Modeling and Design of Cobalt Hydroxyl Sulfate Production Circuit

PROJECT METALLURGIST
Modeling and design of

Cobalt hydroxyl-sulfate
production circuit
Selective precipitation of metallic elements,
Selective oxidation of metallic elements and
Zinc solvent extraction using Cyanex 272 as
extractant
Kafumbila Kasonta Joseph
Sponsor
Mr. KASEKA TSONGO ERIC ABRAHAM
Directeur Gérant de la société
Alpha Business Company SARL
2023
Modeling and design of Cobalt hydroxyl-sulfate production circuit
© 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.

Contents
1. Introduction ............................................................................................................ 6
2. Flow diagram .......................................................................................................... 7
2.1. Introduction 7
2.2. Simplest cobalt circuit 7
2.3. Ferrous oxidation step 9
2.4. Two and three stages of Fe and Al removal step 12
2.5. Mg removal step in cobalt precipitation cake 22
2.6. Mn removal step in cobalt circuit 26
3. Precipitation process ........................................................................................ 29
3.1. Definition 29
3.2. Precipitation – condition 29
3.3. Simultaneous precipitation of at least two cations 30
3.4. Thermodynamic approach 33
4. Realistic Simulation Model (RSM) ............................................................... 37
4.1. Characterization of pulp 37
4.2. Specific gravity 37
4.3. Soluble compounds 40
5. Estimation of Free Gibbs Energy of solid compound ........................... 49
5.1. Free Gibbs Energy of formation form literature 49
5.2. Estimation of Al hydroxyl sulfate 50
5.3. Estimated Free Gibbs Energy of formation of solid compounds form
lab test results 52
6. Neutralization reagents ................................................................................... 53
6.1. Types of neutralization 53
6.2. Limestone 53
6.3. Quick lime 54
6.4. MgO 56
7. Prediction of dithionate and iron saturation concentrations ........... 58
7.1. Introduction 58
7.2. Observations 58
7.3. Pilot plant description 58

7.4. Modeling of Calcium concentration in solution during reductive
leach solution using SO2 gas as reducing agent 62
7.5. Modeling of Dithionate concentration in solution during reductive
leaching of Cobalt using SO2 as reducing agent 64
7.6. Modeling of Iron saturation concentration in solution during
reductive leaching of Cobalt using SO2 gas as reducing agent 73
8. Modeling of Zinc solvent extraction using Cyanex 272 as extractant
................................................................................................................................... 76
8.1. Cyanex 272 76
8.2. Mechanism of metal extraction of Cyanex 272 76
8.3. Modeling of metal extraction of Cyanex 272 78
9. Oxidation of Ferrous , Manganese and Cobalt........................................ 79
9.1. Oxidation of Manganese and Cobalt hydroxides by oxygen at high
pH 79
9.2. Oxidation of Cobalt by γ-MnOOH at high pH 80
9.3. Oxidation of Fe(II), Manganese and dithionate using the mixture
Air/𝐒𝐎𝟐 at low pH 81
9.4. Disproportional reaction of MnOOH at low pH 85
9.5. Dissolution of CoOOH by Mn(II) ion at low pH 85
10. Modeling and Mass balance of copper cathode production circuit 87
10.1. Configuration 87
10.2. Mass balance 91
11. Mass balance of Cobalt circuit –A...............................................................109
12. Mass balance of Cobalt circuit –B ...............................................................130
13. Mass balance of Cobalt circuit –C ...............................................................148
14. Mass balance of Copper circuit and Cobalt circuit - D........................167

15. Reference .............................................................................................................211

1. Introduction
The simulation program is used in the plant design to estimate the flow rate of
pulp. The design criteria come from lab tests or pilot plant. In the case of cobalt
hydroxyl-sulfate production circuit, the circuit contains successive selective
precipitation steps and dissolution steps. The simulation program must be used only for
the circuit having known design criteria. In case of unknown design criteria, it is
impossible to make the extrapolation because of selective precipitation steps.
In the publication, realistic simulation program based on thermodynamic

equilibrium condition is established. The simulation program can simulated a cobalt
production circuit only from chemical composition of the feed solution. The purpose of
the publication is to:
 Find the solid compounds that can precipitate in cobalt hydroxyl sulfate
production circuit.
 Estimate unknown thermodynamic data of solid compounds from lab
test.
 Establish some models for complex process as oxidation of Fe, Mn and Co
using the mixture Air/SO2, Oxidation of Mn(OH)2 and Co(OH)2 at high
pH into MnOOH and CoOOH, dissolution of CoOOH by Mn(+2) at low pH
and Zinc solvent extraction using Cyanex 272 as extractant.
The realistic simulation program is applied to example of cobalt hydroxyl-

sulfate production plant.

2. Flow diagram
2.1. Introduction
In Central Africa, copper oxide ores contain a certain amount of cobalt. After
reductive leaching using sulfur dioxide, the soluble cobalt leaves copper circuit through
water balance bleed. This water balance bleed becomes the feed solution of cobalt
circuit. Cobalt circuit contains two circuits: The first circuit called “impurity removal
step” contains Acid neutralization, iron removal, Al removal, Manganese removal, Zn
removal and copper removal steps and the second circuit called “cobalt removal step”
contains cobalt precipitation, manganese removal and magnesium removal.
2.2. Simplest cobalt circuit

Flow diagram on Figure (2.1) gives a conventional copper circuit and simplest
cobalt circuit (Chemaf – Usoke - DRC).
The first precipitation pH is ranged from 4.5 to 4.8. Limestone is used as

neutralization agent. Al concentration is ranged from 100 to 50mg/L. Al precipitates
first as amorphous aluminum phosphate (AlPO4 . 2H2 O) and the remaining Al
precipitates as amorphous Al hydroxyl-sulfate (Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O). Ferric
precipitates first as amorphous copper ferrite (CuFe2 O4 . 2H2 O) and the remaining Ferric
precipitates as Ferrihydrite (Fe(OH)3). There is mixed precipitation of Co(OH)2 with
Ferrihydrite (Fe(OH)3) (substances having the same anion (OH − )). There is partial
oxidation of Co(OH)2 into CoOOH by oxygen from Air. Fe(II) remains in solution. The
remaining phosphate precipitates as amorphous cobalt phosphate (Co3 (PO4 )2 . 8H2 O).
At pH high than 4.8, the remaining Al, after amorphous Al phosphate

precipitation, precipitates as amorphous Cobalt, Copper and Zinc aluminates
(CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O). Co loss increases in the solid.
At pH ranged from 4.5 to 4.8, Cobalt concentration in feed solution must be

more than 4g/L for a better selectivity after Fe and Al precipitation. The ratio of Co onto
Al concentrations must be more than 200 after Al removal step.

Figure 2.1: Conventional copper circuit with simplest cobalt circuit
Co precipitation is done at pH ranged 8.2 to 8.4 using MgO as precipitation agent

to have Co grade in the cake more than 30% and Co concentration in solution after
precipitation is ranged from 0.20 to 0.10g/L.
Al precipitates as amorphous cobalt, Copper and Zinc aluminates

(CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O). Fe(II) precipitates as Fe(OH)2.
There is a total oxidation of Fe(OH)2 to Fe(OH)3 by oxygen from Air. In presence of Cu,
Fe(OH)3 is transformed in amorphous Cu ferrite (CuFe2 O4 . 2H2 O) according to
dissolution and precipitation process in a presence of two salts having different
solubility products. The remaining Cu precipitates as Co2 Cu3 (OH)6 (SO4 )2 . 5H2 O. Zn
precipitates as ZnCo3 (OH)6 SO4 . 3H2 O. Mn precipitates as Mn(OH)2. There is partial
oxidation of Mn(OH)2 to MnOOH by oxygen from Air. Co adsorbs on MnOOH is oxidized
to CoOOH (James W. Murray et al, 1979). Phosphate precipitates as amorphous Co
phosphate (Co3 (PO4 )2 . 8H2 O). Carbonate precipitates as Mn and Co carbonates (MnCO3
and CoCO3 ). The remaining Co precipitates as Co5 (OH)6 (SO4 )2 . 10H2 O and Co(OH)2.
There is partial oxidation of Co(OH)2 to CoOOH by oxygen from Air. Co is adsorbed on

