PROJECT METALLURGIST

Design of Cobalt
electrowinning unit
operation
KAFUMBILA KASONTA JOSEPH

2023
Design of Cobalt electrowinning unit operation
© Joseph Kafumbila 2023
[email protected]

Joseph Kafumbila Page 1

 Process simulation
Chemical engineering can be defined from many different aspects. However, all
the scientists and professionals agree that the process is the center of it. To make a
distinction from any other discipline, the role of chemical engineering could be defined
with its purpose to develop, design, construct, control, optimize and mange any process
involving physical and/or chemical changes and make this process profitable.

Process simulation as discipline uses mathematical models as basis for analysis

prediction, testing, detection of a process behavior unrelated to whether the process is
existing in reality or not. Process simulation is there to increase the level of knowledge
for a particular process and chemical engineering in general.

So, when those two concepts are put together, we can look into the chemical
engineering as a discipline defining how the process should be developed and
simulation as the tool helping us to explore the options. Chemical engineering needs to
know how the process should be designed while chemical engineers use the simulation
to explore all the process design options and define the optimal one.

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 Abstract
This publication reviews the design criteria of Cobalt electrowinning unit
operation. This publication gives the difference between Umicore Cobalt electrowinning
unit operation and other Cobalt electrowinning unit operations using undivided cells
from the point of view of design criteria. The use of Realistic Simulation Program helps
in the comprehensive effect of temperature and the additive (sodium sulfate) on the
electrolyte pH, current efficiency and power consumption.

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 Contents

1. Introduction 6
2. Cobalt electrowinning 8
2.1. Cathode 8
2.1.1. First group of chemical reactions 8
2.1.2. Second group of chemical reactions 10
2.2. Anodic reaction 12
2.3. Cell voltage 13
2.3.1. Reversible voltage 14
2.3.2. Over potential of Cobalt on the cathode 14
2.3.3. Over potential of oxygen on the anode 14
2.3.4. Electrode contact resistance voltage drop 14
2.3.5. Electrode internal resistance voltage drop 14
2.3.6. Electrolyte resistance voltage drop 15
2.4. Energy consumption 15
2.5. Observations 15
3. Simulation of Cobalt electrowinning existing unit operation 18
3.1. Free acid concentration in Cobalt electrowinning electrolyte 18
3.1.1. First free acid concentration 18
3.1.2. Second free acid concentration 19
3.2. Specific gravity of solution at high temperature 20
3.3. Activity of soluble species 21
3.3.1. Ionic strength 21
3.3.2. Water activity 21
3.3.3. Activity coefficients 22
3.4. Simulation of Cobalt electrowinning existing unit operation 23
3.4.1. Luilu Gecamines (DRCongo) 23
3.4.2. Nkana (Zambia) 24
3.4.3. Chambishi (Zambia) 26
3.4.4. Mintek (South Africa) 27
3.4.5. Umicore (Belgium) 28
3.5. Simulation of optimal Cobalt electrowinning unit operation 31

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 3.5.1. Flow diagram 31
3.5.2. Configuration without Mg and Na 31
3.5.3. Configuration with Mg and without Na 34
3.5.4. Configuration with Mg and with Na 36
4. Cell and Electrode Data 39
5. References 41

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1. Introduction
The design of Cobalt solvent extraction using Cyanex 272 as extractant starts by
the extraction and the scrubbing unit operations (J. Kafumbila (1), 2023). Figure (1.1)
gives the flow diagram of the stripping and Cobalt electrowinning loop circuit. Scrubbing
loaded organic is sent to stripping unit operation. In Counter current spent electrolyte is
sent also to stripping unit operation. Cobalt is stripped from organic phase to give
advance electrolyte and stripped organic. Acid solution is added the stripping unit
operation to reach operational pH.

Figure 1.1: Loop circuit of stripping and Cobalt electrowinning

Abbreviations of lines between unit operations:

 ScLO: Scrubbing loaded organic phase.

 SO: Stripped organic phase.
 ADE: Advance electrolyte
 SPE: Spent electrolyte

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  EWB: Electrowinning bleed.

A bleed solution is taken from advance electrolyte to maintain the Magnesium

concentration in the loop circuit at 5g/L. The remaining advance electrolyte is sent the
Cobalt electrowinning unit operation. The electrical current is applied in the undivided
cells. At the anode, there is decomposition of water in oxygen gas. At the cathode, there
are the electrolytic deposition of Cobalt the cathode and formation of hydrogen gas from
hydrogen ion in solution.

Figure (1.1) shows that Cobalt is stripped from loaded organic phase using
spent electrolyte. The first step is to describe the Cobalt electrowinning circuit.

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2. Cobalt electrowinning

2.1. Cathode

2.1.1. First group of chemical reactions

2.1.1.1. Chemical reactions

The first group is constituted with electrochemical reactions that appear due to
decreasing of cathodic potential. These electrochemical reactions are the following:

°
Co+2 + 2e− = Coo Eh(2.a) =-0.28V (25°C) (2.a)

°
2H + + 2e− = H2 ‘ Eh(2.b) =0.000V (25°C) (2.b)

Equation (2.1) gives the current density which is the sum of current densities
used respectively for the chemical reactions (2.a) and (2.b). Where “ic ” is cathodic
current density (A/m2), “i(2.a) ” is current density used to plate Cobalt (A/m2) and “i(2.b) ”
is current density used to produce hydrogen gas (A/m2).

ic =i(1.a) +i(1.b) (2.1)

The kinetic of the electrochemical reaction is defined by Tafel Equation

(electron transfer rate). Tafel Equation (Equation (2.2)) gives the relationship between
the over-potential and current density. Where “ρ” is over-potential (V), “i” is current
density (A/m2 ) and “b” is slope of Tafel Equation. The electron transfer rate is high
when the value of Tafel slope is small (Scott, A.C. et al, 1987).

ρ=a+b*log(i) (2.2)

2.1.1.2. Current density (𝐢(𝟐.𝐛) )

It has been observed that for the reaction in which gas is evolved (hydrogen on
the cathode and the oxygen on the anode); the charge transfer kinetic is very slow
because of the mechanism (Scott, A.C. et al, 1987). The mechanism of the hydrogen
evolution has three possible reaction steps (Kelly, E.J et al; 1984):
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 H + +e− =Hads (Volmer reaction) (2.c)

H + +Hads +e− =H2 (Heyrovsky reaction) (2.d)

2Hads =H2 (Tafel reaction) (2.e)

These reactions can follow several different pathways on the cathode, most
consisting of two reaction steps: the Volmer-Tafel pathway, the Volmer-Heyrovsky
pathway, and the Tafel-Heyrovsky pathway.

