Design of Cobalt Solvent Extraction and Cobalt Electrowinning Circuit From Pure Cobalt Solution

PROJECT METALLURGIST
Design of Cobalt solvent

extraction and Cobalt
electrowinning circuit from
pure Cobalt solution
KAFUMBILA KASONTA JOSEPH
2023
Design of Cobalt solvent extraction and Cobalt electrowinning circuit from pure
Cobalt solution.
© Joseph Kafumbila 2023
jokafumbila@hotmail.com
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.

Abstract
This publication presents a design procedure of cobalt solvent extraction using
Cyanex 272 as extractant and cobalt electrowinning circuit in two ways: Design
procedure using experimental tests and design procedure using Realistic Simulation
Program. In the design procedure using experimental tests, the pH-loading and the
isotherm curves are generated using Realistic Simulation Program in the only reason to
explain the design procedure. The design procedure resolves the problem of the
optimization of the extractant volume percentage in organic phase and the number of
stages by using the Cobalt recovery on extraction step as the target. Realistic Simulation
Program models the effect of temperature and the presence of sulfate salt on pH of
cobalt electrolyte in Cobalt electrowinning circuit. This facilitates the design of optimal
Cobalt electrowinning circuit.

Contents
1. Introduction 6
2. Procedure 7
2.1. Experimental methodology 7
2.2. Modeling 9
2.2.1. Concept 9
2.2.2. Realistic Simulation Program (RSP) 9
3. Extraction unit operation 10
3.1. Experimental procedure 10
3.1.1. Flow diagram 10
3.1.2. pH-loading curve 10
3.1.3. Isotherm curve 11
3.1.4. McCabe Thiele diagram 12
3.1.5. Optimal extractant volume percentage in organic 15
3.2. Modeling 19
3.2.1. Concept 19
3.2.2. Flow diagram of extraction step 19
3.2.3. Simulation 21
3.2.4. Observations 22
4. Cobalt electrowinning 23
4.1. Fundamental principle 23
4.1.1. Cathode 23
4.1.2. Anodic reaction 28
4.1.3. Cell voltage 29
4.1.4. Energy consumption 30
4.2. Simulation of Cobalt electrowinning existing unit operation 33
4.2.1. Free acid concentration in Cobalt electrowinning electrolyte 33
4.2.2. Specific gravity of solution at high temperature 35
4.2.3. Activity of soluble species 36
4.2.4. Equilibrium constant of chemical reaction 38
4.2.5. Simulation of Cobalt electrowinning existing unit operation 38

4.3. Simulation of optimal Cobalt electrowinning unit operation 47
4.3.2. Configuration pure cobalt solution 47
4.3.3. Configuration with Cobalt and Sodium 50
4.4. Cell and Electrode Data 52
5. Stripping and cobalt electrowinning unit operations 54
5.1.2. Isotherm curve 55
5.2. Modeling 59
5.2.1. Concept 59
5.3. Observations 63
6. Extraction, Stripping and cobalt electrowinning unit operations 64
6.2. Modeling 71
7. References 77

1. Introduction
Cobalt is one of high-value base metal that presents in Copper and nickel ores at
relatively low concentrations; hence, it is usually produced at low tonnages as a by-
product of Cu and Ni. The largest Co reserves and producers are located on the
Copperbelt in the Democratic Republic of Congo (DRC) and Zambia. Other important
producers include Australia, Brazil, Cuba, Russia, and China.
Cobalt is often recovered as an intermediate hydroxide or carbonate product,

which is sold to cobalt refineries to produce London Metal Exchange (LME) quality
cobalt metal. The Cobalt content of the intermediate hydroxide product is typically 17%
(m/m) when lime is used as precipitant and 35% to 40% (m/m) when MgO is used as
precipitant. The inconsistent domestic electricity supply in the DRC is a concern for
domestic Cobalt refining. Direct Cobalt electrowinning (EW) from a bleed solution of
Copper production circuit in a typical Cu-Co flow sheet presents an opportunity for
technology development to produce improved quality Co products, hence higher value,
at lower capital (capex) and operating costs (opex).
This publication presents a design procedure of cobalt solvent extraction using

Cyanex 272 as extractant and cobalt electrowinning circuit in two ways: Design
procedure using experimental tests and design procedure using Realistic Simulation
Program. In the design procedure using experimental tests, the pH-loading and the
isotherm curves are generated using Realistic Simulation Program in the only reason to
explain the design procedure. The design procedure resolves the problem of the
optimization of the extractant volume percentage in organic phase and the number of
stages by using the Cobalt recovery on extraction step as the target. Realistic Simulation
Program models the effect of temperature and the presence of sulfate salt on pH of
cobalt electrolyte in Cobalt electrowinning circuit. This facilitates the design of optimal
Cobalt electrowinning circuit.

2. Procedure
2.1. Experimental methodology

The pH-loading curves, the isotherm curve and batch counter-current test
(Figure 2.1) are most commonly used to determine metal recovery and number of
stages for a solution having a known chemical composition. Figure (2.1) gives batch
counter-current test for 5 stages where “FA” is fresh aqueous phase and “FO” is fresh
organic (Uthaiwan Injarean et al, 2014).
The pH-loading curves are used to known, on the extraction step, the pH range
of extraction of the element. The pH-loading curves are used to known, on the scrubbing
step, which element can be replaced by the main metal on the organic phase or which
element can be wash by acid solution on organic before the main metal. On the stripping
step, the pH-loading curves are used to known the pH that can be applied to strip
impurities and the main metal.
The extraction, the scrubbing or the stripping isotherm curves can be generate
by contacting a known aqueous solution (i.e. PLS, the scrub solution or the strip
solution) with the organic solution at different O/A volume ratios. The main purpose of
isotherm curves is the construction of McCabe Thiele diagram helping to obtain the
number of stages.
It is not easy to determine the impurities, that are extracted at pH high than the
main metal, the extraction efficiency using McCabe Thiele diagram. The batch counter-
current test is used for this purpose. When there are enough budgets, a pilot testing
must be done to confirm number of stages and impurity transfer.
pH – loading and isotherm curves can be done at different temperature. But the
batch counter-current test is done at room temperature.
In a design practice, the pH-loading and isotherm curves are obtained from the
lab test. In this publication, the pH-loading and isotherm curves are generated by the
simulation program in the only goal to explain the methodology of cobalt solvent
extraction.

Figure 2.1: Batch counter-current scheme used for extraction

2.2. Modeling
2.2.1. Concept
Simulation program is developed to significantly simplify the overall circuit
design for solvent extraction plants. The simulation program calculates the
simultaneous equations of multiple equilibrium systems based on pre-generated
equilibrium data. The pre-generated equilibrium data cover various metals, metal
concentrations, acidities, extractant volume percent and temperatures.
For ordinary simulation program, given a known feed composition, the O/A
ratio, the targeted equilibrium pH, the expected stage mixing efficiency and the
extractant volume percent, the program calculates the aqueous and organic mixer outlet
composition from equilibrium database.
The advantageous of simulation program is that the overall plant (extraction,

scrubbing and stripping) can be simulated simultaneously.
2.2.2. Realistic Simulation Program (RSP)

In this way, Realistic Simulation Program (RSP) has been developed to simulate
Copper and Cobalt hydrometallurgical circuits. The program of RSP is based on the
thermodynamic equilibrium of soluble species in the solution. The models of copper
solvent extraction using Lix984N and Cobalt solvent extraction using Cyanex 272 have
been developed for Realistic Simulation Program (RSP) (J. Kafumbila, 2023).
These models have been developed for room temperature only. It is known that
the increase of temperature increases the equilibrium constant of Cobalt extraction with
Cyanex 272 (H.A. Evans, 2008). Another work shows that the maximum extraction
efficiency of cobalt using Cyanex 272 is obtained at 35°C (D. Kyembo, 2015).
Comparatively other simulation program, Realistic Simulation Program can

optimize the extractant volume percent for known feed composition, the O/A ratio, the
targeted equilibrium pH, the expected stage mixing efficiency, number of stages and
metal recovery.

3. Extraction unit operation
3.1. Experimental procedure
3.1.1. Flow diagram

Figure (3.1) gives the flow diagram of Extraction step. The cobalt rich solution
contains 2g/L of Cobalt.
Figure 3.1: Flow diagram of extraction step
3.1.2. pH-loading curve

pH-loading curve is developed for a rich solution containing 2g/L of Co and at
pH 4.5. Realistic Simulation Program is used to develop pH-loading curve at room
temperature. Figure (3.2) gives the pH-loading curve for solution containing 2g/L of Co
at initial pH 4.5 with organic phase containing 8% of Cyanex 272 at room temperature
(O/A=1). NaOH solution containing 100g/L of NaOH is used as acid neutralization
reagent.
The results show that pH50 (pH against 50% of Cobalt extraction) is 4.64. At
99% of Cobalt extraction pH is 6.4. The optimal pH of Cobalt solvent extraction is taken
as 5.5 (middle of pH50 and pH99).