MnOOH surface and MnOOH oxidized adsorbed Co into CoOOH. Mg precipitates as
Mg(OH)2.
2.3. Ferrous oxidation step
2.3.1. Oxygen from Air as oxidation agent

The oxidation kinetic of Fe(II) to Fe(III) using oxygen from Air as oxidation
agent is significant at pH greater than 4.8 (Barak Morgan et al, 2007). If an important
portion of Fe is as ferrous in the feed solution (solution from reducing leaching), the
oxidation of ferrous to ferric at pH 4.8 using oxygen from Air as oxidation agent can be
used (KMT project - DRCong). Figure (2.2) gives the flow diagram of simplest cobalt
circuit with ferrous oxidation step using oxygen from Air as oxidation agent.
Figure 2.2: Simplest cobalt circuit with Fe(II) oxidation step using Oxygen from Air as
oxidation agent
Depending of Ferrous quantity in solution, oxidation time is ranged from 3 and

6hours and the quantity of Oxygen from Air injected in the pulp must be 10 times than
the stoichiometric quantity.


precipitates as Ferrihydrite (Fe(OH)3). The remaining phosphate precipitates as
amorphous cobalt phosphate (Co3 (PO4 )2 . 8H2 O). Ferrous is oxidized slowly into ferric
by oxygen from Air and ferric precipitates as Ferrihydrite (Fe(OH)3 ). There is mixed
precipitation of Co(OH)2 with Ferrihydrite (Fe(OH)3 ) (substances having the same
anion (OH − )). There is partial oxidation of Co(OH)2 into CoOOH by oxygen from Air.
2.3.2. Mixture Air/𝐒𝐎𝟐 as oxidation agent

It has been observed that the mixture Air/SO2 when is used in certain condition
oxidizes Fe(II) to Fe(III) (Wensheng Zhang et al, 2000). Ferrous oxidation pH must be
less than 2.0 and Eh must be between 0.7 and 0.8V to have more than 90% oxidation of
ferrous without oxidation of dithionate, Mn and Co. Figure (2.3) gives flow diagram of
simplest cobalt circuit with Fe(II) oxidation step using mixture Air/SO2 as oxidation
agent without acid neutralization.
Figure 2.3: Simplest cobalt circuit with Fe(II) oxidation step using mixture Air/SO2 as
oxidation agent

There is oxidation of ferrous to ferric by the mixture Air/SO2 . Eh is control to
reach 0.1g/L of ferrous in solution. At this level of ferrous in solution and pH, there is not
oxidation of dithionate. SO2 is oxidized in sulfate. The solution is discharge in Fe and Al
precipitation stage.

precipitates as Ferrihydrite (Fe(OH)3). There is mixed precipitation of Co(OH)2 with
Ferrihydrite (Fe(OH)3) (substances having the same anion (OH − )). There is partial
oxidation of Co(OH)2 into CoOOH by oxygen from Air. Ferrous remains in solution. The
remaining phosphate precipitates as amorphous cobalt phosphate (Co3 (PO4 )2 . 8H2 O).
2.3.3. CoOOH and MnOOH as oxidation agent

CoOOH and MnOOH produced from cobalt precipitation step can be used as
Fe(II) oxidation agent. Figure (2.4) gives the flow diagram of cobalt circuit in which
CoOOH and MnOOH are used as Fe(II) oxidation agent.
Figure 2.4: Simplest cobalt circuit with Fe(II) oxidation step using mixture MnOOH as
oxidation agent

Cobalt precipitation step is done in two stages. The first precipitation stage is
done at pH 7.8. Co concentration in solution is ranged from 1.0 to 0.5g/L. The
precipitation efficiency of Mn is less than 10% and the oxidation of Mn(OH)2 into
MnOOH is negligible. The second precipitation stage is done at pH ranged from 8.2to 8.4.
Mn precipitates as Mn(OH)2. There is partial oxidation of Mn(OH)2 to MnOOH by oxygen
from Air. 80% of Mn in solid is as MnOOH. Co precipitates as Co5 (OH)6 (SO4 )2 . 10H2 O
and Co(OH)2. There is partial oxidation of Co(OH)2 to CoOOH by oxygen from Air. Co is
adsorbed on MnOOH surface and MnOOH oxidizes adsorbed Co into CoOOH. 50% of Co
in the solid is as CoOOH.
Underflow of the second cobalt precipitation is recycled to Fe(II) oxidation

stage. The Fe(II) oxidation stage pH must be equal or less than 2.0 (addition of acid to
maintain pH at 2.0). There is first disproportionation of MnOOH giving MnO2 and
soluble Mn. MnO2 and CoOOH react with Ferrous and dithionate in solution and the
products of reactions are Ferric and sulfate. Al can precipitates as alumino-copiapite
(Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O) depending on the pH. Pulp is discharge in the Fe and Al
precipitation step.

neutralization agent. Al concentration is ranged from 100 to 50mg/L. There is
dissolution of alumino-copiapite (Al(2/3) Fe3 (SO4 )6(OH)2 . 20H2 O). Al precipitates first as
amorphous aluminum phosphate (AlPO4 . 2H2 O) and the remaining Al precipitates as
amorphous Al hydroxyl-sulfate (Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O). Ferric precipitates first
as amorphous copper ferrite (CuFe2 O4 . 2H2 O) and the remaining Ferric precipitates as
Ferrihydrite (Fe(OH)3). There is mixed precipitation of Co(OH)2 with Ferrihydrite
(Fe(OH)3 ) (substances having the same anion (OH − )). There is partial oxidation of
Co(OH)2 into CoOOH by oxygen from Air. The remaining phosphate precipitates as
amorphous cobalt phosphate (Co3 (PO4 )2 . 8H2 O).
2.4. Two and three stages of Fe and Al removal step
2.4.1. Purpose
The purpose for using two precipitation stages of Fe and Al are:
 First to have less than 20mg/L of Al in the solution. This practice comes
from Ni laterite production flow diagram. The Al grade in the Ni
hydroxyl-sulfate must be very when the re-leach of Ni hydroxyl-sulfate is
done in ammoniacal solution.

 Second to precipitate copper as amorphous copper aluminate and the
solid of the second precipitation stage is re-leach in the copper circuit for
copper recovering as copper metal.
2.4.2. Two precipitation stage and recycling of UF of second

precipitation stage thickener to first precipitation
stage
Figure (2.5) gives the flow diagram of two stages of Fe and Al removal step with
recycling of UF of second stage precipitation thickener to first precipitation stage.
Figure 2.5: Two precipitation stages of Fe and Al precipitation with recycling of UF of

the second stage precipitation to first precipitation stage
There is dissolution of amorphous Cu, Co and Zn aluminates (CoAl2 O4 . 2H2 O,

CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O) and amorphous Al hydroxyl-sulfate
(Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O) in the Ferrous oxidation step. Acid is added to control
pH at 2.0 to have dissolution efficiency more than 98%. UF of the second cobalt
precipitation is recycled to Fe(II) oxidation stage. There is first disproportionation of
MnOOH giving MnO2 and soluble Mn. MnO2 and CoOOH react with Ferrous and
dithionate in solution and the products of reactions are Ferric and sulfate. There is
precipitation of alumino-copiapite (Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O).