Equation (2.3) gives Tafel Equation of hydrogen evolution. Value of Tafel slope
of hydrogen evolution depends on the nature of the electrode.

ρ(2.b) =a(2.b) +b(2.b)*log(i(2.b) ) (2.3)

Equation (2.4) gives the over potential of the chemical reaction (2.b). “ρ(2.b) ” is
°
hydrogen over-potential (V), “Eh(2.b) ” is standard potential of reaction (2.b) (0.0V) and
“E(c) ” is cathodic potential (V).

°
ρ(2.b) =E(c) - Eh(2.b) (2.4)

2.1.1.3. Current density (𝐢(𝟐.𝐚) )

Equation (2.5) gives the value of the Cobalt limiting current density from which
l
Cobalt powder starts to be produced. Where “ICo ” is the limiting current density (A/m2 ),
“z” is moles of electrons per mole of Cobalt, “F” is Faraday constant (c/mole), “k Co ” is the
transfer coefficient (m/s) and “CCo ” is the bulk electrolyte of Cobalt (mole/m3).

l
ICo = z * F * k Co * CCo (2.5)

The value of mass transfer coefficient is depended on the electrolyte properties

and electrolyte agitation. Maximum current density that can be applied in industrial
operations is normally about 30-40% of the limiting current density. A rule-of-thumb is
that the ratio current density (A/m2) on metal concentration in spent electrolyte (g/L)
must be less than 10.

Equation (2.6) gives Tafel Equation of Cobalt plating.

ρ(2.a) =a(2.a) +b(2.a) *log(i(2.a)) (2.6)

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 Equation (2.7) gives the over potential of the chemical reaction (2.a). “ρ(2.a) ” is
°
Cobalt plating over-potential (V), “E(2.a) ” is standard potential of reaction (1.a) (-0.28V)
and “E(c) ” is cathodic potential (V).

°
ρ(2.a) =E(c) - Eh(2.a) (2.7)

The mass of Cobalt deposited on the cathode is given by Faradays law. Faraday
law is given by Equation (2.8). Where “MCo ” is the mass of Cobalt (gram), “F” is the
Faraday constant (c/mole), “58.93” is Cobalt molar mass (g/mole), “2” is moles of
electron per mole of Cobalt, “T” is the time when current has been applied (seconds) and
“I” is the current amperage (A).

1 58.93
MCo = F * *T*I (2.8)
2

The values of current amperage and current efficiency are given by Equations
(2.9) and (2.10). Where “I” is the current amperage (A), “A” is the cathode active area
(m2) and “CE(2.a) ” is current efficiency.

I =i(1.a) *A (2.9)

i(2.a)
CE(1.a) = (2.10)
i(c)

2.1.2. Second group of chemical reactions

2.1.2.1. Chemical reactions

The second group is constituted with electrochemical reactions of Cobalt

corrosion in acidic water (Cheng Tzong Hong, 1968). These electrochemical reactions
are the following:

°
2H + + 2e− = H2 ‘ Eh(2.f) =0.000V (25°C) (2.f)

°
Coo = Co+2 + 2e− Eh(2.g) =-0.28V (25°C) (2.g)

Cobalt metal corrodes with the evolution of hydrogen. There are two half-
reactions as shown above and each half reaction has its own electrode potential and
exchange current density.

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 At time t=0 when metal is immersed into the solution, there is an adsorption of
hydrogen ion on the active surface of the metal. On the active surface of Cobalt metal
there is a place where electron is in excess; hydrogen ions take these electrons and form
hydrogen gas. At this moment there is an electronic deficit in Cobalt metal structure.
There is another place on the active surface of Cobalt metal, Cobalt metal is oxidized in
Cobalt ion and releases electrons to fill the electronic deficit in the Cobalt metal
structure. It appears an electronic movement in the Cobalt metal from the place where
the metal is oxidized called anodic electrode to the place where hydrogen ion is reduced
called cathodic electrode. At this moment there is a polarization of the electrochemical
system.

The cathodic potential decreases from potential E(2.f) when the global current is
corr
zero to the potential E(2.f) where the global current is corrosion current (I(2.f) ). Equation
(2.11) gives the value of E(2.f) . Equation (2.12) gives cathodic Tafel Equation. Where
“a(H+) ” is the activity of hydrogen ion on contact surface and “C(H2 ) ” is the concentration
of soluble hydrogen gas, and “ρ(2.f) ” is cathodic over-potential.

2.303∗R∗T a +
°
E(2.f) =E(2.f) + *log(C(H ) ) (2.11)
F (H2 )

corr
ρ(2.f) =E(2.f) - E(2.f) = a(2.f) -b(2.f) *log(I(2.f) ) (2.12)

The anodic potential increases from potential E(2.g) when the global current is
corr
zero to the potential E(2.g) where the global current is corrosion current (I(2.g)). Equation
(2.13) gives the value of E(2.g) . Equation (2.14) gives anodic Tafel Equation. Where
“a(Co+2 ) ” is the activity of Cobalt ion on contact surface and “a(Co) ” is the activity of
Cobalt in the Cobalt metal structure, “ρ(2.g) ” is anodic over-potential.

2.303∗R∗T a(Co+2 )
°
E(2.g) =E(2.g) + *log( ) (2.13)
2∗F aCo

corr
ρ(2.g) =E(2.g) -E(2.g) =a(2.g) +b(2.g) *log(I(2.g)) (2.14)

corr corr
The difference between E(2.f) and E(2.g) is the over-potential due to the electrical
resistance of Cobalt metal (Equation 2.15). Where “R” is the electrical resistance of
Cobalt metal.

corr corr
E(2.f) -E(2.g) =R*Icorr (2.15)

The difference between E(2.f) and E(2.g) gives the global over-potential (Equation
2.16). Where “ρ(2.f) ” is cathodic over-potential, “ρ(2.g)” is anodic over-potential, and “R” is

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the electrical resistance of the metal. Equation (2.17) gives the correlation between Icorr ,
I(1.f) and I(1.g)

E(1.f) - E(1.g) =ρ(1.g) + R*Icorr - ρ(1.f) (2.16)

Icorr =I(1.f) =I(1.g) (2.17)

Figure (1.2) gives the polarization curves of the corrosion of Cobalt metal in the
acidified water.

Figure 1.2: Polarization of anodic and cathodic reactions to reach corrosion potential

2.1.2.2. Observation

The Cobalt corrosion rate in acidic solution increases with increasing

temperature. This phenomenon is due to the reduction of over-potential of hydrogen
evolution on Cobalt surface with increasing temperature (Cheng Tzong Hong, 1968).

2.2. Anodic reaction

Electrochemical reactions at the anode surface are given by the chemical
reaction (2.h).