Figure 3.2: pH-loading curve for solution containing 2g/L of Co with organic phase
containing 8.0% of Cyanex 272 at room temperature (O/A=1) generated by
RSP
3.1.3. Isotherm curve

Table (3.1) gives the values of Cobalt concentration in the isotherm curve
generated by RSP for a solution containing 2g/L of Cobalt at initial pH of 4.5 at room
temperature. Volume percent of Cyanex 272 is 8.0% and the isotherm pH is 5.5. NaOH
solution containing 100g/L of NaOH is used as acid neutralization reagent. Figure (3.3)
illustrates Cobalt isotherm curve (blue line).
Table 3.1: Values of Cobalt isotherm curve for solution containing 2g/L of Co at pH 5.5 with
organic phase containing 8.0% v/v of Cyanex 272 at room temperature by RSP
O/A Cobalt concentration (g/L)

Organic Aqueous
10.00 0.199 0.011
5.00 0.395 0.024
3.50 0.561 0.037
2.50 0.777 0.057
2.00 0.961 0.077
1.50 1.254 0.117
1.00 1.774 0.220
0.50 2.721 0.628
0.20 3.372 1.313
0.10 3.555 1.636

Figure 3.3: Cobalt isotherm curve for solution containing 2g/L of Co at pH 5.5 with organic
phase containing 8% v/v of Cyanex 272 at room temperature generated by RSP
3.1.4. McCabe Thiele diagram

Figure (3.4) gives McCabe Thiele diagram of a stage on extraction train. The
procedure of McCabe Thiele construction of Cobalt based on Figure (3.4) is the
following:
Figure 3.4: McCabe Thiele of stage on extraction train

 Equation (3.1) gives the extrapolation mathematical expression of
isotherm curve of Cobalt for solution containing 2g/L of Co at pH 5.5
with organic phase containing 8% v/v of Cyanex 272 at room
Co
temperature generated by RSP (J. Kafumbila. 2017). Where “COrg ” is the
Co
Cobalt concentration in organic phase (g/L) and “Caq ” is Cobalt
concentration in aqueous phase (g/L).
Co Co 2 Co
Log(COrg )=-0.18*(log(Caq )) +0.2658*log(Caq )+0.50 (3.1)
 The construction starts by the first stage on the extraction (stage 1).
A
 The concentration in aqueous in point (A) (Caq ) is Cobalt concentration
in aqueous in the feed solution (2g/L).
A
 The concentration in organic in point (A) (Cor ) is calculated using
Equation (3.2) (on the operating line).
A CA
aq
Cor = (O/A) (3.2)
B
 The concentration in organic in point (B) (Cor ) is equal to the
A
concentration in organic in point (A) (Cor ).
B
 The concentration in aqueous in point (B) (Caq ) is random number less
A
than the concentration in aqueous in point A (Caq )(2g/L).
B
 The concentration in aqueous in point (C) (Caq ) is equal to the
B
concentration in aqueous in point B (Caq ).
A
 The concentration in organic in point (C) (Cor ) is calculated using
C CCaq
Cor = (O/A) (3.3)
.
E
 The concentration in aqueous in point (E) (Caq ) is calculated using
Equation (3.4) where “MF” is mixing efficiency.
E A (CA B
aq −Caq )
Caq =Caq - (3.4)
MF

E
 The concentration in organic in point (E) (Cor ) is calculated using
Equation (3.5).
(CB C
E C or −Cor )
Cor =Cor + (3.5)
MF
E
 The concentration in organic in point (E) (Cor ) is calculated also using
Equation (3.6).
E E
Log(COrg )=-0.18*(log(Caq ))2+0.2658*log(Caq
E
)+0.50 (3.6)
B
 The value of concentration in aqueous in point (B) (Caq ) is optimized
using Excel solver where the variable is the concentration in aqueous in
B
point (B) (Caq ) and the constraint is that the concentration in organic in
E
point E (Cor ) calculated with Equations (3.5) and (3.6) are equals.
 Repeat the procedure for the second stage where the coordinates of
point (C) of first stage are equal to the coordinates of point (A) in the
B
second stage. The value of concentration in aqueous in point (B) (Caq ) is
optimized using Excel solver where the variable is the concentration in
B
aqueous in point (B) (Caq ) and the constraint is that the concentration in
E
organic in point E (Cor ) calculated with Equations (3.5) and (3.6) are
equals.
 Repeat the procedure for the third stage where the coordinates of point
(C) of second stage are equal to the coordinates of point (A) in the third
B
stage. The value of concentration in aqueous in point (B) (Caq ) is
B
E
equals.
Table (3.2) gives the coordinates of points (A, B, C and E) in 3 stages on the
McCabe Thiele diagram (Number of stage=3, Mixing efficiency=90%, concentration of
Cyanex 272 in organic=8%, room temperature=25°C, pH=5.5 and Cobalt
efficiency=99%). Figure (3.5) gives the McCabe Thiele from Table (3.2)
The results shows that Cobalt concentration in the raffinate with 8% of Cyanex
272 in organic, 90% of mixing efficiency, 3 stages at room temperature, pH 5.5, and 1.25
of O/A ratio is 0.009 g/L. (O/A) ratio gives the organic continuous regime in the mixer
that gives lower aqueous entrainment in organic.

Table (3.2): Coordinates of points (A, B, C, and E) (Number of stage=3, Mixing efficiency=90%,
concentration of Cyanex 272 in organic=8%, room temperature=25°C, pH=5.5 and
Cobalt efficiency 99%)
Cobalt concentration (g/L)

Aqueous Organic
2.000 1.600 A
0.393 1.600 B
Stage 1
0.393 0.314 C
0.214 1.743 E
0.393 0.314 A
0.058 0.314 B
Stage 2
0.058 0.046 C
0.020 0.344 E
0.058 0.046 A
0.009 0.046 B
Stage 3
0.009 0.007 C
0.003 0.050 E
Figure (3.5): McCabe Thiele diagram (Number of stage=3, Mixing efficiency=90%,

concentration of Cyanex 272 in organic=8%, room temperature=25°c, Cobalt
efficiency 99%, pH=5.5 and 0/A ratio=1.25)
3.1.5. Optimal extractant volume percentage in organic

Extractant volume percentage in organic of 8% of Cyanex 272 is not the optimal
concentration to have 0.02 g/L of Cobalt in raffinate with (O/A) ratio of 1.25, 90% of
mixing efficiency and 3 stages at room temperature and pH 5.5. The isotherm curves are

generated for 6%, 8%, 10% and 12% by RSP at room temperature and pH 5.5. Equation
(3.7) gives the extrapolation Equation of isotherm. Where “a”, “b” and “c” are variables
whose values depend on the value of extractant volume percentage in organic phase.
The values of “a”, “b” and “c” are given by Equations (3.8), (3.9) and (3.9). Where
(v/v%) is the extractant volume percentage in organic.
E E
Log(COrg )=a*(log(Caq ))2+b*log(Caq
E
)+c (3.7)
a=-5.00*10−5 *(v/v%)2 +3.02*10−3*(v/v%)-0.2011 (3.8)
b=1.719*10−3 *(v/v%)2 -5.458*10−2 *(v/v%)+0.5936 (3.9)
b=-4.694*10−3*(v/v%)2 +1.536*10−1*(v/v%)-0.4315 (3.10)
procedure of McCabe Thiele construction of Cobalt based on Figure (3.4) is the following
to obtain the optimal extractant volume percentage in organic:
 The initial value of the extractant volume percentage in the organic

phase is the lowest (6%). This value gives the values of variable “a”, “b”
and “c” for the extrapolation Equation of isotherm curve.
A
A
 The concentration in organic in point (A) (Cor ) is calculated using
A CA
aq
Cor = (O/A) (3.2)
B
A
B
A
B
B

A
C CCaq
Cor = (O/A) (3.3)
.
E
E A (CA B
aq −Caq )
Caq =Caq - (3.4)
MF
E
Equation (3.5).
(CB C
E C or −Cor )
Cor =Cor + (3.5)
MF
E
Equation (3.11).
E E
E
)+c (3.11)
B
B
E
B
B
E
equals.
stage. The value of concentration in aqueous in point (C) is equal to 0.02.
The value of (v/v%) is optimized using Excel solver where the variable is
the value (v/v%) and the constraint is that the concentration in organic
E
in point E (Cor ) calculated with Equations (3.5) and (3.11) are equals.

McCabe Thiele diagram (Number of stage=3, (O/A)=1.25, Mixing efficiency=90%, room
temperature=25°C, pH=5.5 and Cobalt efficiency=99%). The optimal (v/v%) is equal to
6.521%.
The isotherm curve is generated for solution containing 2g/L of cobalt and
organic containing 6.521% of volume percentage of Cyanex 272 at room temperature
(25°C) and pH of 5.5. Table (3.4) gives the values of cobalt concentrations for the
isotherm. Figure (3.6) gives the McCabe Thiele from Table (3.3)
Table (3.3): Coordinates of points (A, B, C, and E) (Number of stage=3, (O/A)=1.25, Mixing
efficiency=90%, concentration of Cyanex 272 in organic=6.521%, room
temperature=25°C, pH=5.5 and Cobalt efficiency 99%)

Aqueous Organic
2.000 1.600 A
0.597 1.600 B
Stage 1
0.597 0.477 C
0.441 1.725 E
0.597 0.477 A
0.114 0.477 B
Stage 2
0.114 0.091 C
0.060 0.520 E
0.114 0.091 A
0.020 0.091 B
Stage 3
0.020 0.016 C
0.010 0.099 E
Table 3.4: Values of Cobalt isotherm curve for solution containing 2g/L of Co at pH 5.5 with
organic phase containing 6.521% v/v of Cyanex 272 at room temperature by RSP

Organic Organic
10.00 0.198 0.019
5.00 0.391 0.042
3.50 0.553 0.064
2.50 0.759 0.100
2.00 0.930 0.136
1.50 1.193 0.206
1.00 1.616 0.376
0.50 2.241 0.866
0.20 2.627 1.464
0.10 2.741 1.719

Figure (3.6): McCabe Thiele diagram (Number of stage=3, (O/A)=1.25, Mixing efficiency=90%,
concentration of Cyanex 272 in organic=6.521%, room temperature=25°c, Cobalt
efficiency 99% and pH=5.5)
3.2. Modeling
3.2.1. Concept
The modeling of extraction step of Cobalt solvent extraction takes account the
flow rate of NaOH solution used for acid neutralization and the aqueous entrainment in
organic phase.
3.2.2. Flow diagram of extraction step
3.2.2.1. Flow diagram
Figure (3.7) gives the flow diagram of extraction circuit having “n” stages.

Figure 3.7: From diagram of extraction step with “n” stages
Abbreviations of unit operations:
 Extraction Ep: Stage of rank “p” in Extraction train
Abbreviations of lines between unit operations:
 RS: Rich solution.

