of the manifold armthis spacing
is 0.5 of the separation distance between cathode centres
in a cell with cathodes correctly in place. The bolts are
positioned to be equidistant from each cathode face, at
the centre of the space between cathode and anode. When
the manifold is in operation, jets of air and electrolyte
4ow across the face of each cathode from the nozzle of
each venturi bolt. During operation, the degree to which
the gasliquid jets issuing from an ori.ce can penetrate
into the electrolyte bath can be observed using an acrylic
model insert of one-half of a full cathode, upon which a
graduated measurement scale is marked. In the fully implemented system, a matching jet from the opposite arm
of the manifold would service the second half of each
cathode face.
The electrolyte was continually recirculated through
the manifold by a variable 4ow centrifugal pump circuit.
The total 4owrates of the electrolyte and air streams into
the manifold were measured using ultrasonic and variable area 4owmeters, and the pressure of each stream was
noted immediately prior to entry into the manifold. Individual 4ows from each ori.ce were measured using a
modi.ed double-valve void fraction probe (Hewitt, 1978)
that contained a tightly .tting pipe which sealed over the
venturi bolt being tested and also allowed the capability

G. D. Rigby et al. / Chemical Engineering Science 56 (2001) 63296336

6333

Table 1
Operational parameters for electrowinning trial (stainless-steel cathode, modi.ed TiO2 mesh=PbSnCa anode)
Trial number

Electrolyte strip (gCu2+ kg1 )


Feed comp. (g kg1 H2 SO4 )
Feed comp. (g kg1 Cu2+ )
Current density (A m2 )
Applied voltage (V)

Electrolyte temperature ( C)
Ori.ce diameter (mm)
Electrolyte 4ow (106 m3 s1 )
Gas 4owa (106 m3 s1 )
a Per

EW1

EW2

2
130 150
30 40
600
2.0
50
6
37.5

2
130 150
30 40
600
2.0
50
2
37.5
7.5

2 mm ori.ce, as recommended by Harvey et al. (1978).

of volumetric 4ow measurement of the electrolyte after


air disengagement from the 4uid in an over4ow pipe.

Fig. 3. EJect of ori.ce diameter on pressure factor and pumping


energy.

3.2. Electrowinning cell


The venturi bolt manifold method for the delivery of
the electrolyte and air bubbles was tested using a fully
automated 5000A industrial-scale electrowinning pilot
plant. This plant is capable of operation with up to seven
full-scale (1 m2 ) electrodes; however, for these trials, a
one cathode=two anode electrode set was utilized. Four
venturi bolt jetsone for each half face of the cathode
were used. Two sets of electrowinning trials were conducted to evaluate the eJectiveness of the venturi bolt
electrolyte delivery system. Table 1 lists the operational
parameters employed in each trial.
4. Results and discussion
A methodology for the selection of the optimal diameter, di , for the manifold venturi bolt ori.ce, based on
three simpli.ed single-phase criteria was developed in
Section 2, and described in Eqs. (3), (5) and (9). In this
section, the criteria are .rstly evaluated for experimental conditions described in Table 1 to determine the venturi bolt design. Once di has been .xed, the applicability
of this selection methodology to the gasliquid operating system, and the sensitivity to variations in electrolyte
and air 4owrates are evaluated and presented in terms of
an operating 4ow map. Following this, results of electrowinning pilot-scale operations using the venturi bolts
are provided below.
4.1. Optimal design of ori<ce diameter in venturi bolt
Fig. 3 shows the relationship between the required electrolyte pumping energy (in terms of pressure loss) and
di as described in Eq. (3). In this .gure, if K1 is maintained constant (by setting a constant Qorif for all ori.ces
along the manifold, then it can be seen that there is a

Fig. 4. EJect of ori.ce diameter on normalised jet centreline velocity


(xm ; Qorif = constant).

sharp decrease in the curve for 0 6 di 6 1:9 mm, beyond which there is little variation in the required pressure. Based on the criterion of minimisation of pumping
energy (Criterion 1 in Section 2.1), an ori.ce diameter
of di 1:9 mm should be selected.
In Fig. 4, the eJect of ori.ce diameter on the jet centreline velocity, Um normalised for Qorif and centreline
spatial position, xm , is considered. For the design of the
venturi bolt, the value of Um is considered to be a measure
of the degree of mixing in the 4uid across the cathode
face. The .gure shows that due to the inverse relationship
with di , the centreline velocity, Um decreases rapidly as
di is increased, and the criterion (Criterion 2 in Section
2.1) for maximisation of electrolyte mixing is indicated
to occur for di 2:5 mm.
The equal application of the two criteria (1 and 2)
in Section 2.1 for minimisation of pumping energy and
maximisation of electrolyte mixing Equations (3) and
(5) to all ori.ces along the manifold depends upon an