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 1 °
H2 O = 2H + + 2 O2 + 2e− Eh(2.h) =1.23V (25°C) (2.h)

One of the more generally accepted pathways of oxygen evolution consists of

reactions (2.i), (2.j) and (2.k) (Fabbri, E. et al, 2014).

OH − =OHads +e− (2.i)

OH − +OHads =H2 O+e− +Oads (2.j)

2Oads =O2 (2.k)

The mass of oxygen gas produced is the mass of oxygen produced by the
chemical reaction (2.h). The mass of oxygen gas on the anode is given by Faradays law.
Faraday law is given by Equation (2.18). Where “ MO “ is the mass of oxygen (gram), “F”
is Faraday constant (coulombs per mole), “32” is oxygen gas molar mass (grams per
mole), “4” is moles of electron per mole of oxygen gas, “T” is the time when current has
been applied (seconds), “I” is the current amperage (Amps)

1 32
MO = F * *T*I (2.18)
4

The values of current amperage and current efficiency are given by Equations
(2.19) and (2.20). The value of CEO is around 98% taking account 2% of short circuit.
Where “I” is the current amperage (Amps), “A” is the anode active area (m2), “CE(2.h) ” is
global oxygen current efficiency, and “i(a) ” is anodic current density.

I =i(2.h) *A (2.19)

i(2.h)
CE(2.h) = (2.20)
i(a)

2.3. Cell voltage

The chemical reactions (2.a) on the cathode and (2.h) on the anode are used to
calculated the cell voltage.

Equation (2.21) gives the value of operating cell voltage. Where “VRCo ” is the
reversible voltage, “ρ(2.a) ” is absolute value of cathode over-potential, “ρ(2.h) ” is absolute
value of anode over-potential, “Vῼc ” is electrode contact resistance voltage drop, “VOῼi ”
is operating electrode internal resistance voltage drop, and “VOῼe ” is operating
electrolyte resistance voltage drop.

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 VOC = VRCo + ρ(2.a) + ρ(2.h) + Vῼc +VOῼi +VOῼe (2.21)

2.3.1. Reversible voltage

°
Reversible voltage (VRCo ) is given by Equation (2.22). Where “E(2.h) ” is the
°
electrode standard potential of the chemical reaction (2.h) at 25°C (1.23 V) and “E(2.a) ”
is the electrode standard potential of the chemical reaction (2.a) at 25°C (-0.28V).

° °
VRCo = E(2.h) - E(2.a) (2.22)

2.3.2. Over potential of Cobalt on the cathode

Equation (2.23) gives the cathodic Cobalt over potential. Where “ρ(2.a) ” is Cobalt
over-potential (V) and “Iex ” is Cobalt exchange current density (A/m2 ), “b(2.a) ” is Tafel
slope and “I(2.a) ” is Cobalt current density (A/m2 ).

Iex
ρ(2.a) =b(2.a) *log(I ) (2.23)
(2.a)

2.3.3. Over potential of oxygen on the anode

Equation (2.24) gives the anodic over potential of oxygen evolution. Where
“ρ(2.h) ” is oxygen over potential (V) and “I(2.h) ” is oxygen current density (A/m2 ), “b(2.h) ”
is Tafel slope and “Iex ” is exchange current density (A/m2 ).

I(2.h)
ρ(2.h) =b(2.h) *log( ) (2.24)
Iex

2.3.4. Electrode contact resistance voltage drop

In the modern Cobalt electrowinning cell-house, the range of electrode contact
voltage drop is from 5 to 25% of the total cell voltage. Electrode contact resistance
voltage drop is estimated at 10% of total cell voltage.

2.3.5. Electrode internal resistance voltage drop

Equation (2.25) gives the electrode internal resistance voltage drops. Where
“VOῼi ” is operating electrode internal resistance voltage drop (V), “Ic ” is the cathodic
current density (A/m2), “ῼc ” is the cathodic material resistivity (Ω-m), “Tc ” is the

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thickness of cathode (m), “Ia ” is the anodic current density (A/m2), “ῼa ” is the anodic
material resistivity (Ω-m), and “Ta ” is the thickness of cathode (m), .
.
VOῼi = Ic * ῼc * Tc +Ia * ῼa * Ta (2.25)

2.3.6. Electrolyte resistance voltage drop

Equation (2.26) gives operating electrolyte resistance voltage drops. Where
“VOῼe ” is operating electrolyte resistance voltage drop (V), “Ic ” is the cathodic current
density (A/m2), “ῼel ” is the electrolyte resistivity (Ω-m), and “De ” is the distance face-to-
face between anode and cathode (m).

VOῼe = Ic * ῼel * De (2.26)

2.4. Energy consumption

The energy consumption for an electrowinning cell is calculated according to

Equation (2.27). Where “EC” is the energy consumption (kWh/kg), “Voc ” is the operating
cell voltage over the deposition cycle (V), “Ic ” is the cathodic current (A), “t” is time (s)
and “Mac ” is the deposit mass (g).

Voc ∗Ic ∗t
EC = (2.27)
MCo

2.5. Observations

The literature shows that:

 The increase in Cobalt concentration leads to higher conductivity of

solution that decreases power consumption and leads to higher current
efficiency (D. Lowe et al, 1968). From 50g/L of Cobalt in solution, the
viscosity of solution increases (N. Mulaudzi et al, 2013).
 The increase in the sulfuric acid concentration leads to high conductivity
of solution that decreases power consumption and leads to lower current
efficiency. The Cobalt current efficiency increases with the increase of pH
and the hydrogen current efficiency decreases with the increase of pH
(D. Lowe et al, 1968). Figure (1.3) shows the Cobalt current efficiency
versus pH at 20°C and 60°C at 200A/m2 (R. Breckpot et al, 1969).

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Figure (1.3): Cobalt current efficiency versus pH at 20°C and 60°C (200A/m2)

 In pure Cobalt electrolyte, the current efficiency increases with the

increase of temperature because the activation energy of Cobalt electron
transfer kinetic is a function of temperature. Figure (1.3) shows that at
pH 1.5; the Cobalt current efficiency is 51% and 90% respectively at 20°C
and 60°C and at 70% of Cobalt current efficiency; pH is 1.22 and 1.8
respectively at 60°C and 20°C.
 The power consumption decreases with the increase of temperature
because the electrolyte conductivity increases with the increase of
temperature (D. Lowe et al, 1968). The operational temperature is
between 60°C and 80°C.
 The increase in concentration of sulfate salts (Na2SO4, MgSO4 and
(NH4)2SO4) leads to higher conductivity of solution that decreases power
consumption (D. Lowe et al, 1968) and leads to higher current efficiency
up to 5g/L of Mg and 15g/L of Na2SO4 (N. Mulaudzi et al, 2013 and
Sharma et al., 2005). The operational concentration of Na2SO4 is 65 g/L
based on earlier work at Mintek. Magnesium, for instance, can be a good
conductor, but an excess of Mg will increase the viscosity of the solution
and, hence, inhibit mass transfer due to poor agitation at the cathode
surface (Sharma et al., 2005). The maximum concentration of Mg is
5 g/L.