 EpRaf: Raffinate of stage of rank “p”.
 SO: Stripped organic
 EpLO: Loaded organic of stage of rank “p” in extraction train.
 ASO: Aqueous entrainment of stripped organic.
 EpALO: Aqueous entrainment of loaded organic of stage of rank “p” in
extraction train.
 EpNa: NaOH solution of stage of rank “p” in extraction train.
3.2.2.2. Plant description
Rich solution is fed to the first stage of extraction train. The raffinate of
extraction stage of rank “p-1” is fed to the extraction stage of rank (p). The raffinate of
extraction stage of rank “n” is final raffinate. Stripped organic is fed to extraction stage of
rank “n”. The loaded organic of extraction stage of rank “p+1” is fed to extraction stage
of rank “p”. The loaded organic of extraction stage 1 is the final loaded organic. During
this process, Cobalt is extracted from solution to organic phase and organic phase
releases hydrogen ions in aqueous phase. NaOH solution is added in each stage to
maintain the pH at the target value.

3.2.3. Simulation
3.2.3.1. Design Criteria
Design criteria of extraction circuit mass balance are the following:
 Rich solution composition:

o Cobalt: 2g/L.
o pH: 4.5.
 Type of extractant: Cyanex 272.
 O/A ratio:
o External: 1.25.
o Internal: 1.25
 Number of stage: 3.
 Mixing efficiency:
o Stage E1: 90%.
o Stage E2: 90%.
o Stage E3: 90%
 Aqueous entrainment in organic:
o Stage E1: 500ppm.
o Stage E2: 500ppm.
o Stage E3: 500ppm
 Cobalt loss in extraction stage 3 raffinate: 1% of Cobalt in the rich
solution
 NaOH concentration: 100g/L of NaOH in NaOH solution.
 pH profile:
o Stage E1: 5.5.
o Stage E2: 5.5.
o Stage E3: 5.5
3.2.3.2. Simulation results
Table (3.5) gives the summary results. Tables (3.6 and 3.7) give the mass
balance results.

Table 3.5: Summary results
Extractant volume percentage 6.390 %

LO flow rate 250 m3/h
NaOH consumption 537.99 kg/h
Recovery Co
Global 99.00 %
E1 68.89 %
E2 80.52 %
E3 83.47 %
Table 3.6: Mass balance of extraction step with 3 stages
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

RS E1Na E2LO E2ALO E1Raf E1LO E1ALO E2Na
Liquid
mass t/h 201.022 4.088 0.125 204.844 0.125 1.483
volume m3/h 200.000 3.746 250.000 0.124 203.880 250.000 0.124 1.359
SG liquid t/m3 1.005 1.091 1.005 1.005 1.005 1.091
Co g/l 2.000 0.481 0.118 0.610 1.584 0.610
Na g/l 0.000 57.475 1.430 1.056 1.056 57.475
S g/l 1.089 1.061 1.069 1.069
Ac g/l 0.004 0.000 0.000 0.000
pH g/l 4.500 5.500 5.500 5.500
9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00

E3LO E3ALO E2Raf E3Na SO ASO E3Raf
Liquid
mass t/h 0.125 206.231 0.299 206.386
volume m3/h 250.000 0.124 205.288 0.274 250.000 205.448
SG liquid t/m3 1.005 1.005 1.091 1.005
Co g/l 0.081 0.019 0.118 0.000 0.019
Na g/l 1.504 1.430 57.475 1.504
S g/l 1.060 1.061 1.060
Ac g/l 0.000 0.000 0.000
pH g/l 5.500 5.500 5.500
3.2.4. Observations
The optimal value of extractant volume percentage in the organic is about
6.39% lower than 6.521% obtained using experimental procedure. The decrease of
optimal value of extractant volume percentage in organic is due to the dilution of
aqueous caused by introduction of NaOH solution.

4. Cobalt electrowinning
4.1. Fundamental principle
4.1.1. Cathode
4.1.1.1. First group of chemical reactions
4.1.1.1.1. 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(3.a) =-0.28V (25°C) (4.a)
°
2H + + 2e− = H2 ‘ Eh(3.b) =0.000V (25°C) (4.b)
Equation (4.1) gives the current density which is the sum of current densities
used respectively for the chemical reactions (4.a) and (4.b). Where “ic ” is cathodic
current density (A/m2), “i(4.a) ” is current density used to plate Cobalt (A/m2) and “i(4.b) ”
is current density used to produce hydrogen gas (A/m2).
ic =i(4.a) +i(4.b) (4.1)
The kinetic of the electrochemical reaction is defined by Tafel Equation

(electron transfer rate). Tafel Equation (Equation (4.2)) 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) (4.2)
4.1.1.1.2. Current density (𝐢(𝟒.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):
H + +e− =Hads (Volmer reaction) (4.c)
H + +Hads +e− =H2 (Heyrovsky reaction) (4.d)
2Hads =H2 (Tafel reaction) (4.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 (4.3) gives Tafel Equation of hydrogen evolution. Value of Tafel slope
of hydrogen evolution depends on the nature of the electrode.
ρ(4.b) =a(4.b) +b(4.b)*log(i(4.b) ) (4.3)
Equation (4.4) gives the over potential of the chemical reaction (4.b). “ρ(4.b) ” is
°
hydrogen over-potential (V), “Eh(4.b) ” is standard potential of reaction (4.b) (0.0V) and
“E(c) ” is cathodic potential (V).
°
ρ(4.b) =E(c) - Eh(4.b) (4.4)
4.1.1.1.3. Current density (𝐢(𝟒.𝐚) )
Equation (4.5) 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 (4.5)
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 (4.6) gives Tafel Equation of Cobalt plating.
ρ(4.a) =a(4.a) +b(4.a) *log(i(4.a)) (4.6)

Equation (4.7) gives the over potential of the chemical reaction (4.a). “ρ(4.a) ” is
°
Cobalt plating over-potential (V), “E(4.a) ” is standard potential of reaction (4.a) (-0.28V)
and “E(c) ” is cathodic potential (V).
°
ρ(4.a) =E(c) - Eh(4.a) (4.7)
The mass of Cobalt deposited on the cathode is given by Faradays law. Faraday
law is given by Equation (4.8). 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 (4.8)
2
The values of current amperage and current efficiency are given by Equations
(4.9) and (4.10). Where “I” is the current amperage (A), “A” is the cathode active area
(m2) and “CE(4.a) ” is current efficiency.
I =i(4.a) *A (4.9)
i(4.a)
CE(4.a) = (4.10)
i(c)
4.1.1.2. Second group of chemical reactions
4.1.1.2.1. 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(3.f) =0.000V (25°C) (4.f)
°
Coo = Co+2 + 2e− Eh(3.g) =-0.28V (25°C) (4.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.

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.
4.1.1.2.2. Cathodic potential
The cathodic potential decreases from potential E(4.f) when the global current is
corr
zero to the potential E(4.f) where the global current is corrosion current (I(4.f) ). Equation
(4.11) gives the value of E(4.f) . Equation (4.12) 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(4.f) ” is cathodic over-potential.
2.303∗R∗T a +
°
E(4.f) =E(4.f) + *log(C(H ) ) (4.11)
F (H2 )
corr
ρ(4.f) =E(4.f) - E(4.f) = a(4.f) -b(3.f) *log(I(4.f) ) (4.12)
4.1.1.2.3. Anodic potential
The anodic potential increases from potential E(4.g) when the global current is
corr
zero to the potential E(4.g) where the global current is corrosion current (I(4.g)). Equation
(4.13) gives the value of E(4.g) . Equation (4.14) 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(4.g) ” is anodic over-potential.
2.303∗R∗T a(Co+2 )
°
E(4.g) =E(4.g) + *log( ) (4.13)
2∗F aCo
corr
ρ(4.g) =E(4.g) -E(4.g) =a(4.g) +b(4.g) *log(I(4.g)) (4.14)

4.1.1.2.4. Cobalt cathode electrical resistance potential
corr corr
The difference between E(4.f) and E(4.g) is the over-potential due to the electrical
resistance of Cobalt metal (Equation 4.15). Where “R” is the electrical resistance of
Cobalt metal.
corr corr
E(4.f) -E(4.g) =R*Icorr (4.15)
4.1.1.2.5. Global over-potential
The difference between E(4.f) and E(4.g) gives the global over-potential (Equation
4.16). Where “ρ(3.f) ” is cathodic over-potential, “ρ(3.g)” is anodic over-potential, and “R” is
the electrical resistance of the metal. Equation (4.17) gives the correlation between Icorr ,
I(3.f) and I(3.g)
E(4.f) - E(4.g) =ρ(4.g) + R*Icorr - ρ(4.f) (4.16)
Icorr =I(4.f) =I(4.g) (4.17)
Figure (4.1) gives the polarization curves of the corrosion of Cobalt metal in the
acidified water.
Figure 4.1: Polarization of anodic and cathodic reactions to reach corrosion potential

4.1.1.2.6. 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).
The co-deposition of same impurities that present lower value of Tafel slope of
hydrogen evolution can affect greatly the current efficiency. In the case of Zinc, the co-
deposition of these impurities (Co, Ni, Cu, Ge, Te, Sb and Se) affects greatly the current
efficiency.
4.1.2. Anodic reaction

Electrochemical reactions at the anode surface are given by the chemical
reaction (4.h).
1 °
H2 O = 2H + + 2 O2 + 2e− Eh(3.h) =1.23V (25°C) (4.h)
One of the more generally accepted pathways of oxygen evolution consists of

reactions (4.i), (4.j) and (4.k) (Fabbri, E. et al, 2014).
OH − =OHads +e− (4.i)
OH − +OHads =H2 O+e− +Oads (4.j)
2Oads =O2 (4.k)
The mass of oxygen gas produced is the mass of oxygen produced by the
chemical reaction (4.h). The mass of oxygen gas on the anode is given by Faradays law.
Faraday law is given by Equation (4.18). 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 (4.18)
4
The values of current amperage and current efficiency are given by Equations
(4.19) and (4.20). 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(3.h) ” is
global oxygen current efficiency, and “i(a) ” is anodic current density.