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G. D. Rigby et al. / Chemical Engineering Science 56 (2001) 63296336

Fig. 5. Variation in electrolyte 4ow through individual manifold ori.ces. Legend: di = 6 mm; ; QT =2 = 3 103 m3 s1 ;
; QT =2 = 2 103 m3 s1 .
Fig. 7. Schematic of air bubble distribution over cathode face (single
jet only displayed).

as a function of di for QT equivalent to operation at


600 A m2 . Fig. 6 shows that for a suitable maximum
limit of 5% variation in Qvar , the criterion (Criterion
3 in Section 2.1) for minimising the variation in electrolyte 4ow from ori.ces along the manifold occurs for
di 3:25 mm.
The design criteria for the venturi bolt ori.ce presented
in Figs. 3 6 indicate that 1:9 6 di 6 2:5 mm provides the
range in which the three stated criteria can be satis.ed.
Based on these data, a venturi bolt ori.ce diameter of
di = 2:0 mm was selected for the subsequent gasliquid
and electrowinning trials.
Fig. 6. Variation in electrolyte 4ow through individual manifold
ori.ces with ori.ce diameter.

even rate of 4ow from all ori.ces. In Eqs. (6) (9), a


model for the prediction of Qorif was developed; however,
before applying this model, it was veri.ed experimentally using the apparatus described in Section 3.1. Fig. 5
shows a comparison of experimental measurements with
the predicted variation in ori.ce 4ow for one manifold
arm and di = 6 mmcorresponding to typical operating
conditions in industrial plant prior to venturi bolt modi.cations. From the .gure it can .rstly be seen that for
two sets of conditions, relating to operation at 300 and
600 A m2 with a strip of 2 gCu2+ kg1 , the 4ow of electrolyte out of the manifold was investigated and found
to be unevendeviating signi.cantly from the average
4owwith the 4ow associated with the .rst 20% cathode positions having a much reduced 4ow compared with
that for the remainder along the manifold. It can also
be seen that there is reasonable agreement between the
model of Eq. (9) and the experimental data.
In Fig. 6, the model predictions are given for the maxQorif (min)
) 100,
imum variation in 4ow Qvar (%) = ( Qorif (max)
Qorif (max)

4.2. Operating conditions for venturi bolt


Fig. 7 shows a schematic representation of the operation of a gasliquid jet from one side of the manifold, and
de.nes a side and central region on the cathode. For a selected ori.ce diameter the extent of coverage of the gas
bubbles across the half face of the cathode is determined
by the rates of gas and electrolyte 4ow through the ori.ce,
and adequate mixing in the region close to the cathode
relies upon an even coverage of bubbles across the whole
half face of the cathode. In Fig. 8, a 4ow map of experimental observations of the behaviour of the air-electrolyte
jets is given. For Qorif 20 106 m3 s1 , the .gure
shows that there is insu?cient momentum within the jet
to enable the bubbles to penetrate su?ciently into the cell
to provide coverage in the centre of the electrode, and
performance is deemed to be unacceptable in that region.
Similarly, for low air 4ows (Qorif 20 106 m3 s1 )
the low air void fraction in the jet allows the bubbles to
be fully entrained within the jet, meaning that no disengagement occurs close to the manifold, and performance
is unacceptable in the side region. Between these two
extremes, a region of acceptable coverage occurs, sur-

G. D. Rigby et al. / Chemical Engineering Science 56 (2001) 63296336

6335

Fig. 9. Experimental copper cathode from 1 m2 electrodes, current


density = 600 A m2 .

Fig. 8. Flow map for bubble coverage over cathode from electrolyte jets (Marker Point Reference: 1, 400 A m2 ; 2, 500 A m2 ;
3, 600 A m2 ).
Table 2
Experimental 4ow
2 gCu2+ kg1 )

conditions

during

electrowinning

(strip =

Flow conditions (A m2 )
400
Electrolyte 4ow (106 m3 s1 )
Gas 4ow (106 m3 s1 ),
QG =QT = 0:2
OPPathway (kPa), excl. nozzle
Static electrolyte head (kPa)
OPL (kPa) for QG = 0
OPL (kPa) for QG =QT = 0:2
OPG (kPa) for QG =QT = 0:2