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  For pH greater than 3.6, Cobalt deposit is brittle. Between pH 2.4 and 2.6,
Cobalt deposit does not have coherent structure. The concentration of
hydrogen in the structure is high and causes the bursting of Cobalt
deposit. For pH less than 2.4, Cobalt deposit is ductile. When Cobalt
deposition starts at pH greater than 2.4 given brittle structure, the
structure remains brittle during de Cobalt deposition even if solution pH
decreases to less than 2.4. For a good structure of Cobalt deposit, the
Entry solution pH must be between 1.5 and 1.8 and Exit solution acid
concentration can be between 10 to 15g/L (around pH 1.1). (R. Breckpot
et al, 1969).
 The increase in current density increases the cell voltage that increases
the power consumption. The range of current density is 200 – 400 A/m2.
The current density more than 400A/m2 leads to lower current efficiency
because the current density is in transition zone that is the mixing of
electron transfer and diffusion mechanism of plating. The maximum
value of power consumption is 6kwh/kgCo.

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3. Simulation of Cobalt electrowinning
existing unit operation

3.1. Free acid concentration in Cobalt electrowinning

electrolyte

3.1.1. First free acid concentration

The pure solution of Cobalt in sulfate medium contains the following soluble
substances: H + , Co+2 , HSO− −2
4 , SO4 , H2 SO4 and CoSO4 . The chemical reaction (3.a), (3.b)
and (3.c) give the equilibrium reactions of soluble compounds.

H + +SO−2 −
4 =HSO4 (3.a)

2H + +SO−2
4 =H2 SO4 (3.b)

Co+2 +SO−2
4 =CoSO4 (3.c)

pH and total Cobalt concentration are known values. Equation (3.1) and (3.2)
gives the concentration of H + (C( H+) ) and total Cobalt concentration (C( CoT) ). Where
“γ( p) ” is activity coefficient of soluble compound “p” and “C( p) ” is the molar
concentration of soluble compound “p”.

10(−pH)
C( H+) = (3.1)
γ( H+ )

C( CoT) =C(Co+2 )+C( CoSO4) (3.2)

The concentration of CoSO4 (C( CoSO4 )) is given by Equation (3.3). Where “K ( 3.c)”
is equilibrium constant of chemical reaction (3.c). The concentration of HSO− 4 (C( HSO−4)
)
and H2 SO4 (C(H2 SO4 ) ) are given by Equations (3.4) and (3.5).

γ(Co+2 ) ∗γ( SO−2 )

C( CoSO4 ) =K ( 3.c)*C(Co+2 )*C(SO−2
4 )
* 4
(3.3)
γ( C( CoSO ) )
4

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 γ(H+ ) ∗γ( SO−2 )
C(HSO−4 ) =K ( 3.a) *C(H+ ) *C(SO−2
4 )
* 4
(3.4)
γ( C
(HSO−
4 )
)

(C(H+ ) )2 ∗γ( SO−2 )

C(H2 SO4 ) =K ( 3.b) *(C(H+) )2 *C(SO−2
4 )
* 4
(3.5)
γ( C(H SO ) )
2 4

Equation (3.6) gives the electrical neutrality of solution. The resolution of

Equations (3.2), (3.3), (3.4), (3.5) and (3.6) gives the values of C(Co+2 ) ; C( CoSO4 ), C(HSO−4 ) ,
C(H2 SO4 ) and C(SO−2
4 )
.

C(H+ ) +2C(Co+2 )=C(HSO−4 )+2C(SO−2

4 )
(3.6)

Hydrogen ions (H + ) are in electrical charge equilibrium with anion (HSO− 4 ).

Equation (3.7) gives the concentration (G(H2 SO4 )) (g/L) of free acid is solution. Where
“98.075” is molar mass of H2 SO4 . Equation (3.8) gives the total sulfur concentration
(G(ST) ). Where “32.065” is molar mass of sulfur.

G(H2 SO4) =(C( H+) +C(H2 SO4 ) )*98.075 (3.7)

G(ST) )=( C( CoSO4) +C(HSO−4 ) +C(H2 SO4 ) +C(SO−2

4 )
)*32.065 (3.8)

This value of acid concentration in solution obtained by using Equation (3.7) is

used in Realistic Simulation Program (J. Kafumbila (2), 2023), by R. Breckpot (R.
Breckpot et al, 1969) and by Umicore Cobalt electrowinning design.

3.1.2. Second free acid concentration

The pure solution of Cobalt in sulfate medium contains the following soluble
substances: H2 SO4 and CoSO4 . Equation (3.9) gives the concentration (G(H2 SO4) ) (g/L) of
free acid is solution. Where “G(ST) ” is total concentration of sulfur in solution (g/L),
“G(CoT) ” is total concentration of Cobalt in solution (g/L), “58.93” is molar mass of
Cobalt.

32.065 98.075
G(H2 SO4) =(G(sT ) - G(CoT) * 58.93 )*32.065 (3.9)

This value of acid concentration in solution obtained by using Equation (3.9) is

equal to the analytical free acid concentration obtained from chemical analysis
laboratory. This is used in the design of Cobalt electrowinning unit operation of Mintek
(South Africa), FQM (Australia), Luilu-Gecamines (DRC), Chambishi (Zambia) and
Nkana (Zambia).

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3.2. Specific gravity of solution at high temperature
Equation (3.10) gives the approximate value of specific gravity of liquid in as
function of liquid chemical composition at 25°C (J. Kafumbila (2), 2023). Where “ SGL ”
is liquid specific gravity (t/m3) and “GT ” is total concentration of soluble compounds
(g/L)

SGL = -6.139 * 10−7 x [GT ]2 + 9.742 * 10−4 * GT + 1 (3.10)

The specific gravity of solution at high temperature is obtained by using this

procedure:

 The mass of solution is known value.

 The volume of solution is calculated from the value of mass and specific
gravity of solution (25°C).
 Total mass of soluble compounds is calculated from volume of solution
(25°C) and total concentration of soluble compounds.
 Water mass is mass of solution minus mass of soluble compounds.
 Water mass and specific gravity of water at 25°C is given in Table (3.1)
give water volume (25°C).