I =i(4.h) *A (4.19)
i(4.h)
CE(4.h) = (4.20)
i(a)
4.1.3. Cell voltage

The chemical reactions (4.a) on the cathode and (4.h) on the anode are used to
calculated the cell voltage.
Equation (4.21) gives the value of operating cell voltage. Where “VRCo ” is the
reversible voltage, “ρ(4.a) ” is absolute value of cathode over-potential, “ρ(4.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.
VOC = VRCo + ρ(3.a) + ρ(2.h) + Vῼc +VOῼi +VOῼe (4.21)
4.1.3.1. Reversible voltage

°
Reversible voltage (VRCo ) is given by Equation (4.22). Where “E(4.h) ” is the
°
electrode standard potential of the chemical reaction (4.h) at 25°C (1.23 V) and “E(4.a) ”
is the electrode standard potential of the chemical reaction (4.a) at 25°C (-0.28V).
° °
VRCo = E(4.h) - E(4.a) (4.22)
4.1.3.2. Over potential of Cobalt on the cathode
Equation (4.23) gives the cathodic Cobalt over potential. Where “ρ(4.a) ” is Cobalt
over-potential (V) and “Iex ” is Cobalt exchange current density (A/m2 ), “b(4.a) ” is Tafel
slope and “I(4.a) ” is Cobalt current density (A/m2 ).
Iex
ρ(4.a) =b(4.a) *log(I ) (4.23)
(4.a)
4.1.3.3. Over potential of oxygen on the anode
Equation (4.24) gives the anodic over potential of oxygen evolution. Where
“ρ(4.h) ” is oxygen over potential (V) and “I(4.h) ” is oxygen current density (A/m2 ), “b(4.h) ”
is Tafel slope and “Iex ” is exchange current density (A/m2 ).

I(4.h)
ρ(4.h) =b(4.h) *log( ) (4.24)
Iex
4.1.3.4. 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.
4.1.3.5. Electrode internal resistance voltage drop
Equation (4.25) 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
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 (4.25)
4.1.3.6. Electrolyte resistance voltage drop
Equation (4.26) 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 (4.26)
4.1.4. Energy consumption
The energy consumption for an electrowinning cell is calculated according to

Equation (4.27). 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 = (4.27)
MCo

4.1.5. 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 (4.2) shows the Cobalt current efficiency versus pH at
20°C and 60°C at 200A/m2 (R. Breckpot et al, 1969).
Figure (4.2): 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 (4.2) 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.
 For pH greater than 3.6, Cobalt deposit is brittle. Between pH 2.4 and 3.6,
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 the 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.

4.2. Simulation of Cobalt electrowinning existing unit
operation
4.2.1. Free acid concentration in Cobalt electrowinning

electrolyte
4.2.1.1. 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 (4.l), (4.m)
and (4.n) give the equilibrium reactions of soluble compounds.
H + +SO−2 −
4 =HSO4 (4.l)
2H + +SO−2
4 =H2 SO4 (4.m)
Co+2 +SO−2
4 =CoSO4 (4.n)
pH and total Cobalt concentration are known values. Equations (4.28) and
(4.29) give 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+) = (4.28)
γ( H+ )
C( CoT) =C(Co+2 )+C( CoSO4) (4.29)
The concentration of CoSO4 (C( CoSO4 )) is given by Equation (4.30). Where

“K ( 4.n) ” is equilibrium constant of chemical reaction (4.n). The concentration of HSO−
4
(C( HSO−4 ) ) and H2 SO4 (C(H2 SO4 )) are given by Equations (4.31) and (4.32).
γ(Co+2 ) ∗γ( SO−2 )

C( CoSO4 ) =K ( 4.n)*C(Co+2 )*C(SO−2
4 )
* 4
(4.30)
γ( C( CoSO ) )
4
γ(H+ ) ∗γ( SO−2 )

C(HSO−4 ) =K ( 4.l)*C(H+ ) *C(SO−2
4 )
* 4
(4.31)
γ( C − ))
(HSO4

(C(H+ ) )2 ∗γ( SO−2 )
C(H2 SO4 ) =K ( 4.m) *(C(H+) )2 *C(SO−2
4 )
* 4
(4.32)
γ( C(H SO ) )
2 4
Equation (4.33) gives the electrical neutrality of solution. The resolution of

Equations (4.29), (4.30), (4.31), (4.32) and (4.33) 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 )
(4.33)
Hydrogen ions (H + ) are in electrical charge equilibrium with anion (HSO− 4 ).

Equation (4.34) gives the concentration (G(H2 SO4)) (g/L) of free acid in solution. Where
“98.075” is molar mass of H2 SO4 . Equation (4.35) 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 ≃ 10−pH *98.075 (4.34)
G(ST) )=( C( CoSO4) +C(HSO−4 ) +C(H2 SO4 ) +C(SO−2

4 )
)*32.065 (4.35)
This value of acid concentration in solution obtained by using Equation (4.34) is

used in Realistic Simulation Program (J. Kafumbila (2), 2023), by R. Breckpot (R.
Breckpot et al, 1969) and by Umicore Cobalt electrowinning design.
4.2.1.2. Second free acid concentration
The pure solution of Cobalt in sulfate medium contains the following soluble
substances: H2 SO4 and CoSO4 . Equation (4.36) 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 (4.36)
This value of acid concentration in solution obtained by using Equation (4.36) 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), Luilu-Gecamines (DRC), Chambishi (Zambia) and Nkana (Zambia).

4.2.2. Specific gravity of solution at high temperature
Equation (4.37) 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 (4.37)
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 that is given in Table
(4.1) give water volume (25°C).
Table 4.1: 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).

 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)
4.2.3. Activity of soluble species
4.2.3.1. Ionic strength
The ionic strength of the system is given by Equation (4.38). Where “Cp ” is the
concentration (mole/L) of soluble compound “p” and “Zp ” is electrical charge of the
soluble compound “p”.
1
I = 2x∑ Cp ∗ Zp2 (4.38)
4.2.3.2. Water activity
The activity of water (solvent) (𝑎𝑤 ) is given by Equation (4.39). “ϕ” is the
osmotic coefficient, “W” is the molecular weight of water (18.016) and “𝑚𝑝 ” is the
concentration (mole/kg water) of soluble compound “p” (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 (4.39) becomes Equation (4.40).
W
ln (aw ) = - 1000 *ϕ *∑p mp (4.39)
W
ln (aw ) = - 1000 *ϕ *∑p Cp (4.40)
The calculations of osmotic coefficient have been approximated by Equation

(4.41) (H.C. Helgeson, 1969). The value of “u” is given by Equation (4.42). Table (4.2)
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 (4.3). “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] + + + (4.41)
a3 ∗I 2 3 4
u=1+a*√I (4.42)

Table 4.2: 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
4.2.3.3. Activity coefficients
Activity of soluble compound “p” in water is given by Equation (4.43). “γp ” is

activity coefficient and Cp is the concentration (mole/L) of soluble compound “p”.
ai = γp * Cp (4.43)
The calculations of individual ion activity coefficient have been approximated by

Equation (4.44) in concentrated as well as dilute electrolyte solutions involved in
geochemical processes at high temperatures and pressures (H.C. Helgeson et al, 1981)
and suitable for overall equilibrium diagram calculations. “γp ” Is the activity coefficient
of soluble compound “p”, “Zp ” is the electrical charge of compound “p” 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 (4.3) gives values of parameters “A”,
“B” and “b” at different temperatures (B. Beverskog et al, 1998). “ä” (in angstrom) is a
distance of closest approach, which may be taken to be equal to that of NaCl (3.72
10−10m).
Z2p A√I
Log(γp )= - (1+Bä√I) – log(1+0.018015*I)+b*I (4.44)
Table 4.3: 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).

4.2.4. Equilibrium constant of chemical reaction
The simplest assumption to be made is that the heat capacity change of reaction
is zero at all temperatures (i.e., the standard molar enthalpy of reaction does not vary
with temperature). In that case; Equation (4.45) gives the values of equilibrium constant
at temperature different of 25°C (298°K) (Ignasi Puigdomenech et al, 1999). Where
“K °(T) ” is equilibrium constant of chemical reaction at temperature (T°K), “K °(298) ” is
°
equilibrium constant of chemical reaction at temperature (298°K), “ΔH(298) ” is the
enthalpy of the chemical reaction at 298°K, “T” is temperature in degree kelvin and “R”
is equal to 8.314 (J/(mol*K).
ΔH°(298) 1 1
Log(K °(T) )=log(K °(298) )+ *( - ) (4.45)
R∗ln(10) 298 T
The values of equilibrium constant at 25°C (K °(T) ) of chemical reactions (4.l),

(4.m) and (4.n) are given in the Realistic Simulation Program (J. Kafumbila (2), 2023).
Table (4.4) gives the values of enthalpy of chemical reactions (4.l), (4.m) and (4.n) at
25°C.
Table (4.4): Enthalpy of reaction at 25°C
Reaction ° Reference
Enthalpy (ΔH(298) ) J/mole
3.l 22,000.00 MINTEQA2-V.4, 1999
3.m 0.00 MINTEQA2-V.4, 1999
3.n 6,200.00 MINTEQA2-V.4, 1999
4.2.5. 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.
4.2.5.1. Luilu Gecamines (DRCongo)
4.2.5.1.1. Flow diagram
Figure (4.3) gives the flow diagram of Cobalt electrowinning unit operation

Figure 4.3: Flow diagram of Cobalt electrowinning unit operation
4.2.5.1.2. Design criteria
Table (4.5) gives design criteria of Luilu Cobalt electrowinning unit operation.
Table 4.5: 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
4.2.5.1.3. Mass balance
Table (4.6) gives the mass balance of Luilu Cobalt electrowinning unit operation
Table 4.6: 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 70.00 70.00

4.2.5.1.4. 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.
4.2.5.2. Nkana (Zambia)
Table (4.7) gives design criteria of Nkana Cobalt electrowinning unit operation.
Table 4.7: Nkana design criteria of Cobalt electrowinning unit operation
Description Values
Entry acid (2) (g/L) 2.0
Entry Co (g/L) 40
Exit acid (2) (g/L) 10.0
Table (4.8) gives the mass balance of Nkana Cobalt electrowinning unit
operation

Table 4.8: 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
 Exit Cobalt concentration is 35.21 g/L (ΔCo = 4.79 g/L).