The first stage precipitation pH must be around 4.0 to remove Cu as amorphous
Cu ferrite (CuFe2 O4 . 2H2 O). There is dissolution of alumino-copiapite
(Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). At pH 4.0 Al precipitates first as amorphous Al
phosphate (AlPO4 . 2H2 O) and the remaining Al precipitates as Al hydroxyl-sulfate
(Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O) in large proportion and Alumino-copiapite
(Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). The saturation concentration of Al must be controlled
at around 1.0g/L. Ferric precipitates as Ferrihydrite (Fe(OH)3 ). There is mixed
precipitation of Co(OH)2 with Ferrihydrite (Fe(OH)3 ) (substances having the same
anion (OH − )). There is partial oxidation of Co(OH)2 into CoOOH by oxygen from Air.
Limestone is used as neutralization agent.
In the case there is an excess of phosphate comparatively to Al concentration,

All Al precipitates as amorphous Al phosphates (AlPO4 . 2H2 O). The remaining
phosphate precipitates as amorphous ferric phosphate (FePO4 . 2H2 O).
The second precipitation stage is done at pH ranged from 4.9 to 5.0. Al

saturation concentration is ranged from 20 to 10mg/L. Copper precipitates as
amorphous copper ferrite with the remaining ferric (CuFe2 O4 . 2H2 O). The remaining
phosphate precipitates as amorphous Al phosphate (AlPO4 . 2H2 O). Al precipitates as Al
hydroxyl-sulfate (Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O) in large portion and as amorphous Cu,
Co and Zn aluminates (CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O). Lime is used
as neutralization agent.
2.4.3. Two precipitation stage and recycling of UF of second

precipitation stage thickener to Copper circuit
Figure (2.6) gives the flow diagram of two stages of Fe and AL removal step with
recycling of UF of second precipitation stage thickener to copper circuit. The recycling of
UF of second precipitation stage is done at leach circuit in the case of conventional
circuit (Figure 2.7) and at CCD 1 in case of split circuit (Figure 2.8). The purpose of this
configuration is to recycle copper from cobalt circuit to copper circuit.
The first precipitation is done at pH less than 3.5 to avoid any copper
precipitation as amorphous copper ferric (CuFe2 O4 . 2H2 O). Al precipitates first as
amorphous Al phosphate (AlPO4 . 2H2 O). The remaining Al precipitates as alumino-
copiapite (Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). The remaining ferric precipitates as
Ferrihydrite (Fe(OH)3). There is mixed precipitation of Co(OH)2 with Ferrihydrite
(Fe(OH)3 ) (substances having the same anion (OH − )). There is partial oxidation of
Co(OH)2 into CoOOH by oxygen from Air.

Figure 2.6: Two stages of Fe and Al precipitation with recycling of UF of the second
stage precipitation to copper circuit
Figure 2.7: Copper conventional circuit with recycling of UF of the second stage
precipitation to leach circuit
When there is not enough ferric to maintain Al concentration at less than

1.0g/L, phosphoric acid can be added to control Al concentration at less than 1.0g/L.
Limestone is used as neutralization agent.

Figure 2.8: Copper split circuit with recycling of UF of the second stage precipitation to
CCD1

saturation concentration is ranged from 10 to 1.0mg/L. Copper precipitates as
phosphate precipitates as amorphous Al phosphate (AlPO4 . 2H2 O). Al precipitates as
amorphous Cu, Co and Zn aluminates (CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and
ZnAl2 O4 . 2H2 O). Lime is used as neutralization agent.
In the case of recycling of second stage precipitation thickener UF to CCD1 the

quantity of acid must be enough to dissolve elements from UF solid. The recycling of
second precipitation stage thickener UF to leach circuit increases the concentration of
Co in copper circuit solution. In consequence there are the increase of production of
dithionate in the leach circuit and the Co loss in copper circuit.
In the case when the cobalt dissolution keeps on in the CCD circuit using
Ferrous and dithionate as reducing agent, Al can precipitate as Alumino-copiapite
(Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O) in CCD circuit due to the increase of ferric
concentration.

2.4.4. Two precipitation stages, recycling of UF of second
precipitation stage thickener to first precipitation
stage and Using Cu solvent extraction for Cu
recovering from cobalt circuit
Figure (2.9) gives flow diagram of Fe and Al removal circuit with recycling of
second precipitation stage thickener UF to first precipitation stage and using Cu solvent
extraction to recover copper from cobalt circuit. Figure (2.10) gives the copper
conventional circuit with organic bleed configuration.
Figure 2.9: Two stages of Fe and Al precipitation with recycling of UF of the second
stage precipitation to first precipitation stage and using Cu solvent extraction
for copper recovering from cobalt circuit


Figure 2.10: Copper conventional circuit with organic bleed
The first precipitation stage is done at pH less than 3.5 to avoid any copper
precipitation as amorphous copper ferric (CuFe2 O4 . 2H2 O), There is dissolution of
alumino-copiapite (Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). Al precipitates as amorphous Al
phosphate (AlPO4 . 2H2 O) and Alumino-copiapite (Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). Al
saturation concentration depends on Ferric and phosphate concentration. The
remaining ferric precipitates as Ferrihydrite (Fe(OH)3 ). There is mixed precipitation of
Co(OH)2 with Ferrihydrite (Fe(OH)3 ) (substances having the same anion (OH − )). There
is partial oxidation of Co(OH)2 into CoOOH by oxygen from Air. The first precipitation
stage uses limestone as neutralization agent. The first precipitation is followed by
decantation and filtration circuit and copper solvent extraction.
A bleed of stripped organic is sent to Copper solvent extraction step in cobalt

circuit. Copper solvent extraction comes after first stage of Fe and Al removal step. The
pH of copper solvent extraction feed solution must be low than 2.0 to decrease the co-
extraction of Fe(III) on organic phase. The flowrate of stripped organic bleed is setup to
have 20mg/L of copper in the raffinate of Copper solvent extraction. This configuration
is better than the configuration with recycling of second stage precipitation thickener UF
to copper circuit.

saturation concentration is ranged from 10 to 1.0mg/L. Copper precipitates as

phosphate precipitates as amorphous Al phosphate (AlPO4 . 2H2 O). Al precipitates as
amorphous Cu, Co and Zn aluminates (CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and
ZnAl2 O4 . 2H2 O). Lime is used as neutralization agent.
2.4.5. Tree stages of Fe and Al removal circuit with copper

solvent for copper recovering from cobalt circuit
Figure (2.11) gives the flow diagram in which Fe and Al removal step is done in
three stages. This configuration is used when phosphate concentration in the feed
solution is low and there is no addition of phosphoric acid to control Al saturation
concentration.

The first precipitation stage is done at pH less than 3.5 to avoid any copper
precipitation as amorphous copper ferric (CuFe2 O4 . 2H2 O), There is dissolution of
alumino-copiapite (Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). Al precipitates as amorphous Al
phosphate (AlPO4 . 2H2 O) and Alumino-copiapite (Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). Al
saturation concentration depends on Ferric and phosphate concentration. The
remaining ferric precipitates as Ferrihydrite (Fe(OH)3 ). There is mixed precipitation of
Co(OH)2 with Ferrihydrite (Fe(OH)3 ) (substances having the same anion (OH − )). There
is partial oxidation of Co(OH)2 into CoOOH by oxygen from Air. The first precipitation
stage uses limestone as neutralization agent. The first precipitation is followed by
decantation and filtration circuit and copper solvent extraction.
The second precipitation stage is done at pH 4.2 after copper solvent extraction.
Al precipitates as hydroxyl-sulfate (Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O) and Al saturation
concentration is less than 1.0g/L. the second precipitation stage uses lime as
neutralization agent. The second precipitation stage is followed by decantation circuit.
UF of thickener is sent to the filtration of the first precipitation stage.

Figure 2.11: Three stages of Fe and Al precipitation with recycling of UF of the third
stage precipitation to first precipitation stage and using Cu solvent extraction
for copper recovering from cobalt circuit
The third precipitation stage is done at pH 5.2. Al precipitates as amorphous Cu,

Co and Zn aluminates (CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O). The
saturation concentration of Al is around 1.0mg/L. lime is used as neutralization agent.
UF of the third precipitation stage is sent to Fe(II) oxidation step.
2.4.6. Two stages of Fe and Al removal circuit with Cyanex

272 for Zn removal from cobalt circuit
Depending on Zn concentration in feed solution of cobalt circuit, when pH of last
stage of Fe and Al precipitation is more than 4.9 in the Fe and Al removal configuration
containing at least 2 stages there is important accumulation of Zinc in Fe and Al removal
circuit. Zinc precipitates as amorphous zinc aluminate and Zinc aluminate is dissolved in
ferrous oxidation step, copper leach circuit or CCD1. Zinc solvent extraction using
Cyanex 272 as extractant can be used to remove Zn in Fe and Al removal circuit.