Table 3.1: Specific gravity of water vs temperature

Temperature Water specific gravity

(°C) (t/m3)
25 0.997
30 0.996
35 0.994
40 0.992
45 0.990
50 0.988
55 0.986
60 0.983
65 0.981
70 0.978
75 0.975
80 0.972
85 0.969
90 0.965
95 0.962
100 0.958

 The volume of soluble compounds is the volume of solution (25°C) minus

water volume (25°C).

Joseph Kafumbila Page 20

  The water volume (t°C) is calculated from water mass and water specific
gravity (t°C).
 The volume solution (t°C) is the sum of water volume (t°C) and volume
soluble compounds.
 Specific gravity of solution (t°C) is calculated with the mass of solution
and volume of solution (t°C)

3.3. Activity of soluble species

3.3.1. Ionic strength

The ionic strength of the system is given by Equation (3.11). Where “Ci ” is the
concentration (mol/L) of soluble compounds “i” and “Zi ” is electrical charge of the
soluble compounds “i”.

1
I = 2x∑ Ci ∗ Zi2 (3.11)

3.3.2. Water activity

The activity of water (solvent) (𝑎𝑤 ) is given by Equation (3.12). “ϕ” is the
osmotic coefficient, “W” is the molecular weight of water (18.016) and “𝑚𝑖 ” is the
concentration (mole/kg water) of soluble compounds (Charles E. Harvie et al, 1984). In
this case, the concentrations of soluble compounds are very low; in consequence the
molarity is close to the molarity. Equation (3.12) becomes Equation (3.13).

W
ln (aw ) = - 1000 *ϕ *∑i mi (3.12)

W
ln (aw ) = - 1000 *ϕ *∑i Ci (3.13)

The calculations of osmotic coefficient have been approximated by Equation

(3.14) (H.C. Helgeson, 1969). The value of “u” is given by Equation (3.15). Table (3.2)
gives values of parameters “a”, “b”, “c” and “d” at different temperatures. “A” comes from
Debrye-Huckel Equation for activity coefficient and is function of temperature. The value
of “A” is in Table (3.3). “I” is the ionic strength (mole/kg of water). In this case, the ionic
strength is given in mole/L.

2.303∗A 1 b∗I 2c∗I2 3d∗I3

ϕ=1- [u -2ln(u) -u] + + + (3.14)
a3 ∗I 2 3 4

u=1+a*√I (3.15)

Joseph Kafumbila Page 21

 Table 3.2: values of a, b, c and d

Temperature (°C) a b c d
25 1.454 0.02236 9.38*10−3 -5.362*10−4
100 1.555 0.03648 6.437*10−3 -7.132*10−4
200 1.623 0.04589 4.522*10−3 -8.312*10−4

3.3.3. Activity coefficients

Activity of soluble compound “I” in water is given by Equation (3.16). “γi ” is
activity coefficient and Ci is the concentration (mole/L) of soluble compound.

ai = γi * Ci (3.16)

The calculations of individual ion activity coefficient have been approximated by

Equation (3.17) in concentrated as well as dilute electrolyte solutions involved in
geochemical processes at high temperatures and pressures (H.C. Helge son et al, 1981)
and suitable for overall equilibrium diagram calculations. “γi ” Is the activity coefficient
of soluble compound “I”, “Zi ” is the electrical charge of compound “i” and “I” is the ionic
strength (mol/kg of water) (in this case ionic strength is given in mole/L). “A”, “B” and
“b” are temperature-dependent parameters. Table (3.3) gives values of parameters “A”,
“B” and “b” at different temperatures (B. Beverskog et al, 1998). “ä” is a distance of
closest approach, which may be taken to be equal to that of NaCl (3.72 10−10m).

Z2 A√I
Log(γi )= - (1+Bä√I)
i
– log(1+0.018015*I)+b*I (3.17)

Table 3.3: values of A, B and b parameter

Temperature (°C) A B b
25 0.509 0.328 0.064
100 0.600 0.342 0.076
150 0.690 0.353 0.065
200 0.81 0.361 0.046

For neutral aqueous species it is usually approximated that the activity

coefficients are unity at all values of ionic strength and temperature. The approximate
applicability is up to value of ionic strength around 5 (mole/kg of water) (H.C. Helgeson
et al, 1981).

Joseph Kafumbila Page 22

3.4. Simulation of Cobalt electrowinning existing unit
operation
All the Cobalt electrowinning existing unit operation uses undivided cell. The
simulation of Cobalt electrowinning existing unit operation uses the Realistic Simulation
Program. The effect of temperature on specific gravity of solution, activity of soluble
compound and activity of water has been discussed in chapters (3.2) and (3.3).

3.4.1. Luilu Gecamines (DRCongo)

3.4.1.1. Flow diagram

Figure (3.1) gives the flow diagram of Cobalt electrowinning unit operation

Figure 3.1: Flow diagram of Cobalt electrowinning unit operation

3.4.1.2. Design criteria

Table (3.4) gives design criteria of Luilu Cobalt electrowinning unit operation.

Table 3.4: Luilu design criteria of Cobalt electrowinning unit operation

Description Values
Entry pH 6.5
Entry Co (g/L) 45
Temperature (°C) 70
Exit acid (2) (g/L) 7.5
Current efficiency (%) 80

Joseph Kafumbila Page 23

3.4.1.3. Mass balance

Table (3.5) gives the mass balance of Luilu Cobalt electrowinning unit operation

Table 3.5: Mass balance of Luilu Cobalt electrowinning unit operation

1.00 2.00 3.00 4.00 5.00

Entry Solution Co Cathode Oxygen Hydrogen Exit solution
Solid
mass t/h 0.275
Gas
mass t/h 0.093 0.002
Liquid
mass t/h 66.516 66.144
volume m3/h 61.155 61.127
SG liquid t/m3 1.088 1.082
Co g/l 45.000 40.514
S g/l 24.487 24.499
Ac (1) g/l 0.000 1.379
Ac (2) g/l 0.000 7.500
pH 6.500 2.025
t°C 70.000 70.00

3.4.1.4. Observations

The observations of mass balance show that:

 Exit Cobalt concentration is 40.514 g/L (ΔCo = 4.49 g/L).

 Exit pH is 2.025.
 Exit acid (1) concentration is 1.379g/L.
 Cobalt deposit structure is brittle.

3.4.2. Nkana (Zambia)

3.4.2.1. Flow diagram

Figure (3.1) gives the flow diagram of Cobalt electrowinning unit operation

3.4.2.2. Design criteria

Table (3.6) gives design criteria of Nkana Cobalt electrowinning unit operation.