25
5.0
8
11
98
98
13

500
31
6.2
10
11
126
130
25

600
37.5
7.5
17
11
150
168
32

rounded by regions of marginal performance. The expected target operating conditions for higher current density (QG =Qorif = 0:2; ID = 400; 500; 600 A m2 ) are also
marked in Fig. 8 and fall within the region of acceptable coverage, indicating that the selection of a venturi
bolt ori.ce diameter of di = 2 mm does not preclude operation within a range of industrial conditions. Operating
parameters relating to the total required pressure within
gas and liquid feed systems, and frictional pressure losses
during the 4ow are given in Table 2.
4.3. Electrowinning trials
Following the appropriate design of the venturi bolt
(Section 4.1) and con.guration of electrolyte and air
4ow operating parameters (Section 4.2), pilot scale
electrowinning trials were conducted. Fig. 9 shows the
results of two trials conducted for conditions indicated
in Table 1. In Trial EW1 (Fig. 9a), no gas sparging
was employed, and the electrolyte was introduced into
the cell through ori.ces with di 6 mm (therefore

producing negligible jetting and 4uid mixing). This


method is comparable to current industrial practice. For
the current density conditions employed, insu?cient
mass transport enhancement was produced in the depleted concentration boundary layer, and poor to very
poor quality copper was produced, as clearly indicated
by the highly nodulised, dendritic surface of the cathode.
In Trial EW2 (Fig. 9b), a venturi sparger unit
(di = 2 mm) was used to introduce the electrolyte and
gas into the cell, and excellent cathode was produced
at 600 A m2 . The quality of the cathode from visual
inspection was very good, with little apparent evidence
of dendrites and only a low number of small nodules
present in a vertical band around the centre of the cathode. Based on the demonstrated success of the venturi
bolt sparger system using full-scale electrodes at process
plant scale, further implementation studies using true
industrial electrolyte feed in multiple electrode cells are
planned.
5. Conclusions
This study has investigated a method based on the modi.cation of existing process equipment for assisting the
commercial electrowinning of copper at current densities
up to 600 A m2 . The method largely removes the impediment to operation of present equipment at these higher
current densities where correspondingly higher productivities are made possible by minimising the Cu2+ concentration boundary layer around the cathode and increasing the level of mixing in the electrowinning bath. The
mixing is introduced via a concentric pipe manifold system that runs the length of the cell and delivers electrolyte
and air to venturi bolt ori.ces where mixing processes
produce a bubbly jet that is directed out across the base
of each cathode.
For a set current density and copper strip level, the
ori.ce diameter of the venturi bolt ori.ce was found
to be the critical design parameter. Three potentially
competing criteria for selection of the ori.ce

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G. D. Rigby et al. / Chemical Engineering Science 56 (2001) 63296336

diameter were proposed. These related to: minimisation


of energy required for electrolyte pumping; maximisation of mixing in the region of the cathode face; and
minimisation of the variation in the volumetric 4ow out
of each ori.ce along the length of the cell. Application
of the design criteria resulted in a selection of bolt ori.ce
diameter of di = 2:0 mm for gasliquid scoping studies
and electrowinning trials.
Experimental visualisation of the air-electrolyte jets for
diJerent air and liquid 4owrates into the venturi bolt allowed construction of a 4owmap that showed evidence
of acceptable mixing performance for current densities in
the range 400 600 A m2 . Operating parameters relating
to the total required pressure within gas and liquid feed
systems, and frictional pressure losses during the 4ow are
also provided.
Pilot-scale electrowinning experiments conducted using full-scale electrodes showed that for a current density of 600 A m2 , the use of the venturi bolt spargers
resulted in the production of a high quality cathode with
little apparent evidence of dendrites or nodules. In comparison, trials where there was no sparging or increased
mixing levels produced industrially unacceptable quality copper cathode, characterized by a highly nodulised,
dendritic surface.
Notation
AC
AO
cI
CC
C i ; Co
CS
db ; di
F
ID
K1
K2
K3
MM
nC
OP
Qi
Qorif
QT
Qvar
Ui
Um

surface area per cathode, m2


ori.ce area, m2
metal plating ionic charge, C
ori.ce coe?cient, dimensionless
Cu2+ concentration in electrolyte feed and
outlet, g l1
copper ion electrolyte strip, g l1
bubble, ori.ce diameter, m
Faradays constant, C mol1
current density applied to each cell, A m2
constant, kg m3 s2
constant, m2 s1
constant, m2 s2
mass 4ux of copper from deposition, kg s1
number of cathodes, dimensionless
pressure drop across ori.ce, Pa
volumetric 4ow rate in manifold approaching
ori.ce i, m3 s1
electrolyte 4owrate through ori.ce, m3 s1
total 4ow of fresh electrolyte into electrowinning cell, m3 s1
maximum 4ow variation between ori.ces on
manifold, %
4uid velocity in manifold approaching ori.ce
i, m s1
jet centreline velocity, m s1

UO
WM
xm
e

ori.ce electrolyte velocity, m s1


copper molecular weight, g mol1
horizontal distance from ori.ce, m
electrolyte density, kg m3

Acknowledgements
The authors wish to acknowledge the assistance of
Garry Smith (BHP Minerals Technology) in venturi
bolt design; Scott SciJer with aspects of 4ow modelling; Georgina Mahoney with experimental work; and
Andrew Shook and Mike Eamon for positive discussions
and review of the work.
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