 Cobalt deposit structure is ductile.
4.2.5.3. Chambishi (Zambia)
Table (4.9) gives design criteria of Chambishi Cobalt electrowinning unit

operation.

Table 4.9: Chambishi design criteria of Cobalt electrowinning unit operation
Description Values
Entry pH 6.3
Entry Co (g/L) 40
Exit pH 1.9
Table (4.10) gives the mass balance of Chambishi Cobalt electrowinning unit
operation
Table 4.10: Mass balance of Chambishi Cobalt electrowinning unit operation
1.00 2.00 3.00 4.00 5.00

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


4.2.5.4. Mintek (South Africa)
Table (4.11) gives design criteria of Mintek Cobalt electrowinning unit

operation.
Table 4.11: Mintek design criteria of Cobalt electrowinning unit operation
Description Values
Entry pH 3.0
Entry Co (g/L) 55
Entry Na2SO4 (g/L) 50
ΔCo (g/L) 5.0
The soluble compounds of sodium sulfate in solution are: Na+ and NaSO− 4 . The
chemical reaction (4.o) gives the equilibrium reaction of soluble compounds. The value
of equilibrium constant is given in Realistic Simulation Program (J. Kafumbila (2), 2023).
The value of enthalpy is 1,000.00 J/mole (MINTEQA2-V.4, 1999).
Na+ +SO−2 −
4 =NaSO4 (4.o)
Table (4.12) gives the mass balance of Mintek Cobalt electrowinning unit
operation

Table 4.12: Mass balance of Mintek Cobalt electrowinning unit operation
1.00 2.00 3.00 4.000 5.00

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

 Exit acid (1) concentration is 1.304g/L
4.2.5.5. Umicore (Belgium)
Figure (4.4) gives the flow diagram of Umicore Cobalt electrowinning unit
operation

Figure 4.4: Flow diagram of Umicore Cobalt electrowinning unit operation
Table (4.12) gives design criteria of Umicore Cobalt electrowinning unit

operation.
Table 4.12: Umicore design criteria of Cobalt electrowinning unit operation
Description Values
Advance electrolyte pH 2.5
Advance electrolyte Co (g/L) 60
Entry solution Co (g/L) 45
Entry solution pH Between 1.5 and 1.8
Spent electrolyte Co (g/L) 40
Tables (4.13) and (4.14) give the mass balance of Umicore Cobalt
electrowinning unit operation

Table 4.13: 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 4.14: 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
 Exit acid(2) concentration is 36.979 g/L

 Cobalt deposit structure is ductile.

4.3. Simulation of optimal Cobalt electrowinning unit
operation
4.3.1. Flow diagram

Figure (4.5) gives the flow diagram of optimal Cobalt electrowinning unit
operation
Figure 4.5: Flow diagram of optimal Cobalt electrowinning unit operation
4.3.2. Configuration pure cobalt solution
4.3.2.1. Design criteria
Table (4.15) gives design criteria of optimal Cobalt electrowinning unit

operation.

Table 4.15: 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
Entry solution Co(g/L) 55
Entry solution pH less than 2.0
Exit electrolyte Co (g/L) 50
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 less than 2.0 (ductile structure of Cobalt deposit). The temperature of 60°C is to
decrease the water evaporation (N. Mulaudzi et al, 2013).
4.3.2.2. Mass balance
Tables (4.16) and (4.17) give the mass balance of optimal Cobalt electrowinning
unit operation
Table 4.16: 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

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

 Advance electrolyte (60°C) Acid (1) concentration: 0.689g/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.
The results show that the increase in temperature leads to higher pH, lower
acid(1) concentration and the same value of acid(2) concentration.

4.3.3. Configuration with Cobalt and Sodium
4.3.3.1. Design criteria
Table (4.18) gives design criteria of optimal Cobalt electrowinning unit

operation.
Table 4.18: 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) Na (g/L) 16.185
Recirculated electrolyte Co(g/L) 55
Exit electrolyte Co (g/L) 50
Sodium sulfate is added in the advance electrolyte to reach 50g/L of Na2SO4.
4.3.3.2. Mass balance
Tables (4.19) and (4.20) give the 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 0.564
Gas
Mass t/h
Liquid
mass t/h 70.763 70.763 58.713 129.476
volume m3/h 60.000 60.825 50.921 111.747
SG liquid t/m3 1.179 1.163 1.153 1.159
Co g/l 60.000 59.186 50.000 55.000
Na g/l 16.185 15.966 15.996 15.979
S g/l 45.506 44.889 44.973 44.927
Ac (1) g/l 1.349 0.639 3.391 1.749
Ac (2) g/l 4.804 4.739 20.219 11.793
pH 2.000 2.322 1.602 1.887
Temp °C 25.000 60.000 60.000 60.000

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 128.715 70.002 70.002
volume m3/h 111.633 60.712 59.640
SG liquid t/m3 1.153 1.153 1.174
Co g/l 50.000 50.000 50.898
Na g/l 15.996 15.996 16.283
S g/l 44.973 44.973 45.781
Ac (1) g/l 3.391 3.391 6.830
Ac (2) g/l 20.219 20.219 20.583
pH 1.602 1.602 1.300
Temp °C 60.000 60.000 60.000
4.3.3.3. Observations
 .Advance electrolyte (60°C) pH: 2.322.

 Entry solution pH: 1.887
 Exit pH: 1.602
 Exit acid (1) concentration: 3.391g/L.
 Exit acid(2) concentration: 20.219g/L
 Spent electrolyte (25°C) pH: 1.300.
The presence of sodium in Cobalt electrolyte increases the exit solution pH form
1.508 to 1.602. This means that the current efficiency increases and the power
consumption decreases.

4.4. 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
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

5. Stripping and cobalt electrowinning unit
operations
5.1.1. Flow diagram

Figure (5.1) gives the flow diagram of stripping and cobalt electrowinning unit
operations working with a pure cobalt solution. The loaded organic comes from Table
(3.3). The cobalt concentration in the loaded organic is 1.6g/L with 6.521% (v/v) of
Cyanex 272 in organic. The chemical compositions of solutions in cobalt electrowinning
unit operation are given in Tables (4.16) and (4.17). The chemical composition of spent
electrolyte at 25°C is 50.903g/L of Cobalt at pH 1.232.
The water is added to spent electrolyte to compensate the difference in weight

between the mass of hydrogen transferred from solution to organic phase in stripping
unit operation and the masses of oxygen and hydrogen released in cobalt electrowinning
unit operation.
Figure 5.1: Stripping and cobalt electrowinning unit operations

5.1.2. Isotherm curve
generated by RSP for a solution containing 50.903g/L of Cobalt at pH of 1.232 at room
temperature with organic containing 1.6g/L of Cobalt and 6.521% of volume percent of
Cyanex 272. Figure (5.2) illustrates Cobalt isotherm curve (blue line).
Table 5.1: Values of Cobalt isotherm curve for solution containing 50.903g/L of Co at pH 1.232
with organic phase containing 1.6 g/L of Cobalt and 6.521% v/v of Cyanex 272 at
room temperature by RSP

Organic Aqueous
7.00 0.0212 61.811
6.00 0.0059 60.347
5.00 0.0029 58.791
2.50 0.0010 54.855
2.00 0.0009 54.066
1.50 0.0008 53.276
1.00 0.0007 52.485
0.50 0.0006 51.694
0.20 0.0006 51.219
0.10 0.0006 51.061
Figure 5.2: Cobalt isotherm curve for solution containing 50.903g/L of Co at pH 1.232 with
organic phase containing 1.6g/L Cobalt and 8% v/v of Cyanex 272 at room
temperature generated by RSP

Figure (5.3) gives McCabe Thiele diagram of a stage on stripping train. The
following:
Figure 5.3: McCabe Thiele of stage on stripping train

isotherm curve of Cobalt for solution containing 50.903g/L of Co at pH
1.232 with organic phase containing 1.6g/L of Cobalt and 6.521% v/v of
Co
Cyanex 272 at room temperature generated by RSP. Where “COrg ” is the
Co
Cobalt concentration in organic phase (g/L) and “Caq ” is Cobalt
Co
Log(Caq )=1.757*10−2 *(log(Cor
Co 3
)) +9.312*10−2 *(log(Cor
Co 2
)) +1.802*10−1 *log(Cor
Co
)+1.914 (5.1)
 The construction starts by the first stage on the stripping (stage 1).
A
 The concentration in organic in point (A) (Cor ) is Cobalt concentration in
loaded organic (1.6g/L).
A
in advance electrolyte.