Figure (2.12) gives flow diagram of two precipitation stages of Fe and Al
removal circuit with recycling of UF of the second precipitation stage to first
precipitation stage and Cyanex 272 for zinc removal from cobalt circuit.
Figure 2.12: Two precipitation stages of Fe and Al removal circuit with recycling of UF
of the second precipitation stage to first precipitation stage and using Cyanex
272 for zinc removal from cobalt circuit


The first precipitation stage is done at pH 4.0 to precipitate copper precipitation
as amorphous copper ferric (CuFe2 O4 . 2H2 O). There is dissolution of alumino-copiapite
(Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O). Al precipitates as amorphous Al phosphate
(AlPO4 . 2H2 O) and amorphous Al hydroxyl-sulfate (Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O).
Ferric precipitates as Ferrihydrite (Fe(OH)3). There is mixed precipitation of Co(OH)2
with Ferrihydrite (Fe(OH)3 ) (substances having the same anion (OH − )). There is partial
oxidation of Co(OH)2 into CoOOH by oxygen from Air. The first precipitation stage uses
limestone as neutralization agent. The first precipitation is followed by decantation and
filtration circuit.
Zn solvent extraction is done at pH 2.5 where Zn and Al are extracted

abundantly. Zn solvent extraction contains one stage of extraction and one stage of
stripping. The advance ratio (O/A) on extraction and stripping stages are respectively
1.25 and 30. The acid concentration in tripping acid solution is 150g/L. The extractant
concentration in the organic phase is setup to have 80% of zinc extraction efficiency. Al
solvent extraction efficiency is around 50%.

saturation concentration is ranged from 20 to 10mg/L. Copper precipitates as
phosphate precipitates as amorphous Al phosphate (AlPO4 . 2H2 O). Al precipitates as Al
hydroxyl-sulfate (Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O) in large portion and as amorphous Cu,
Co and Zn aluminates (CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O). Lime is used
as neutralization agent.
2.5. Mg removal step in cobalt precipitation cake
2.5.1. Purpose
Mg(OH)2 adsorbs great quantity of hydration water molecule. High grade of Mg
in the Co precipitation cake increases the moisture content. There are two ways to
removal Mg in the Co precipitation cake:
 First - the use of two Co precipitation stages. The UF of the second Co

precipitation cake is sent to the first Co precipitation stage.
 Second – the dissolution of Mg from Co precipitation cake.

2.5.2. Two Co precipitation stages
The use of two stage of cobalt precipitation increases MgO reaction extent.
Figure 2.12 gives the flow diagram with two stages of cobalt precipitation in which the
UF of second cobalt precipitation stage thickener is sent to Fe(II) oxidation step.
Figure 2.13 gives the flow diagram of cobalt circuit where there are two stages
of Co precipitation. Both cobalt precipitation stages use MgO as precipitation agent. But
the UF of second stage of cobalt precipitation thickener is sent to the first cobalt
precipitation stage. This configuration is used when Mn concentration is very low in the
cobalt circuit feed solution. Air/SO2 is used to oxidize Fe(II).
Figure 2.13: Two stages of cobalt precipitation with recycling of UF of the second stage
Co precipitation to first Co precipitation stage
Cobalt precipitation step is done in two stages. The first precipitation stage is
done at pH ranged from 7.5 to 7.8. Co concentration in solution is ranged from 1.0 to
0.5g/L. Al precipitates as amorphous cobalt, Copper and Zinc aluminates

precipitates as ZnCo3 (OH)6 SO4 . 3H2 O. Mn precipitates as Mn(OH)2. The partial
oxidation of Mn(OH)2 to MnOOH by oxygen from Air is negligible. The precipitation
efficiency of Mn is less than 10%. Phosphate precipitates as amorphous Co phosphate
(Co3 (PO4 )2 . 8H2 O). Carbonate precipitates as Mn and Co carbonates (MnCO3 and
CoCO3 ). The remaining Co precipitates as Co5 (OH)6 (SO4 )2 . 10H2 O and Co(OH)2. The
partial oxidation of Co(OH)2 to CoOOH by oxygen from Air is negligible. MgO utilization
is around 82%.
The second precipitation stage is done at pH ranged from 8.2to 8.4. Mn

precipitates as Mn(OH)2 . There is partial oxidation of Mn(OH)2 to MnOOH by oxygen
in the solid is as CoOOH. MgO utilization is around 70%.
UF of the second cobalt precipitation is recycled to the first cobalt precipitation

stage. There is dissolution of Mn and Co as Mn(OH)2, Co5 (OH)6 (SO4 )2 . 10H2 O and
Co(OH)2. There is not dissolution of Mn and Co as MnOOH and CoOOH. Un-reacted MgO
in the solid of UF from the second precipitation is re-leached to reach 82% of MgO
utilization at pH ranged from 7.5 to 7.8.
2.5.3. Dissolution of Mg in the Co precipitation cake

The best way to decrease the grade of Mg in Co precipitation cake is to dissolve
Mg from Co precipitation Cake. Figure (2.14) gives flow diagram of Co precipitation with
Mg dissolution step.
Co precipitation is done at pH ranged 8.2 to 8.4 using MgO as precipitation

agent. MgO utilization is around 70%. Co concentration in solution ranged from 0.20 to
0.10g/L.
Al precipitates as amorphous cobalt, Copper and Zinc aluminates

precipitates as ZnCo3 (OH)6 SO4 . 3H2 O. Mn precipitates as Mn(OH)2. There is partial
oxidation of Mn(OH)2 to MnOOH by oxygen from Air. Co adsorbs on MnOOH is oxidized
to CoOOH. Phosphate precipitates as amorphous Co phosphate (Co3 (PO4 )2 . 8H2 O).
Carbonate precipitates as Mn and Co carbonates (MnCO3 and CoCO3 ). The remaining Co
precipitates as Co5 (OH)6 (SO4 )2 . 10H2 O and Co(OH)2. There is partial oxidation of

Co(OH)2 to CoOOH by oxygen from Air. Co is adsorbed on MnOOH surface and MnOOH
oxidizes adsorbed Co into CoOOH. Mg precipitates as Mg(OH)2 . After decantation UF is
sent to Mg dissolution step.
Figure 2.14: Cobalt precipitation with dissolution of Mg from Cake
The Mg dissolution step is done at pH 7.0. There is dissolution of un-reacted

MgO in the solid to reach 90% of MgO utilization at pH 7.0. There is dissolution of Cu, Zn,
Mn, Mg and ferric as CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O, CuFe2 O4 . 2H2 O,
Co2 Cu3 (OH)6 (SO4 )2 . 5H2 O, ZnCo3 (OH)6 SO4 . 3H2 O, Mn(OH)2, Co3 (PO4 )2 . 8H2 O, MnCO3 ,
CoCO3 , Co5 (OH)6 (SO4 )2 . 10H2 O, Co(OH)2 and Mg(OH)2. There is not dissolution of Co
and Mn as MnOOH and CoOOH.
There is re-precipitation of elements as CoAl2 O4 . 2H2 O, CuAl2 O4 . 2H2 O and

ZnAl2 O4 . 2H2 O, CuFe2 O4 . 2H2 O, Co2 Cu3 (OH)6 (SO4 )2 . 5H2 O, ZnCo3 (OH)6 SO4 . 3H2 O,
Co3 (PO4 )2 . 8H2 O, MnCO3 , CoCO3 , Co5 (OH)6 (SO4 )2 . 10H2 O in large portion than Co(OH)2.
After filtration the filtrate is sent to Co precipitation step.

2.6. Mn removal step in cobalt circuit
2.6.1. Methods
There are two ways to remove Mn in the Cobalt circuit:
 First – using the mixture Air/SO2 to oxidize Mn at pH ranged from 2.5 to

3.0 (TFM - DRCono).
 Second – using disproportional reaction of MnOOH at low pH to remove
Mn in the Cobalt circuit.
2.6.2. Mixture Air/𝐒𝐎𝟐 as Mn oxidation agent

Figure (2.15) gives the flow diagram where Mn is removed from cobalt circuit
by the mixture Air/SO2 as oxidation agent.
There is dissolution of elements from solid of second stage of Fe and Al removal

step. Dissolution pH must be less than 2.0 to reach dissolution efficiency of 98%. Acid in
added to control pH at 2.0.
The pulp is discharged into the Mn oxidation step using mixture Air/SO2 as
oxidation agent. First Ferrous is oxidized in Ferric. At pH ranged from 2.5 to 3.0, Ferric
precipitates first as amorphous ferric phosphate (FePO4 . 2H2 O). The remaining ferric
precipitates as alumino-copiapite (Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O) and Ferrihydrite
(Fe(OH)3 ). The dithionate is oxidized in sulfate in the second position and sulfate
precipitates as gypsum (CaSO4 . 2H2 O). Mn is oxidized as hydrated MnO2 . Cobalt is
adsorbed on the surface of MnO2 and there is oxidation of Cobalt adsorbed on the
surface of MnO2 into CoOOH (James W. Murray et al, 1979). Mn oxidation reaction
extent depends on residence time and Eh. Eh is fixed by the flowrate of SO2 . SO2 in the
mixture Air/SO2 is oxidized in sulfate and sulfate precipitates as gypsum (CaSO4 . 2H2 O).
Pulp is discharged in neutralization step at pH ranged from 3.5 to 4.0 for copper
precipitation as amorphous copper ferrite (CuFe2 O4 . 2H2 O). There is dissolution of
ferric as FePO4 . 2H2 O, Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O and Fe(OH)3 . There is
precipitation of Al as amorphous Al phosphate (AlPO4 . 2H2 O) and hydroxyl-sulfate
(Al4 (OH)(11.36) (SO4 )(0.32) . 5H2 O). Ferric precipitates as amorphous copper ferrite
(CuFe2 O4 . 2H2 O) and the remaining ferric precipitates as Ferrihydrite (Fe(OH)3 ).