Joseph Kafumbila Page 24

 Table 3.6: Nkana design criteria of Cobalt electrowinning unit operation

Description Values
Entry acid (2) (g/L) 2.0
Entry Co (g/L) 40
Temperature (°C) 70
Exit acid (2) (g/L) 10.0
Current efficiency (%) 70

3.4.2.3. Mass balance

Table (3.7) gives the mass balance of Nkana Cobalt electrowinning unit
operation

Table 3.7: Mass balance of Nkana Cobalt electrowinning unit operation

1.00 2.00 3.00 4.00 5.00

Entry solution Co Cathode Oxygen Hydrogen Exit solution
Solid
Mass t/h 0.294
Gas
Mass t/h 0.112 0.004
Liquid
mass t/h 65.948 65.538
volume m3/h 61.157 61.130
SG liquid t/m3 1.078 1.072
Co g/l 40.000 35.211
S g/l 22.421 22.431
Ac (1) g/l 0.339 2.099
Ac (2) g/l 2.000 10.000
pH 2.636 1.846
t°C 70.000 70.000

3.4.2.4. Observations

The observations of mass balance show that:

 Exit Cobalt concentration is 35.21 g/L (ΔCo = 4.79 g/L).

 Exit pH is 1.846.
 Exit acid (1) concentration is 2.099g/L.
 Cobalt deposit structure is ductile.

Joseph Kafumbila Page 25

3.4.3. Chambishi (Zambia)

3.4.3.1. Flow diagram

Figure (3.1) gives the flow diagram of Cobalt electrowinning unit operation

3.4.3.2. Design criteria

Table (3.8) gives design criteria of Chambishi Cobalt electrowinning unit

operation.

Table 3.8: Chambishi design criteria of Cobalt electrowinning unit operation

Description Values
Entry pH 6.3
Entry Co (g/L) 40
Temperature (°C) 70
Exit pH 1.9
Current efficiency (%) 70

3.4.3.3. Mass balance

Table (3.9) gives the mass balance of Chambishi Cobalt electrowinning unit
operation

Table 3.9: Mass balance of Chambishi Cobalt electrowinning unit operation

1.00 2.00 3.00 4.00 5.00

Entry solution Co Cathode Oxygen Hydrogen Exit solution
Solid
Mass
Gas 0.328
Mass 0.127 0.005
Liquid
mass t/h 65.845 65.385
volume m3/h 61.158 61.128
SG liquid t/m3 1.077 1.070
Co g/l 40.000 34.657
S g/l 21.767 21.777
Ac (1) g/l 0.000 1.856
Ac (2) g/l 0.001 8.925
pH 6.300 1.900
t°C 70.000 70.000

Joseph Kafumbila Page 26

3.4.3.4. Observations

The observations of mass balance show that:

 The exit Cobalt concentration is 34.656 g/L (ΔCo = 5.35 g/L)

 Exit acid (2) concentration is 8.925g/L.
 Exit acid (1) concentration is 1.856g/L.
 Cobalt deposit structure is brittle.

3.4.4. Mintek (South Africa)

3.4.4.1. Flow diagram

Figure (3.1) gives the flow diagram of Cobalt electrowinning unit operation

3.4.4.2. Design criteria

Table (3.10) gives design criteria of Mintek Cobalt electrowinning unit

operation.

Table 3.10: Mintek design criteria of Cobalt electrowinning unit operation

Description Values
Entry pH 3.0
Entry Co (g/L) 55
Temperature (°C) 70
Entry Na2SO4 (g/L) 50
ΔCo (g/L) 5.0
Current efficiency (%) 80

3.4.4.3. Mass balance

Table (3.11) gives the mass balance of Mintek Cobalt electrowinning unit
operation

Joseph Kafumbila Page 27

 Table 3.11: Mass balance of Mintek Cobalt electrowinning unit operation

1.00 2.00 3.00 4.000 5.00

Entry solution Co Cathode Oxygen Hydrogen Exit solution
Solid
Mass 0.308
Gas
Mass 0.104 0.003
Liquid
mass t/h 70.168 69.754
volume m3/h 60.953 60.897
SG liquid t/m3 1.151 1.145
Co g/l 55.000 50.000
Na g/l 16.185 16.200
S g/l 41.579 41.617
Ac (1) g/l 0.136 1.304
Ac (2) g/l 1.113 9.519
pH 3.000 2.020
t°C 65.000 65.000

3.4.4.4. Observations

The observations of mass balance show that:

 Exit acid(2) concentration is 9.514 g/L

 Exit pH is 2.02.
 Exit acid (1) concentration is 1.304g/L
 Cobalt deposit structure is brittle.

3.4.5. Umicore (Belgium)

3.4.5.1. Flow diagram

Figure (3.2) gives the flow diagram of Umicore Cobalt electrowinning unit
operation

Joseph Kafumbila Page 28

 Figure 3.2: Flow diagram of Umicore Cobalt electrowinning unit operation

3.4.5.2. Design criteria

Table (3.14) gives design criteria of Umicore Cobalt electrowinning unit

operation.

Table 3.14: Umicore design criteria of Cobalt electrowinning unit operation

Description Values
Advance electrolyte pH 2.5
Advance electrolyte Co (g/L) 60
Temperature (°C) 70
Entry solution Co (g/L) 45
Entry solution pH Between 1.5 and 1.8
Spent electrolyte Co (g/L) 40
Current efficiency (%) 70

3.4.5.3. Mass balance

Tables (3.15) and (3.16) give the mass balance of Umicore Cobalt
electrowinning unit operation

Joseph Kafumbila Page 29

 Table 3.15: Mass balance of Umicore Cobalt electrowinning unit operation

1.00 2.00 3.000 4.00

Advance Recirculated Entry Solution Co Cathode
electrolyte Electrolyte
Solid
Mass 1.233
Gas
Mass
Liquid
mass t/h 68.603 201.45 270.05
volume m3/h 61.145 183.44 244.58
SG liquid t/m3 1.122 1.098 1.104
Co g/l 60.000 40.000 45.000
S g/l 33.718 33.857 33.822
Ac (1) g/l 0.447 10.916 6.738
Ac (2) g/l 3.270 36.979 28.552
pH 2.500 1.119 1.327
t°C 70.000 70.000 70.00

Table 3.16: Mass balance of Umicore Cobalt electrowinning unit operation

5.00 6.00 7.00 8.00

Oxygen Hydrogen Exit solution Spent
electrolyte
Solid
Mass
Gas
Mass 0.478 0.018
Liquid
mass t/h 268.319 66.87
volume m3/h 244.330 60.89
SG liquid t/m3 1.098 1.098
Co g/l 40.000 40.000
S g/l 33.857 33.857
Ac (1) g/l 10.916 10.916
Ac (2) g/l 36.979 36.979
pH 1.119 1.119
t°C 70.00 70.000

3.4.5.4. Observations

The observations of mass balance show that:

 Exit acid(2) concentration is 36.979 g/L

 Exit pH is 1.119.
 Exit acid (1) concentration is 10.916g/L.
 Cobalt deposit structure is ductile.