B
 The concentration in aqueous in point (B) (Caq ) is equal to the
A
concentration in aqueous in point (A) (Caq ).
B
 The concentration in organic in point (B) (Cor ) is random number less
A
than the concentration in organic in point A (Cor )(1.6g/L).
A
 The concentration in organic in point (C) (Cor ) is equal to the
B
concentration in organic in point B (Cor ).
C
 The concentration in aqueous in point (C) (Caq ) is calculated using
Equation (5.2). The value of (O/A) is unknown value and is the variable.
The initial value is 6.
.
CB C
aq −Caq
=(O/A) (5.2)
CA B
or −Cor
E
(CB C
E C aq −Caq )
Caq =Caq + (5.3)
MF
E
Equation (5.4).
E A (CA B
or −Cor )
Cor =Cor - (5.4)
MF
E
 The concentration in aqueous in point (E) (Caq ) is calculated also using
Equation (5.5).
E
Co 3
)) +9.312*10−2 *(log(Cor
Co 2
)) +1.802*10−1 *log(Cor
Co
)+1.914 (5.5)
B
 The value of concentration in organic in point (B) (Cor ) is optimized
using Excel solver where the variable is the concentration in organic in
B
point (B) (Cor ) and the constraint is that the concentration in organic in
E
point E (Caq ) calculated with Equations (5.3) and (5.5) are equals.
B
second stage. The value of concentration in organic in point (B) (Cor ) is
B
organic in point (B) (Cor ) and the constraint is that the concentration in

E
aqueous in point E (Caq ) calculated with Equations (5.3) and (5.5) are
equals.
B
stage. The value of concentration in organic in point (B) (Cor ) is
B
E
aqueous in point E (Caq ) calculated with Equations (5.3) and (5.5) are
equals.
 The value of (O/A) ratio is optimized using Excel solver where the
variable is the value of (O/A) ratio and the constraint is that the
C
concentration in aqueous in point (C) (Caq ) in the third stage is equal to
50.903g/L that is the cobalt concentration is spent electrolyte.
McCabe Thiele diagram (Number of stage=3, Mixing efficiency=90%, concentration of
Cyanex 272 in organic=6.521%, room temperature=25°C, and Cobalt concentration in
advance=60g/L). The optimal value of (O/A) ratio is 5.694. Figure (5.4) gives the
McCabe Thiele from Table (5.2)
concentration of Cyanex 272 in organic=6.521%, room temperature=25°C, and
cobalt concentration in advance=60g/L)

Organic Aqueous
1.600 60.000 A
0.168 60.000 B
Stage 1
0.168 51.847 C
0.0090 60.906 E
0.168 51.847 A
0.017 51.847 B
Stage 2
0.017 50.989 C
0.0006 51.943 E
0.017 50.989 A
0.002 50.989 B
Stage 3
0.002 50.903 C
0.0006 50.999 E
The results show that the concentration in organic after 3 stages is around
0.002g/L of Cobalt.

Figure (5.4): McCabe Thiele diagram (Number of stage=3, Mixing efficiency=90%,
concentration of Cyanex 272 in organic=6.521%, room temperature=25°c, and
cobalt concentration in advance=60g/L)
5.2. Modeling
5.2.1. Concept
The modeling of stripping step of Cobalt solvent extraction takes account the
flow rate of the aqueous entrainment in organic phase.
5.2.2. Flow diagram
5.2.2.1. Flow diagram
Figure (5.5) gives the flow diagram of stripping step having “n” stages and
cobalt electrowinning step.

Figure 5.5: Flow diagram of strip step with “n” stages and cobalt electrowinning step
 Stp: Stage of rank “p” in stripping train
 AdEp: Advance electrolyte of stage of rank “p”.

 LO: Loaded organic
 ALO: Aqueous entrainment of loaded organic.
 StpSO: Stripped organic of stage of rank “p” in stripping train.
 StpASO: Aqueous entrainment of stripped organic of stage of rank “p” in
stripping train.

5.2.2.2. Plant description
Diluted spent electrolyte is fed to the stage of rank “n” of stripping train. The
advance electrolyte of stripping stage of rank “p+1” is fed to the stripping stage of rank
(p). The advance of stripping stage of rank “1” is final advance electrolyte. Loaded
organic is fed to stripping stage of rank “1”. The stripped organic of stripping stage of
rank “p-1” is fed to stripping stage of rank “p”. The stripped organic of stripping stage of
rank “n” is the final stripped organic. During this process, Cobalt is extracted from
organic to aqueous phase and aqueous phase releases hydrogen ions in organic phase.
Acid solution is added in stripping stage of rank “1”to maintain the pH of advance
electrolyte at the target value.
5.2.3. Simulation
5.2.3.1.1. Stripping step
 Loaded organic flow rate: Table (3.6)

 Loaded organic composition: Table (3.6)
 Aqueous entrainment of loaded organic: Table (3.6)
 Extractant volume percentage in organic: 6.39% Table (3.5).
 Number of stage: 3 (from experimental procedure).
o Stage St1: 90%.
o Stage St2: 90%.
o Stage St3: 90%
o Stage St1: 500ppm.
o Stage St3: 500ppm
 Acid solution: 200g/L of acid.
5.2.3.1.2. Cobalt electrowinning
Design criteria of cobalt electrowinning step are in Table (4.15).

Table (5.3) gives the summary results. Tables (5.4, 5.5 and 5.6) give the mass
balance results.

Ratio LO/Dilute spent electrolyte flow rate 6.032
Acid consumption 11.47 kg/h
Stripping efficiency Co
Global 99.86 %
St1 89.71 %
St2 89.66 %
St3 87.19 %
Cobalt loss in stripped organic 1.547 %
Table 5.4: Mass balance of stripping step with 3 stages
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

LO ALO St1SO St1ASO St2SO St2ASO St3SO St3ASO
Liquid
mass t/h 0.125 0.125 0.125 0.125
volume m3/h 250.000 0.124 250.000 0.109 250.000 0.110 250.000 0.110
SG liquid t/m3 1.005 1.145 1.138 1.137
Co g/l 1.584 0.610 0.163 60.000 0.017 51.708 0.002 50.815
Na g/l 1.056 1.193 1.195 1.195
S g/l 1.069 34.867 34.931 34.938
Ac(1) g/l 0.000 1.401 7.277 8.046
Ac(2) g/l 4.246 18.237 19.743
pH 5.500 2.000 1.287 1.244
9.00 10.00 11.00 12.00 13.00 14.00 15.00

Diluted AdE3 AdE2 AdE1 Acid Advance Recirculated
Spent (25°C) solution Electrolyte Electrolyte
electrolyte (60°) (60°C)
Liquid
mass t/h 47.161 47.164 47.199 47.578 0.067 47.578 39.355
volume m3/h 41.445 41.483 41.490 41.568 0.057 42.147 35.199
SG liquid t/m3 1.138 1.137 1.138 1.145 1.170 1.129 1.118
Co g/l 50.772 50.815 51.708 60.000 0.000 59.176 50.000
Na g/l 1.196 1.195 1.195 1.193 0.000 1.177 1.178
S g/l 34.971 34.938 34.931 34.867 65.389 34.388 34.439
Ac(1) g/l 8.130 8.046 7.277 1.401 200.000 0.685 4.298
Ac(2) g/l 19.913 19.743 18.237 4.246 200.000 4.187 19.610
pH 1.240 1.244 1.287 2.000 2.311 1.517

16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00

Entry Cobalt Oxygen Hydrogen Exit Solution Spent Spent water
Solution Cathodic electrolyte electrolyte
(60°C) (60°C) (25°C)
Solid
Mass 0.390
Gas
Mass 0.132 0.003
Liquid
mass t/h 86.933 86.408 47.053 47.053 0.108
volume m3/h 77.346 77.283 42.084 41.338 0.108
SG liquid t/m3 1.124 1.118 1.118 1.138 1.000
Co g/l 55.000 50.000 50.000 50.903
Na g/l 1.177 1.178 1.178 1.200
S g/l 34.411 34.439 34.439 35.061
Ac(1) g/l 2.079 4.298 4.298 8.142
Ac(2) g/l 11.206 19.610 19.610 19.964
pH 1.831 1.517 1.517 1.239
5.3. Observations
The values of cobalt concentration in stripped organic of rank “2” and “3” are
close from experimental procedure and modeling because the water dilution of spent
electrolyte is very low.

6. Extraction, Stripping and cobalt
electrowinning unit operations
6.1.1. Flow diagram

Figure (6.1) gives the flow diagram of extraction, stripping and cobalt
electrowinning unit operations working with a pure cobalt solution. The numbers of
stages on extraction and stripping trains are 3 respectively.
Figure 6.1: Extraction, stripping and cobalt electrowinning unit operations

6.1.2.1. Concept
Table (5.2) on stripping McCabe of 3 stages shows that the cobalt concentration
in organic in point (C) of the third stage is 0.002g/L. But Table (3.3) on extraction
McCabe of 3 stages shows that the cobalt concentration in organic in point (C) of the
third stage is 0.016g/L. The Figure (6.1) shows that the two cobalt concentrations must
be the same.
The extraction McCabe Thiele diagram of extraction step must be repeated to

have 0.002g/L of cobalt in organic in point (C) of the third stage by obtaining the new
optimal extractant volume percentage in organic.
6.1.2.2. Extraction McCabe Thiele diagram
procedure of McCabe Thiele construction of Cobalt based on Figure (3.4) is the following
to obtain the optimal extractant volume percentage in organic:
 The initial value of the extractant volume percentage in the organic

phase is the lowest (6%). This value gives the values of variable “a”, “b”
and “c” for the extrapolation Equation of isotherm curve.
A
A
 The concentration in organic in point (A) (Cor ) is random number close
to 1.6g/L.
B
A
B
A
B
B

A
Equation (6.1) (the operating line does not pass through the point (0;0)).
CA B
aq −Caq
C =(O/A) (6.1)
CB
or −Cor
.
E
E A (CA B
aq −Caq )
Caq =Caq - (6.2)
MF
E
Equation (6.3).
(CB C
E C or −Cor )
Cor =Cor + (6.3)
MF
E
Equation (6.4).
E E
E
)+c (6.4)
B
B
E
B
B
E
equals.
stage. The value of concentration in aqueous in point (C) is equal to 0.02.
The value of (v/v%) is optimized using Excel solver where the variable is
the value (v/v%) and the constraint is that the concentration in organic
E
in point E (Cor ) calculated with Equations (6.3) and (6.4) are equals.