Figure 2.15: Mixture Air/SO2 as Mn oxidation agent
2.6.3. Disproportional reaction of MnOOH

Figure (2.16) gives the flow diagram of Cobalt circuit in which the
disproportional reaction of MnOOH is used to remove Mn in cobalt circuit.
Co precipitation must be done in two stages. The first precipitation stage is done
at pH ranged from 7.5 to 7.8. Co concentration in solution is ranged from 1.0 to 0.5g/L.
Al precipitates as amorphous cobalt, Copper and Zinc aluminates (CoAl2 O4 . 2H2 O,
CuAl2 O4 . 2H2 O and ZnAl2 O4 . 2H2 O). Fe(II) precipitates as Fe(OH)2. There is a total
oxidation of Fe(OH)2 to Fe(OH)3 by oxygen from Air. In presence of Cu, Fe(OH)3 is
transformed in amorphous Cu ferrite (CuFe2 O4 . 2H2 O) according to dissolution and
precipitation process in a presence of two salts having different solubility products. The
remaining Cu precipitates as Co2 Cu3 (OH)6 (SO4 )2 . 5H2 O. Zn precipitates as
ZnCo3 (OH)6 SO4 . 3H2 O. Mn precipitates as Mn(OH)2 . The partial oxidation of Mn(OH)2 to
MnOOH by oxygen from Air is negligible. The precipitation efficiency of Mn is less than
10%. Phosphate precipitates as amorphous Co phosphate (Co3 (PO4 )2 . 8H2 O). Carbonate

precipitates as Mn and Co carbonates (MnCO3 and CoCO3 ). The remaining Co
precipitates as Co5 (OH)6 (SO4 )2 . 10H2 O and Co(OH)2. The partial oxidation of Co(OH)2
to CoOOH by oxygen from Air is negligible. MgO utilization is around 82%.
Figure 2.16: Disproportional reaction of MnOOH for Mn removal
The second precipitation stage is done at pH ranged from 8.2to 8.4. Mn

precipitates as Mn(OH)2 . There is partial oxidation of Mn(OH)2 to MnOOH by oxygen
in the solid is as CoOOH. Lime is used as neutralization agent.
UF of the second cobalt precipitation is re-leached at pH 1.5 in Mn precipitation

step. There is dissolution of Mn and Co as Mn(OH)2, Co5 (OH)6 (SO4 )2 . 10H2 O and
Co(OH)2. MnOOH reacts with acid according to disproportional reaction giving MnO2
and Mn in solution as products. Mn in solution reacts with CoOOH as reducing agent
giving MnO2 and Co in solution as products. Co is adsorbed on MnO2 surface and there is
oxidation of this adsorbed Co into CoOOH (James W. Murray et al, 1979).

3. Precipitation process
3.1. Definition
Precipitation reactions occur when cations and anions in aqueous solution
combine to form an insoluble ionic solid called precipitate. The precipitation is a
spontaneously and relatively fast crystallization process.
3.2. Precipitation – condition

In the close system, there is precipitation reaction given by the chemical
reaction (3.a). “υi ” is the stoichiometry coefficient of the substance “i” and “A”, “B”, “C”
and “D” are the chemical substances. “C” is the precipitate.
υa A + υb B + υe e− = υc C + υd D (3.a)
At constant temperature and pressure, Equation (3.1) gives thermodynamic

condition of precipitation reaction (3.a). This condition is called supersaturation.
ΔG=ΔGc +ΔGs -ΔGM <0 (3.1)
“ΔGc ” is the chemical potential energy of the chemical reaction (3.a) and the
value is given by Equation (3.2). Where “μi ” is the chemical potential of the substance “i”,
“F” is faraday constant and “E” is the redox potential.
ΔGc = (υc *μC + υd *μD )-(- υe *F*E + υa *μA + υb *μB ) (3.2)
“ΔGs ” is the surface energy on the precipitate and the value is given by Equation
(3.3). Where “σ” is surface energy of precipitate and “A” is molar surface area of
precipitate.
ΔGs =σ*A (3.3)
“ΔGM ” is the internal energy consumed due to the path of the reaction
mechanism. The mechanism of precipitation of precipitation reaction contains two
steps. The first step is the nucleation. Nucleation is commonly defined as the formation
of the first thermodynamically stable solid. The second step is the growth. Growth is
when the thermodynamically stable nuclei grow into larger particles by deposition of
solute from the supersaturated solution.

Evaluation of values of “ΔGs ” and “ΔGM ” depends on the knowledge of the size of
particles and the path way of the chemical reaction. Therefore Equation (3.4) gives the
simplest surpersaturation coming only from variation of chemical potential of products
and reactants.
(υc ∗μC + υd ∗μD )

>1 (3.4)
(− υe ∗F∗E + υa ∗μA + υb ∗μB )
3.3. Simultaneous precipitation of at least two

cations
3.3.1. Precipitation of cations on solid surface
3.3.1.1. Adsorptions
 Definition
The adsorption is surface complexation reaction on solid surface with adsorbate

when solid is introduced in the solution. “Adsorbate” refers to the solute that adsorbs
onto the solid phase. “Adsorbent” is the solid phase or substrate onto which the
adsorbate adsorbs. “Adsorption” refers to the two-dimensional accumulation of an
adsorbate at a solid surface (Kathleen S. Smith, 1999). There is not detection of second
solid phase on X-rays diffraction analysis (K. G. Karthikeyan et al, 1999).
For adsorption reactions of cations on oxide minerals, pH is master variable.

Cation adsorption increases with increasing pH near zero to nearly 100% over a pH
range of 1 to 2 units. This pH region is termed the adsorption edge and its placement
depends on the characteristic of the particular adsorbate, to the concentrations of
surface binding sites on oxide mineral and to the concentration of adsorbate into
solution. Anion adsorption is the mirror image of cation adsorption in that anion
adsorption tends to decrease with increasing pH.
The term “absorption” is used when there is diffusion of the adsorbate into the
solid phase.

 Example
The removal of heavy metals from wastewater uses adsorption on Iron

hydroxide or Al hydroxide (K. G. Karthikeyan et al, 1999 and Masanori Okazaki et al,
1986).
3.3.1.2. Surface precipitation
Surface precipitation that occurs when solid is introduced in the solution is the
step coming after adsorption. Surface precipitation is a three-dimensional accumulation
of adsorbate at the solid surface. Adsorption, the two dimensional accumulation, acts as
nuclei of surface precipitation. There is detection of second solid phase on X-rays
diffraction analysis. There is a ratio adsorbate/adsorbent above which the surface
precipitation starts (K. G. Karthikeyan et al, 1999).
3.3.2. Precipitation of one solid containing at least two

cations
3.3.2.1. Co-precipitation
 Definition
In this paper, co-precipitation is the simultaneous precipitation of at least two

cations in the form of a homogeneous solid solution (single crystal structure).
 Example
Co-precipitation of Iron (III) and Cr(VI) forms a hydroxide of Fe-Cr

(Fe(0.994) Cr(0.006) OOH) (K. G. Karthikeyan et al, 1999).
3.3.2.2. Atomic substitution or inclusion
 Definition
Atomic substitutions or inclusions occur because some elements have the same
size and charge, and can therefore substitute for one another in a crystal structure. The
ionic radii differ by approximately 15 percent or less. Limited substitution can occur if
the radii differ by 15 to 30 percent, and a difference of more than 30 percent makes
substitution unlikely (Huseyin Basturkcu et al, 2017 and Sanchez Espana J. et al, 2015).