Joseph Kafumbila Page 30

3.5. Simulation of optimal Cobalt electrowinning unit
operation

3.5.1. Flow diagram

Figure (3.3) gives the flow diagram of optimal Cobalt electrowinning unit
operation

Figure 3.3: Flow diagram of optimal Cobalt electrowinning unit operation

3.5.2. Configuration without Mg and Na

3.5.2.1. Design criteria

Table (3.17) gives design criteria of optimal Cobalt electrowinning unit

operation.

Joseph Kafumbila Page 31

 Table 3.17: Design criteria of optimal Cobalt electrowinning unit operation

Description Values
Advance electrolyte (25°C) pH 2.0
Advance electrolyte (25°C) Co (g/L) 60
Temperature (°C) 60
Entry solution Co(g/L) 55
Entry solution pH Greater than 2.0
Exit electrolyte Co (g/L) 50
Current efficiency (%) 80

The delta Cobalt concentration between advance and spent electrolyte of 10g/L
is to have less than 5.0g/L of acid(1) in exit solution to decrease the acid corrosion of
Cobalt deposit (Nik Rozlin Nik Mold Masdek, 2014). The delta Cobalt concentration
between entry and exit solution of 5g/L is taken in the old Cobalt electrowinning
configuration. The pH of 2.0 in the advance electrolyte (25°C) is to have entry solution
pH greater than 2.0 (ductile structure of Cobalt deposit). The temperature of 60°C is to
decrease the water evaporation (N. Mulaudzi et al, 2013).

3.5.2.2. Mass balance

Tables (3.18) and (3.19) give the mass balance of optimal Cobalt electrowinning
unit operation

Table 3.18: Mass balance of optimal Cobalt electrowinning unit operation

1 2 3 4 5
Advance Advance Recirculated Entry Co Cathode
Electrolyte Electrolyte electrolyte Solution
(25°C) (60°C)
Solid
Mass t/h 0.563
Gas
Mass t/h
Liquid
mass t/h 68.503 68.503 56.650 125.152
volume m3/h 60.000 60.836 50.799 111.636
SG liquid t/m3 1.142 1.126 1.115 1.121
Co g/l 60.000 59.175 50.000 55.000
S g/l 34.019 33.552 33.600 33.574
Ac (1) g/l 1.405 0.689 4.403 2.116
Ac (2) g/l 4.191 4.134 19.552 11.150
pH 2.000 2.310 1.508 1.825
Temp °C 25.000 60.000 60.000 60.000

Joseph Kafumbila Page 32

 Table 3.19: Mass balance of optimal Cobalt electrowinning unit operation

6 7 8 9 10
Oxygen Hydrogen Exit Spent Spent
Solution Electrolyte Electrolyte
(60°C) (25°C)
Solid
Mass t/h
Gas
Mass t/h 0.191 0.005
Liquid
mass t/h 124.394 67.744 67.744
volume m3/h 111.548 60.748 59.671
SG liquid t/m3 1.115 1.115 1.135
Co g/l 50.000 50.000 50.902
S g/l 33.600 33.600 34.207
Ac (1) g/l 4.403 4.403 8.285
Ac (2) g/l 19.552 19.552 19.906
pH 1.508 1.508 1.232
Temp °C 60.000 60.000 60.000

3.5.2.3. Observations

The observations of mass balance show that:

 .Advance electrolyte (60°C) pH: 2.310.

 Advance electrolyte (60°C) Acid (1) concentration: 0.689g/L.
 Advance electrolyte (60°C) Acid (2) concentration: 4.134g/L.
 Entry solution pH: 1.825
 Exit pH: 1.508
 Exit acid (1) concentration: 4.403g/L.
 Exit acid(2) concentration: 19.552g/L
 Spent electrolyte (25°C) pH: 1.232.
 Spent electrolyte (25°C) Acid (1) concentration: 8.285g/L.
 Spent electrolyte (25°C) Acid (2) concentration: 19.906g/L.

The results show that the increase in temperature leads to higher pH, lower
acid(1) concentration and the same value of acid(2) concentration.

Joseph Kafumbila Page 33

3.5.3. Configuration with Mg and without Na

3.5.3.1. Design criteria

Table (3.20) gives design criteria of optimal Cobalt electrowinning unit

operation.

Table 3.20: Design criteria of optimal Cobalt electrowinning unit operation

Description Values
Advance electrolyte (25°C) pH 2.0
Advance electrolyte (25°C) Co (g/L) 60
Advance electrolyte (25°C) Mg (g/L) 5
Temperature (°C) 60
Recirculated electrolyte Co(g/L) 55
Exit electrolyte Co (g/L) 50
Current efficiency (%) 80

The scrubbing organic contains Cobalt and Magnesium. In the loop circuit of
stripping and Cobalt electrowinning unit operations, the electrolyte bleed is applied to
maintain the Magnesium concentration at 5g/L.

3.5.3.2. Mass balance

Tables (3.21) and (3.22) give the mass balance of optimal Cobalt electrowinning
unit operation

Joseph Kafumbila Page 34

 Table 3.21: Mass balance of optimal Cobalt electrowinning unit operation

1 2 3 4 5
Advance Advance Recirculated Entry Co Cathode
Electrolyte Electrolyte electrolyte Solution
(25°C) (60°C)
Solid
Mass t/h 0.563
Gas
Mass t/h
Liquid
mass t/h 69.647 69.647 57.686 127.333
volume m3/h 60.000 60.831 50.856 111.687
SG liquid t/m3 1.161 1.145 1.134 1.140
Co g/l 60.000 59.180 50.000 55.000
Mg g/l 5.000 4.932 4.940 4.935
S g/l 40.724 40.167 40.234 40.198
Ac (1) g/l 1.375 0.667 3.843 1.920
Ac (2) g/l 4.529 4.467 19.916 11.502
pH 2.000 2.314 1.556 1.856
Temp °C 25.000 60.000 60.000 60.000

Table 3.22: Mass balance of optimal Cobalt electrowinning unit operation

6 7 8 9 10
Oxygen Hydrogen Exit Spent Spent
Solution Electrolyte Electrolyte
(60°C) (25°C)
Solid
Mass t/h
Gas
Mass t/h 0.191 0.005
Liquid
mass t/h 126.573 68.887 68.887
volume m3/h 111.586 60.730 59.655
SG liquid t/m3 1.134 1.134 1.155
Co g/l 50.000 50.000 50.901
Mg g/l 4.940 4.940 5.029
S g/l 40.234 40.234 40.959
Ac (1) g/l 3.843 3.843 7.456
Ac (2) g/l 19.916 19.916 20.275
pH 1.556 1.556 1.269
Temp °C 60.000 60.000 60.000

3.5.3.3. Observations

The observations of mass balance show that:

 .Advance electrolyte (60°C) pH: 2.314.