C
 The value of concentration in organic in point (C) (Cor ) of the third stage
is equal to 0.002g/L. The value of concentration in organic in point (A)
A
(Cor ) of the first stage is optimized using Excel solver where the variable
A
is the value of concentration in organic in point (A) (Cor ) and the
C
constraint is that the concentration in organic in point (C) (Cor ) on the
third stage is equal to 0.002g/L.
extraction McCabe Thiele diagram (Number of stage=3, (O/A)=1.25, Mixing
efficiency=90%, room temperature=25°C, pH=5.5; Cobalt efficiency=99% and cobalt
concentration in stripped organic=0.002g/L). The optimal (v/v%) is equal to 6.403%.
Table (6.1): Coordinates of points (A, B, C, and E) (Number of stage=3, (O/A)=1.25, Mixing
efficiency=90%, concentration of Cyanex 272 in organic=6.521%, room
temperature=25°C, pH=5.5, Cobalt efficiency 99% and concentration in stripped
organic=0.002g/L)

Aqueous Organic
2.000 1.586 A
0.614 1.586 B
Stage 1
0.614 0.478 C
0.461 1.709 E
0.614 0.478 A
0.118 0.478 B
Stage 2
0.118 0.081 C
0.063 0.522 E
0.118 0.081 A
0.020 0.081 B
Stage 3
0.020 0.002 C
0.009 0.089 E
6.1.2.3. Stripping McCabe Thiele diagram
generated by RSP for a solution containing 50.903g/L of Cobalt at pH of 1.232 at room
temperature with organic containing 1.586g/L of Cobalt and 6.403% of volume percent
of Cyanex 272.

Table 6.2: Values of Cobalt isotherm curve for solution containing 50.903g/L of Co at pH 1.232
with organic phase containing 1.586 g/L of Cobalt and 6.403% v/v of Cyanex 272
at room temperature by RSP

Organic Aqueous
7.00 0.0183 61.735
6.00 0.0054 60.267
5.00 0.0027 58.722
2.50 0.0010 54.821
2.00 0.0009 54.038
1.50 0.0007 53.255
1.00 0.0007 52.471
0.50 0.0006 51.687
0.20 0.0005 51.217
0.10 0.0005 51.060
Figure (5.3) gives McCabe Thiele diagram of a stage on stripping train. The
following:

isotherm curve of Cobalt for solution containing 50.903g/L of Co at pH
1.232 with organic phase containing 1.586g/L of Cobalt and 6.403% v/v
Co
of Cyanex 272 at room temperature generated by RSP. Where “COrg ” is
Co
the Cobalt concentration in organic phase (g/L) and “Caq ” is Cobalt
Co
Co 3
)) +9.659*10−2 *(log(Cor
Co 2
)) +1.905*10−1 *log(Cor
Co
)+1.924 (6.1)
 The construction starts by the first stage on the stripping (stage 1).
A
 The concentration in organic in point (A) (Cor ) is Cobalt concentration in
loaded organic.
A
in advance electrolyte.
B
 The concentration in aqueous in point (B) (Caq ) is equal to the
A
concentration in aqueous in point (A) (Caq ).
B
 The concentration in organic in point (B) (Cor ) is random number less
A
than the concentration in organic in point A (Cor ).

A
 The concentration in organic in point (C) (Cor ) is equal to the
B
concentration in organic in point B (Cor ).
C
 The concentration in aqueous in point (C) (Caq ) is calculated using
Equation (6.2). The value of (O/A) is known value and is the variable.
The initial value is 6.
.
CB C
aq −Caq
=(O/A) (6.2)
CA B
or −Cor
E
(CB C
E C aq −Caq )
Caq =Caq + (6.3)
MF
E
Equation (6.4).
E A (CA B
or −Cor )
Cor =Cor - (6.4)
MF
E
 The concentration in aqueous in point (E) (Caq ) is calculated also using
Equation (6.5).
E
Co 3
)) +9.659*10−2 *(log(Cor
Co 2
)) +1.905*10−1 *log(Cor
Co
)+1.924 (6.5)
B
 The value of concentration in organic in point (B) (Cor ) is optimized
using Excel solver where the variable is the concentration in organic in
B
point (B) (Cor ) and the constraint is that the concentration in aqueous in
E
B
second stage. The value of concentration in organic in point (B) (Cor ) is
B
E
aqueous in point E (Cor ) calculated with Equations (6.3) and (6.5) are
equals.
B
stage. The value of concentration in organic in point (B) (Cor ) is
B
E
aqueous in point E (Cor ) calculated with Equations (6.3) and (6.5) are
equals.
 The value of (O/A) ratio is optimized using Excel solver where the
variable is the value of (O/A) ratio and the constraint is that the
C
concentration in aqueous in point (C) (Caq ) in the third stage is equal to
50.903g/L that is the cobalt concentration is spent electrolyte.
stripping McCabe Thiele diagram (Number of stage=3, Mixing efficiency=90%,
concentration of Cyanex 272 in organic=6.403%, room temperature=25°C, Cobalt
concentration in LO=1.586g/L and Cobalt concentration in advance=60g/L). The
optimal value of (O/A) ratio is 5.744.
concentration of Cyanex 272 in organic=6.403%, room temperature=25°C, Cobalt
concentration in LO=1.586g/L and cobalt concentration in advance=60g/L)

Organic Aqueous
1,586 60,000 A
0,166 60,000 B
Stage 1
0,166 51,843 C
0,0082 60,906 E
0,166 51,843 A
0,017 51,843 B
Stage 2
0,017 50,989 C
0,0006 51,938 E
0,017 50,989 A
0,002 50,989 B
Stage 3
0,002 50,903 C
0,0006 50,998 E
The results show that the concentration in organic in point (C) of the third stage
is 0.002g/L of Cobalt. If the concentration in organic in point (C) of the third stage is
different to 0.002g/L, the extraction and stripping McCabe must be repeated with the
new value of concentration in organic in point (C) of the third stage.

6.2. Modeling
6.2.1. Flow diagram

Figure (6.2) gives the flow diagram of extraction step having “n” stages,
stripping step having “n” stages and cobalt electrowinning step.
Figure 6.2: Flow diagram of extraction step with “n” stages, strip step with “n” stages and
cobalt electrowinning step

 Ep; Stage of rank “p” in extraction train

 Stp: Stage of rank “p” in stripping train
 RS: Rich solution.

 EpRaf: Raffinate of stage of rank “p”.
 LO: Loaded organic of stage of rank “1” in extraction train.
 ALO: Aqueous entrainment of loaded organic.
 EpLO: Loaded organic of stage of rank “p” in extraction train
 EpALO: Aqueous entrainment of loaded organic of stage of rank “p” in
extraction train.
 EpNa: NaOH solution of stage of rank “p” in extraction train.
 AdEp: Advance electrolyte of stage of rank “p”.
 StpSO: Stripped organic of stage of rank “p” in stripping train.
 StpASO: Aqueous entrainment of stripped organic of stage of rank “p” in
stripping train.
6.2.2. Simulation
6.2.2.1.1. Extraction step
 Rich solution composition:

o Cobalt: 2g/L.
o pH: 4.5.
 Type of extractant: Cyanex 272.
 O/A ratio:
o External: 1.25.
o Internal: 1.25
o Stage E1: 90%.
o Stage E2: 90%.
o Stage E3: 90%

o Stage E1: 500ppm.
o Stage E2: 500ppm.
o Stage E3: 500ppm
 Cobalt loss in extraction stage 3 raffinate: 1% of Cobalt in the rich
solution
 NaOH concentration: 100g/L of NaOH in NaOH solution.
 pH profile:
o Stage E1: 5.5.
o Stage E2: 5.5.
o Stage E3: 5.5
o Stage St1: 90%.
o Stage St2: 90%.
o Stage St3: 90%
o Stage St3: 500ppm
 Acid solution: 200g/L of acid.
6.2.2.1.3. Cobalt electrowinning
Design criteria of cobalt electrowinning step are in Table (4.15).
6.2.2.2.1. Extraction step
Table (6.4) gives the summary results. Tables (6.5) and (6.6) give the mass
balance results.


NaOH consumption 547.35 kg/h
Recovery Co
Global 99.01 %
E1 72.72 %
E2 81.87 %
E3 84.21 %
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

RS E1Raf E1Na E2Raf E2Na E3Raf E3Na E1LO
Liquid
mass t/h 201.022 205.056 4.315 206.293 1.323 206.608 0.336
volume m3/h 200.000 204.096 3.954 205.351 1.212 205.653 0.307 250.000
SG liquid t/m3 1.005 1.005 1.091 1.005 1.091 1.005 1.091
Co g/l 2.000 0.534 0.096 0.019 1.608
Na g/l 0.000 1.114 57.475 1.446 57.475 1.530 57.475
S g/l 1.089 1.068 1.061 1.077
Ac(1) g/l 0.004 0.000 0.000 0.000
Ac(2) g/l 0.003 0.000 0.000 0.000
pH 4.500 5.500 5.500 5.500
9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00

E1ALO E2LO E2ALO E3LO E3ALO SO ASO
Liquid
mass t/h 0.125 0.125 0.125 0.125
volume m3/h 0.124 250.000 0.124 250.000 0.124 250.000 0.110
SG liquid t/m3 1.005 1.005 1.005 1.137
Co g/l 0.534 0.445 0.096 0.088 0.019 0.002 50.811
Na g/l 1.114 1.446 1.530 1.260
S g/l 1.068 1.061 1.077 34.982
Ac(1) g/l 0.000 0.000 0.000 8.038
Ac(2) g/l 0.000 0.000 0.000 19.744
pH 5.500 5.500 5.500 1.244
Table (6.7) gives the summary results. Tables (6.8), (6.9) and (6.10) give the
mass balance results.