 Example
In mining drainage and below this pH 3.3 in the presence of ferric iron, Al and
ferric ion may precipitate at a substantial extent to form particles of Al-rich crystals of
H3O+- to K+-jarosite (containing up to molar ratio [Fe/(Fe+Al)]=0.54). This Al
incorporation seems to take place by atomic substitution for Fe3+ in jarosite (Sanchez
Espana J. et al, 2015).
3.3.3. Mixed precipitation - precipitation of at least two

solids containing one common cation or anion
3.3.3.1. Concept
Mixed precipitation occurs during the simultaneous precipitation of two solids

in mixture creating favorable precipitation conditions for one or both solids. The
presence of a common cation or anion in the structure of the two solids promotes mixing
of solids.
The solids are mixed to form either the heterogeneous solid solution in which
there is a juxtaposition of the two solids or the homogenous solid solution in which the
two solids react to form a new solid with new crystalline structure (ideal mixing).
3.3.3.2. Example
The mixed precipitation occurs in the transition zone. On Eh-pH diagram, each
solid that precipitates from aqueous solution has a stability zone. Between two stability
zones of two solids, there is a transition zone where both solids precipitate. The
precipitation of both solids is promoted by the mixture conditions.
The simultaneous precipitation of Langite and Copper hydroxide is the example

of mixed precipitation in transition zone on Eh-pH diagram (R. Nasanen et al, 1949).
Two solids have the common cation.
During precipitation of Al at room temperature, Al starts to precipitate at pH 4.0

without the presence of ferric as hydroxyl-sulfate of Al. In presence of ferric, Al starts to
precipitate at pH 3.5 (Monica M. Jimenez Correa at al, 2016). The first way uses to
explain the nearly precipitation of Al in presence of ferric is the adsorption mechanism
(Sanchez Espana J. et al, 2015). The second way is mixed precipitation of ferrihydrite
and hydroxyl-sulfate of Al because of the common anion (OH).

3.3.4. Solid occlusion
3.3.4.1. Concept
Occlusion is the mechanism of precipitation that occurs when the unintended

ions are mechanically trapped, either as solids or liquids, in the crystal layers of the
parent precipitate. Therefore, it follows that these unintended ions cannot be washed off
the precipitate in an attempt to free them (Masambi S. 2015).
It has been suggested that occlusion is the main mechanism of simultaneous

precipitation in many freshly prepared oxides and hydroxides. This is because of high
supersaturation that leads to higher nucleation rates and lower growth rates thereby
trapping unintended ions between ‘rushed’ crystal layers
3.3.4.2. Example
Example of occlusion - Precipitation of Fe(III) from solution containing 10g/L of

Fe(III), 10g/L of Co, 10g/L of Ni and 10g/L of Zn at pH 2.7 and 50°C gives Iron
precipitate containing 49.4% of Fe, 0.65% of Co, 0.63% of Ni and 0.69% of Zn.
3.4. Thermodynamic approach
3.4.1. Thermodynamic approach of atomic substitution

and inclusion
3.4.1.1. Model 1
 Concept
If A and B are two solids which react to form a solid solution. The reaction (3.b)
gives the reaction between the solids A and B. The Free Gibbs energies of solid A and B
in the solid solution are given by Equations (3.5) and (3.6) where γA and γB are the
activity coefficients and X A and XB are molar fractions (non ideal mixing). The free Gibbs
energy of the solid solution is given by Equation (3.7).
αA + βB = Aα Bβ (3.b)
μA =μ°A +2.303*R*T.log(γA *XA ) (3.5)

μB =μ°B +2.303*R*T.log(γB *XB ) (3.6)
μ(Aα Bβ ) =XA *μA +XB *μB (3.7)
 Example
Radium sulfate and barium sulfate can precipitate together in aqueous solution
to form a solid-solution (Raα , Baβ )SO4. The reaction (3.c) gives the reaction between
Radium sulfate and barium sulfate where α and β are the molar fractions.
αRaSO4 + βBaSO4 = (Raα , Baβ )SO4 (3.c)
The aqueous solubility product K S of Radium sulfate for the reaction (3.d) is
given by Equation (3.8) (V.L. Vinograd et al, 2018). a(Ra+2 ) is activity of Ra+2 in aqueous
solution, a(SO−2
4 )
is activity of SO−2
4 in aqueous solution and a (RaSO4 ) is activity of RaSO4 in
the solid-solution. “α” is the molar fraction of each solid in the mixture and “γ” is the
activity coefficient. In this case the mixing reaction is done in non-ideal condition.
Ra+2 + SO−2
4 = RaSO4 (3.d)
a(Ra+2 ) ∗a(SO−2 ) a(Ra+2 ) ∗a(SO−2 )

Ks= 4
= 4
(3.8)
a(RaSO4 ) γ∗α
3.4.1.2. Model 2
The logarithmic distribution of ions applies according to Equation

(3.9)(Masambi S., 2015).
C C
log(Ci )=λ*log(CPi ) (3.9)
f Pf
where 𝐶𝑖 is the initial concentration of the value metal in solution, 𝐶𝑓 is the final
concentration of the value metal in solution, 𝐶𝑃𝑖 is the initial concentration of
the primary ion to be precipitated in solution, 𝐶𝑃𝑓 is the final concentration of
the primary ion to be precipitated in solution and λ is the logarithmic
distribution coefficient.
The value of λ decreases with the increasing of the temperature.

3.4.2. Thermodynamic approach of mixed precipitation
3.4.2.1. Concept
The major assumption is that the precipitate is the juxtaposition of solid

compounds.
3.4.2.2. Thermodynamic conditions
The thermodynamic conditions of mixed precipitation of solid compounds are

the following (Josep M. Soler, 2007):
 The precipitate is mixture of solid compounds. The activity of solid compound in

the mixture is molar fraction. The chemical potential of solid compounds is
given by Equation (3.10). “X” is the molar fraction.
μ=μ° + R*T*2.303*Log(X) (3.10)
 Each solid compound in the precipitate is independently in equilibrium with all

soluble compounds.
In the close system, there is precipitation reaction given by the chemical

reaction (3.a). “υi ” is the stoichiometry coefficient of the substance “i” and “A”, “B”, “C”
and “D” are the chemical substances. “C” is the precipitate
υa A + υb B + υe e− = υc C + υd D (3.a)
The chemical potential of soluble substance “A” is given by Equation (3.11).

Where “CA ” and “γA ” are respectively the molarity and activity coefficient of soluble
substance “A” in solution.
μA =μ°A + R*T*2.303*Log(CA *γA ) (3.12)
At equilibrium, the chemical potential of soluble substance “A” is given also by

Equation (3.13). Where the chemical potential of precipitate “C” is given by Equation
(3.14).
μA =(υC *μC +υD *μD +υe *F*E-υB *μB )*(1/υA ) (3.13)
μC =μ°C + R*T*2.303*Log(XC ) (3.14)

The chemical potentials of soluble substance “A” given by Equations (3.12) and
(3.13) are equal. This is the thermodynamic constraint of molar fraction “XC ” of solid “C”
in the precipitate.
For the solid in the mixture, the constraint on molar fraction is given by
Equation (3.15).
∑ XN =1 (3.15)

4. Realistic Simulation Model (RSM)
4.1. Characterization of pulp
Generally, the suspension of particles in a solution is called pulp. The suspended
particles will be called solid and form the solid phase while the impregnation solution is
the liquid phase. Therefore, the pulp is always consisted of two components: solid and
liquid.
4.2. Specific gravity
4.2.1. Solid specific gravity
4.2.1.1. Laboratory method
When it is possible to have physically the solid, the laboratory method for
obtaining the specific gravity of solid consisting of mineral rock finely crushed is as
follows:
 Dry the crushed solid in an oven at 80 ° C for 24 hours,