 Advance electrolyte (60°C) Acid (1) concentration: 0.666g/L.
 Advance electrolyte (60°C) Acid (2) concentration: 4.467g/L.

Joseph Kafumbila Page 35

  Entry solution pH: 1.856
 Exit pH: 1.556
 Exit acid (1) concentration: 3.843g/L.
 Exit acid(2) concentration: 19.916g/L
 Spent electrolyte (25°C) pH: 1.269.
 Spent electrolyte (25°C) Acid (1) concentration: 7.456g/L.
 Spent electrolyte (25°C) Acid (2) concentration: 20.275g/L.

The presence of Magnesium in Cobalt electrolyte increases the exit solution pH

form 1.508 to 1.556. This means that the current efficiency increases and the power
consumption decreases.

3.5.4. Configuration with Mg and with Na

3.5.4.1. Design criteria

Table (3.23) gives design criteria of optimal Cobalt electrowinning unit

operation.

Table 3.23: Design criteria of optimal Cobalt electrowinning unit operation

Description Values
Advance electrolyte (25°C) pH 2.0
Advance electrolyte (25°C) Co (g/L) 60
Advance electrolyte (25°C) Mg (g/L) 5
Advance electrolyte (25°C) Na (g/L) 16.185
Temperature (°C) 60
Recirculated electrolyte Co(g/L) 55
Exit electrolyte Co (g/L) 50
Current efficiency (%) 80

Mintek design of Cobalt electrowinning recommends 50g/L of Na2SO4 in Cobalt

electrolyte.

3.5.4.2. Mass balance

Tables (3.24) and (3.25) give the mass balance of optimal Cobalt electrowinning
unit operation

Joseph Kafumbila Page 36

 Table 3.24: Mass balance of optimal Cobalt electrowinning unit operation

1 2 3 4 5
Advance Advance Recirculated Entry Co Cathode
Electrolyte Electrolyte electrolyte Solution
(25°C) (60°C)
Solid
Mass t/h 0.565
Gas
Mass t/h
Liquid
mass t/h 71.809 71.809 59.691 131.500
volume m3/h 60.000 60.819 50.992 111.811
SG liquid t/m3 1.197 1.181 1.171 1.176
Co g/l 60.000 59.192 50.000 55.000
Mg g/l 5.000 4.933 4.943 4.937
Na g/l 16.185 15.968 16.001 15.983
S g/l 52.180 51.477 51.584 51.526
Ac (1) g/l 1.319 0.621 3.107 1.639
Ac (2) g/l 5.048 4.980 20.493 12.055
pH 2.000 2.323 1.629 1.904
Temp °C 25.000 60.000 60.000 60.000

Table 3.25: Mass balance of optimal Cobalt electrowinning unit operation

6 7 8 9 10
Oxygen Hydrogen Exit Spent Spent
Solution Electrolyte Electrolyte
(60°C) (25°C)
Solid
Mass t/h
Gas
Mass t/h 0.192 0.005
Liquid
mass t/h 130.738 71.047 71.047
volume m3/h 111.685 60.693 59.626
SG liquid t/m3 1.171 1.171 1.192
Co g/l 50.000 50.000 50.895
Mg g/l 4.943 4.943 5.031
Na g/l 16.001 16.001 16.287
S g/l 51.584 51.584 52.508
Ac (1) g/l 3.107 3.107 6.349
Ac (2) g/l 20.493 20.493 20.861
pH 1.629 1.629 1.321
Temp °C 60.000 60.000 60.000

3.5.4.3. Observations

The observations of mass balance show that:

 .Advance electrolyte (60°C) pH: 2.323.

Joseph Kafumbila Page 37

  Advance electrolyte (60°C) Acid (1) concentration: 0.621g/L.
 Advance electrolyte (60°C) Acid (2) concentration: 4.980g/L.
 Entry solution pH: 1.904
 Exit pH: 1.629
 Exit acid (1) concentration: 3.107g/L.
 Exit acid(2) concentration: 20.493g/L
 Spent electrolyte (25°C) pH: 1.3.21.
 Spent electrolyte (25°C) Acid (1) concentration: 6.349g/L.
 Spent electrolyte (25°C) Acid (2) concentration: 20.861g/L.

The presence of Magnesium and sodium in Cobalt electrolyte increases the exit
solution pH form 1.508 to 1.629. This means that the current efficiency increases and
the power consumption decreases.

Joseph Kafumbila Page 38

4. Cell and Electrode Data

Current Density
Maximum A/m² 400
Minimum A/m² 200
Current Efficiency
Maximum % 80
Minimum % 70
Cell Voltage (average) V 4
Power consumption
Maximum kWh/t Co 6
Average kWh/t Co 4.5
Operating Temperature
Maximum °C 70
Minimum °C 60
Cathode Blank Size mxm 1.0x1.0
Submerged cathode area per side m2 1.0
Cathode Blank Thickness (minimum) mm 3
Cathode Spacing mm 110
Cathodes per Cell 36
Anodes per Cell 37
Cell Construction Polymer Concrete
Cell dimensions
Internal length mm 4,520
Internal width mm 1,250
Internal height mm 1,320
Permanent Cathode Design 316 SS blade, 2mm
Cathode Deposition Cycle days 3

Joseph Kafumbila Page 39

Anode Composition (typical alloy) % Ca 0.05 - 0.10
% Sn 1.25 - 1.75
% Al 0.005 - 0.02
Balance Pb
Anode Type Solid blade, hot cross rolled
Anode Thickness mm 10
Anode consumption % per year 25
Cathode consumption % per year 10

Joseph Kafumbila Page 40

5. References
1. J. Kafumbila (1), 2023, Design of Cobalt solvent extraction using Cyanex 272
as extractant by combining McCabe Thiele procedure and simulation
program: control of Magnesium concentration in Cobalt electrowinning
circuit, Resarchgate.
(PDF) Design of Cobalt Solvent Extraction using Cyanex 272 as Extractant by
Combining McCabe Thiele Procedure and Simulation Program - Control of
Magnesium in Cobalt electrowinning circuit (researchgate.net)
2. D. Lowe et al, 1968, Electrolytic deposition of Cobalt from a sulphate
electrolyte, Neue Hutte.
3. N. Mulaudzi et al, 2013, Direct Cobalt electrowinning as an alternative to
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