Ratio LO/Dilute spent electrolyte flow rate 5.939
Acid consumption 11.47 kg/h
Stripping efficiency Co
Global 99.86 %
St1 89.66 %
St2 89.61 %
St3 86.78 %
Cobalt loss in stripped organic 1.531 %
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

LO ALO St1SO St1ASO St2SO St2ASO St3SO St3ASO
Liquid
mass t/h 0.125 0.125 0.125 0.125
volume m3/h 250.000 0.124 250.000 0.109 250.000 0.110 250.000 0.110
SG liquid t/m3 1.005 1.145 1.138 1.137
Co g/l 1.608 0.534 0.166 60.000 0.017 51.707 0.002 50.811
Na g/l 1.114 1.258 1.260 1.260
S g/l 1.068 34.914 34.975 34.982
Ac(1) g/l 0.000 1.400 7.267 8.038
Ac(2) g/l 0.000 4.249 18.233 19.744
pH 5.500 2.000 1.288 1.244
9.00 10.00 11.00 12.00 13.00 14.00 15.00

Diluted AdE3 AdE2 AdE1 Acid Advance Recirculated
spent (25°C) solution electrolyte Electrolyte
electrolyte (60°) (60°C)
Liquid
mass t/h 47.911 47.914 47.950 48.333 0.067 48.333 39.979
volume m3/h 42.098 42.139 42.146 42.222 0.057 42.810 35.753
SG liquid t/m3 1.138 1.137 1.138 1.145 1.170 1.129 1.118
Co g/l 50.770 50.811 51.707 60.000 0.000 59.176 50.000
Na g/l 1.262 1.260 1.260 1.258 0.000 1.241 1.243
S g/l 35.016 34.982 34.975 34.914 65.389 34.434 34.485
Ac(1) g/l 8.122 8.038 7.267 1.400 200.000 0.685 4.293
Ac(2) g/l 19.916 19.744 18.233 4.249 200.000 4.190 19.613
pH 1.240 1.244 1.288 2.000 2.311 1.518

16.00 17.00 18.00 19.00 20.00 21.00 22.00 23.00

Entry Cobalt O2 H2 Exit Spent Spent water
Solution Cathodic Solution Electrolyte electrolyte
(60°C) (60°C) (25°C)
Solid
Mass 0.396
Gas
Mass 0.134 0.003
Liquid
mass t/h 88.313 87.779 47.800 47.800 0.111
volume m3/h 78.562 78.499 42.746 41.988 0.111
SG liquid t/m3 1.124 1.118 1.118 1.138 1.000
Co g/l 55.000 50.000 50.000 50.903
Na g/l 1.242 1.243 1.243 1.265
S g/l 34.457 34.485 34.485 35.108
Ac(1) g/l 2.078 4.293 4.293 8.135
Ac(2) g/l 11.209 19.613 19.613 19.968
pH 1.831 1.518 1.518 1.239
6.2.3. Observations
The Extractant volume percentages in organic of experimental procedure and
modeling are respectively 6.043% and 6.82%. The extractant volume percentage of
modeling is high because of the quantity of cobalt in the aqueous entrainment of
stripped organic is 5.581kg/h. The quantity of cobalt increases the quantity of cobalt in
the feed solution of the third stage on extraction train.

7. References
1. Uthaiwan Injarean et al, 2014, Batch simulation of multistage counter
current extraction of Uranium in yellow cake from Monazite processing with
5% TBP/Kerosene, Energy Procedia.
2. J. Kafumbila. 2023. Modeling and design of Cobalt hydroxyl-sulfate
production circuit. researchgate.
https://www.researchgate.net/publication/370631988_Modeling_and_desi
gn_Cobalt_hydroxyl-sulfate_production_circuit
3. H.A. Evans. 2008. Modelling Cobalt extraction with Cyanex 272.
International solvent extraction conference.
4. D. Kyembo, 2015, Cobalt solvent extraction, Thesis, University of the
Witwatersrand.
5. J. Kafumbila. 2017. Design and optimization of copper solvent extraction
configurations. Researchgate
(PDF) Design and optimization of copper solvent extraction configurations
(researchgate.net)
6. Scott, A.C. et al, 1987, A mathematical model of a zinc electrowinning cell,
SAIMM.
7. Kelly, E.J. et al, H.R., 1984, Kinetics and mechanism of the hydrogen evolution
reaction on titanium in acidic media, Journal of the electrochemical society.
8. Cheng Tzong Hong, 1968, Corrosion rates and electrokinetics of Cobalt and
Cobalt-Iron alloys in sulfuric and hydrochloric acids, Masters Theses.
9. Fabbri, E. et al, 2014, Developments and perspectives of oxide-based catalyst
for the oxygen evolution reaction, Catalysis Science and Technology.
10. D. Lowe et al, 1968, Electrolytic deposition of Cobalt from a sulphate
electrolyte, Neue Hutte.
11. N. Mulaudzi et al, 2013, Direct Cobalt electrowinning as an alternative to
intermediate Cobalt mixed hydroxide product, SAIMM.
12. R. Breckpot et al, 1969, Optimisation des conditions d’electro-extraction du
Cobalt, Metallurgie IX.
13. I.G. Sharma et al, 2005, Electrowinning of Cobalt from sulphate solution,
Hydrometallurgy 80, Elsevier.
14. J. Kafumbila (2). 2023. Modeling and design of Cobalt hydroxyl-sulfate
production circuit. researchgate.
https://www.researchgate.net/publication/370631988_Modeling_and_desi
gn_Cobalt_hydroxyl-sulfate_production_circuit
15. Charles E. Harvie et al, 1984, The prediction of mineral solubilities in natural
water: Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O system to high ionic
strengths at 25°C, Geochimica et Cosmochimica Acta.

16. H.C. Helgeson, 1969, Thermodynamics of hydrothermal systems at elevated
temperatures and pressures, Ameraican Journal of Science 267.
17. H.C. Helgeson et al, 1981, Theoretical prediction of the thermodynamic
behavior of aqueous electrolytes at high pressures and temperatures: IV
calculation of activity coefficients, osmotic coefficients, and apparent molal
and standard and relative partial molal properties to 600°C and 5 KB,
American Journal of Science.
18. Bjorn Beverskog, et al, 1998, Pourbaix diagrams for the system copper –
chlorine at 5 – 100°C, SKI Rapport 98:19.
19. Ignasi Puigdomenech et al, 1999, Temperature corrections to
thermodynamic Data and enthalpy calculations, Le seine-st Germain, France.
20. Nik Rozlin Nik Mohd Masdek, 2014, Electrodeposition and corrosion study
of nanocrytalline Cobalt and Cobalt-iron alloy coating, Theses.

Design of Cobalt Solvent Extraction and Cobalt Electrowinning Circuit From Pure Cobalt Solution

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Design of Cobalt Solvent Extraction and Cobalt Electrowinning Circuit From Pure Cobalt Solution

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PROJECT METALLURGIST

Design of Cobalt solvent

Joseph Kafumbila Page 1

Process simulation as discipline uses mathematical models as basis for analysis

Joseph Kafumbila Page 2

Joseph Kafumbila Page 3

Joseph Kafumbila Page 4

Joseph Kafumbila Page 5

Cobalt is often recovered as an intermediate hydroxide or carbonate product,

This publication presents a design procedure of cobalt solvent extraction using

Joseph Kafumbila Page 6

2.1. Experimental methodology

Joseph Kafumbila Page 7

Joseph Kafumbila Page 8

The advantageous of simulation program is that the overall plant (extraction,

2.2.2. Realistic Simulation Program (RSP)

Comparatively other simulation program, Realistic Simulation Program can

Joseph Kafumbila Page 9

3.1. Experimental procedure

3.1.1. Flow diagram

Figure 3.1: Flow diagram of extraction step

3.1.2. pH-loading curve

Joseph Kafumbila Page 10

3.1.3. Isotherm curve

O/A Cobalt concentration (g/L)

Joseph Kafumbila Page 11

3.1.4. McCabe Thiele diagram

Figure 3.4: McCabe Thiele of stage on extraction train

Joseph Kafumbila Page 12

Joseph Kafumbila Page 13

Joseph Kafumbila Page 14

Cobalt concentration (g/L)

Figure (3.5): McCabe Thiele diagram (Number of stage=3, Mixing efficiency=90%,

3.1.5. Optimal extractant volume percentage in organic

Joseph Kafumbila Page 15

a=-5.00*10−5 *(v/v%)2 +3.02*10−3*(v/v%)-0.2011 (3.8)

b=1.719*10−3 *(v/v%)2 -5.458*10−2 *(v/v%)+0.5936 (3.9)

b=-4.694*10−3*(v/v%)2 +1.536*10−1*(v/v%)-0.4315 (3.10)

 The initial value of the extractant volume percentage in the organic

Joseph Kafumbila Page 16

Joseph Kafumbila Page 17

Cobalt concentration (g/L)

O/A Cobalt concentration (g/L)

Joseph Kafumbila Page 18

3.2.2. Flow diagram of extraction step

3.2.2.1. Flow diagram

Joseph Kafumbila Page 19

Abbreviations of unit operations:

 Extraction Ep: Stage of rank “p” in Extraction train

Abbreviations of lines between unit operations:

 RS: Rich solution.

3.2.2.2. Plant description

Joseph Kafumbila Page 20

3.2.3.1. Design Criteria

Design criteria of extraction circuit mass balance are the following:

 Rich solution composition:

3.2.3.2. Simulation results

Joseph Kafumbila Page 21

Extractant volume percentage 6.390 %

Table 3.6: Mass balance of extraction step with 3 stages

1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Table 3.7: Mass balance of extraction step with 3 stages

9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00

Joseph Kafumbila Page 22

a=-5.0010−5 (v/v%)2 +3.0210−3(v/v%)-0.2011 (3.8)

b=1.71910−3 (v/v%)2 -5.45810−2 (v/v%)+0.5936 (3.9)

b=-4.69410−3(v/v%)2 +1.53610−1(v/v%)-0.4315 (3.10)