 Weigh the solid (kg) (weight between 0.100 and 0.300 kg),
 Put the solid in a test tube of one liter,
 Add the water in the test tube up to 500 ml,
 Mix the solid and the water until complete homogenization,
 Add more water in the test tube to the mark of a liter and,
 Weigh the volume of one liter of pulp.
After the practical operations, the other data is determined as follows:
 The weight of water is the difference between the weight of pulp and
the weight of solid.
 The volume of water is the ratio of weight onto the specific gravity of
water (1,000 kg/m3).
 The volume of solid is the difference between the volume of pulp and
the volume of water.
 Finally, the specific gravity of solid is the ratio of the weight onto the
volume of solid.
Table (4.1) shows an example for obtaining the specific gravity of solid by the
laboratory method. This method seems simple, but it requires great accuracy during the
weighing and the measuring of values.
Table 4.1: Specific gravity of solid from the laboratory method
Description Units Equations values

Weight of solid kg 0.141
Weight of pulp kg 1.089
Volume of pulp L 1.000
Weight of water kg Weight of pulp – Weight of solid 0.948
Volume of water L Weight of water/specific gravity of water 0.948
Volume of solid L Volume of pulp – volume of water 0.052
SG of solid kg/m3 Weight of solid/volume of solid*1000 2,711.54
4.2.1.2. Mineralogical composition method
When the solid is not provided in order to obtain its specific gravity by the
laboratory method, the determination of specific gravity of solid is taken place by using
the mineralogical composition method. This method is based on the principle that rock
is a juxtaposition of minerals. Therefore, the mass of rock is the sum of masses of
minerals and the volume of rock is the sum of volumes of minerals. Based on these
assumptions, the method for obtaining the rock specific gravity consists of:
 Knowing the weight percentage of minerals in the solid.

 Calculating the weight of minerals in a unit mass of solid.
 Knowing the respective specific gravity of minerals.
 Calculating the volumes of minerals.
 Determining the volume of solid by the addition of volumes of minerals.
 Calculating the specific gravity of solid
The weakness of this method is that it ignores porosities or structural defects of

solid.
Table (4.2) shows an example for obtaining the specific gravity of solid by using
the mineralogical composition method. The result from Table (4.2) shows that for a total
weight of 1,000 t of solid and a total volume of 359.77 m3 of solid which is the sum of
volumes of minerals, the value of specific gravity of solid is 2,779.55 kg/m3.

Table 4.2: Specific gravity of solid from the mineralogical composition
Minerals Grade weight Specific gravity Volume of Specific

of mineral mineral gravity of
solid
% t t/m3 m3 kg/m3
Cu2(OH)2(CO3) 1.584 15.836 4.00 3.959
Cu3(PO4)2.Cu2(OH)4 0.146 1.456 4.20 0.347
2CuO.2SiO2.3H2O 0.199 1.989 2.20 0.904
CuO 0.503 5.029 6.40 0.786
CuS 0.005 0.055 4.68 0.012
Cu2S 0.005 0.055 5.65 0.010
CuFeS2 0.005 0.055 4.20 0.013
CoOOH 0.507 5.070 4.00 1.268
FeO(OH) 1.954 19.543 3.65 5.354
Ni(OH)2 0.001 0.010 4.10 0.002
CaCO3.MgCO3 0.900 9.000 2.85 3.158
MnO2 0.127 1.266 4.85 0.261
ZnS 0.007 0.067 4.00 0.017
SiO2 77.139 771.393 2.65 291.092
UO3 0.004 0.040 10.97 0.004
Mg2SiO4 5.381 53.805 3.15 17.081
Ca2SiO4 0.011 0.110 2.71 0.041
CaCl2 0.025 0.250 2.15 0.116
Al2SiO5 11.471 114.710 3.25 35.295
Cr2O3 0.026 0.256 5.22 0.049
CdO 0.001 0.006 8.15 0.001
Total 1000 359.77 2,779.55
4.2.2. Liquid specific gravity
4.2.2.1. Laboratory method

When it is possible to have physically the liquid, the laboratory method for
obtaining the specific gravity of liquid is as follows:
 Put the liquid in a test tube of one liter to the mark of a liter,
 Weigh the volume of one liter of liquid (g),
 And the ratio of weight onto the one liter volume of liquid gives the
specific gravity.
The specific gravity obtained in this condition is the approximated value at

ambient temperature.
4.2.2.2. Chemical composition method
Equation (4.1) gives the approximate value of specific gravity of liquid in as

function of liquid chemical composition (Kafumbila J., 2017a).

SGL = -6.139 * 10−7 x [GT ]2 + 9.742 * 10−4 * GT + 1 (4.1)
Where “ 𝑆𝐺𝐿 ” is liquid specific gravity (t/m3) and “𝐺𝑇 ” is total concentration of
soluble compounds (g/L)
4.3. Soluble compounds
4.3.1. Activity of soluble species

 Ionic strength
The ionic strength of the system is given by Equation (4.2). 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 (4.2)
 Water activity
The activity of water (solvent) (𝑎𝑤 ) is given by Equation (4.3). “ϕ” is the
osmotic coefficient, “W” is the molecular weight of water (18.016) and “𝑚𝑖 ” is the
concentration (mol/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 (4.3) becomes Equation (4.4).
W
ln (aw ) = - 1000 *ϕ *∑i mi (4.3)
W
ln (aw ) = - 1000 *ϕ *∑i Ci (4.4)
The calculations of osmotic coefficient have been approximated by Equation

(4.5) (H.C. Helgeson, 1969). The value of “u” is given by Equation (4.6). Table (4.3) gives
values of parameters “a”, “b”, “c” and “d” at 298.15 K. “A” comes from Debrye-Huckel
Equation for activity coefficient and is function of temperature. The value of “A” is
0.5092 at 298.15K. “I” is the ionic strength (mol/kg of water). In this case, the ionic
strength is given in mol/L.
2.303∗A 1 b∗I 2c∗I2 3d∗I3

ϕ=1- [u -2ln(u) - u] + + + (4.5)
a3 ∗I 2 3 4
u=1+a*√I (4.6)

Table 4.3: values of a, b, c and d parameter at 298.15K
a b c d
1.454 0.02236 9.38 x10−3 -5.362x10−4
 Activity coefficients
Activity of soluble compound “i” in water is given by Equation (4.7). “γi ” is

activity coefficient and Ci is the concentration (mol/L) of soluble compound.
ai = γi * Ci (4.7)
The calculations of individual ion activity coefficient have been approximated by

Equation (4.8) 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. “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 mol/L). “A”, “B” and
“b” are temperature-dependent parameters. Table (4.4) gives values of parameters “A”,
“B” and “b” at 298.15 K (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 (4.8)
Table 4.4: values of A, B and b parameter at 298.15K
A B x 10−10 b
0.509 0.328 0.064
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 (mol/kg of water) (H.C. Helgeson
et al, 1981).
4.3.2. Concentration of soluble species

In the case of the simulation of Copper and Cobalt circuit (pH 1.0- 12.0) the
soluble compounds taken as reference are: H + , SO−2 −2 − −
4 , S2 O6 , H2 PO4 , HCO3 , Si(OH)4 ,
Cu+2 , Co+2 , Zn+2, Ni+2 , Mn+2, Mg +2 , Al+3 , Ca+2 , Fe+2, Fe+3, and Na+ . The concentrations
of other soluble compounds are calculated from the known concentrations values of

references. Table (4.5) gives other soluble compounds and equilibrium constant of
chemical reaction between other soluble compounds and references.
Table 4.5: Other soluble compounds and equilibrium constant of chemical reaction
between soluble compounds and references
Species Chemical reaction Log(k) Reference

HSO− 4 H + +SO−2
4 =HSO4
−
1.99 MINTEQ
H2 SO4 2H + +SO−2
4 =H2 SO4 0.08 Jacques Chivot, 2004
H3 PO4 H +H2 PO−
+
4 =H3 PO4 2.148 MINTEQ
H2 CO3 H + +HCO−3 =H2 CO3 6.352 MINTEQ
CuSO4 Cu +SO−2
+2
4 =CuSO4 2.360 MINTEQ
CuH2 PO+ 4 Cu +H2 PO−
+2
4 =CuH2 PO4
+
1.140 Thermoddem
CuHCO3+ Cu+2 +HCO− 3 =CuHCO3
+
1.800 MINTEQ
CoSO4 Co+2 +SO−24 =CoSO4 2.300 MINTEQ
CoHCO3+ Co +HCO−
+2
3 =CoHCO3
+
2.091 MINTEQ
ZnSO4 Zn+2+SO−2 4 =ZnSO4 2.460 Thermoddem
ZnH2 PO+ 4 Zn +H2 PO−
+2
4 =ZnH2 PO4
+
1.590 Thermoddem
ZnHCO+ 3
−
Zn+2+HCO3 =ZnHCO3 +
1.500 MINTEQ
NiSO4 Ni+2 +SO−2
4 =NiSO4 2.35 PSI/Nagra Chemical
NiHCO+ 3 Ni +HCO−
+2
3 =NiHCO3
+
2.091 MINTEQ
MnSO4 Mn+2+SO−2 4 =MnSO4 2.25 MINTEQ
MnH2 PO+ 4 Mn+2+H2 PO− 4 =MnH2 PO4
+
1.340 Thermoddem
MnHCO+ 3 Mn+2+HCO− 3 =MnHCO3
+
1.300 MINTEQ
MgSO4 Mg +2 +SO−24 =MgSO4 2.260 MINTEQ
MgH2 PO+ 4 Mg +2 +H2 PO− 4 =MgH2 PO4
+
1.683 MINTEQ
MgHCO3+ Mg +2 +HCO− 3 =MgHCO3
+
1.010 MINTEQ
NaSO− 4 Na+ +SO−2
4 =NaSO4
−
0.730 MINTEQ
AlSO+4
+3 −2
Al +SO4 =AlSO4 +
3.35 Yoshiyuki Matsushima et al, 1988
AlHPO+ 4 Al+3 +H2 PO− 4 =AlHPO4 +H
+ +
0.190 Thermoddem
AlH2 PO+2 4 Al+3 +H2 PO− 4 =AlH2 PO4
+2
3.100 Thermoddem
FeHSO+ 4 Fe+2+H + +SO−2 4 =FeHSO4
+
3.068 PSI/Nagra Chemical
+2 −2
FeSO4 Fe +SO4 =FeSO4 2.390 MINTEQ
FeH2 PO+ 4 Fe+2+H2 PO− 4 =FeH2 PO4
+
2.700 MINTEQ
FeHCO+ 3 Fe+2+HCO− 3 =FeHCO3
+
1.100 MINTEQ
FeHSO+2 4 Fe+3+H + +SO−2 4 =FeHSO4
+2
4.468 PSI/Nagra Chemical
FeSO+4 Fe+3+SO−24 =FeSO4
+
4.050 MINTEQ
Fe(SO4 )− 2 Fe+3+2SO−2 4 =Fe(SO4 )2
−
5.380 MINTEQ
+3 + −2
FeH(SO4 )2 Fe +H +2SO4 =FeH(SO4 )2 8.100 J. T. Gallardo, 2004
FeHPO+ 4 Fe+3+H2 PO− 4 =FeHPO4 +H
+ +
2.719 MINTEQ
FeH2 PO+2 4 Fe+3+H2 PO− 4 =FeH2 PO4
+2
4.279 MINTEQ
−2
CaSO4 Ca+2 +SO4 =CaSO4 2.30 PSI/Nagra Chemical
CaH2 PO+ 4 Ca+2 +H2 PO− 4 =CaH2 PO4
+
1.350 MINTEQ
CaHCO3+ Ca+2 +HCO3− =CaHCO+ 3 1.270 MINTEQ
Si(OH)4 SiO2 +2H2 O=Si(OH)4 -2.714 PSI/Nagra Chemical

 Hydrogen ion
The molarity of H + (C(H+) ) is given by Equation (4.9) when the pH is known

value. When the pH is not known value the molarity of H + (C(H+) ) is given by the known
value of the total concentration of sulfur (C(s) ) (Equation 4.10).
C(H+ ) =10(−pH) *(γ1 )(−1) (4.9)
C(s) =C(SO−2
4 )
+C(HSO−4 ) +C(H2 SO4) +2*C(S2 O−2
6 )
+C(CuSO4 ) +C(CoSO4 )+C(ZnSO4 )+
C(NiSO4 ) +C(MnSO4 )+C(MgSO4)+C(NaSO−4 ) +C(AlSO+4 ) +C(FeHSO+4 ) +C(FeSO4 )+
C(FeHSO+2
4 )
+C(FeSO+4 ) +2*C(Fe(SO4 )−2 ) +2*C(FeH(SO4 )2 )+C(CaSO4 ) (4.10)
 Sulfate
The molarity of SO−2

4 (C(SO−2
4 )
) is fixed by electrical neutrality of solution. Total
positive electrical charge (Ch+) is given by Equation (4.11) and total negative electrical
charge (Ch-) is given by Equation (4.12). Total positive electrical charge (Ch+) is equal
to total negative electrical charge (Ch-) (Equation 4.13).
Ch+=C(H+) +2*C(Cu+2 ) +C(CuH2 PO+4 ) +C(CuHCO+3 ) +2*C(Co+2 )+C(CoHCO+3 ) +2*C(Zn+2 ) +

C(ZnH2 PO+4 ) +C(ZnHCO+3 ) +2*C(Ni+2 ) +C(NiHCO+3 )+2*C(Mn+2 ) +C(MnH2 PO+4 ) +
C(MnHCO+3 ) +2*C(Mg+2 ) +C(MgH2PO+4 ) +C(MgHCO+3 ) +C(Na+) +3*C(Al+3 ) +C(AlSO+4 )
+C(AlHPO+4 ) +2*C(AlH2 PO+2
4 )
+2*C(Fe+2 ) +C(FeHSO+4 ) +C(FeH2 PO+4 ) +C(FeHCO+3 ) +3
*C(Fe+3 ) +2*C(FeHSO+2
4 )
+C(FeSO+4 ) ++C(FeHPO+4 ) +2*C(CuH2 PO+2
4 )
+2*C(Ca+2 ) +
C(CaH2 PO+4 ) +C(CaHCO+3 ) (4.11)
Ch-=2*C(SO−2
4 )
+C(HSO−4 ) +C(H2 PO−4 ) +C(HCO−3 ) +C(NaSO−4 ) +C(Fe(SO4 )−2 ) (4.12)
Ch+= Ch- (4.13)
 Dithionate
The molarity of S2 O−2

6 (C(S2 O−2
6 )
) is known value.
 Phosphate
The molarity of H2 PO− 4 (C(H2 PO−

4)
) is fixe by the total concentration of
phosphorous (C(P) ) in solution (Equation 4.14)

C(P) =C(H2 PO−4 ) +C(H3 PO4) +C(CuH2 PO+4 ) +C(ZnH2 PO+4 ) +C(MnH2PO+4 ) +C(MgH2PO+4 ) +
C(AlHPO+4 ) +C(AlH2 PO+2
4 )
+C(FeH2 PO+4 ) +C(FeHPO+4 ) +C(FeH2 PO+2
4 )
+C(CaH2 PO+4 )
(4.14)
 Carbonate
First - the molarity of HCO3− (C(HCO−3 ) ) is fixed by the saturation concentration of

S
H2 CO3 (C(H 2 CO3 )
) in equilibrium with CO2 partial pressure (Equation 4.15). P(CO2) in
atmosphere is equal to 3.5*10(−4) atm. P(CO2) in the precipitation tank using limestone as
neutralization agent or leach tank in which there is dissolution of carbonate is pressure
of pulp at H/2 (H is height of volume live of tank). P(CO2) is the thickener working after
precipitation tank using limestone as neutralization agent is pressure of pulp at 1.0m
height.
S
C(H 2 CO3 )
=0.046*P(CO2 )
(4.15)
Second - the molarity of HCO−

3 (C(HCO−
3)
) is fixed by the total concentration of
carbon (C(C) ) in solution (Equation 4.16).
C(C) =C(HCO−3 ) +C(H2 CO3) +C(CuHCO+3 ) +C(CoHCO+3 ) +C(ZnHCO+3 ) +C(NiHCO+3 ) +C(MnHCO+3 )

+C(MgHCO+3 ) +C(FeHCO+3 ) +C(CaHCO+3 ) (4.16)
Third - the molarity of HCO−

3 (C(HCO−
3)
) is fixed by the saturation concentration
S
of HCO3− (C(HCO − ) ) fixed by the saturation concentration of Calcium carbonate (Equation
3
4.17). Ca carbonate precipitation reaction is given par la chemical reaction (4.a).
Ca+2 +HCO−
3 =CaCO3 +H
+
(4.a)
C(H+ ) ∗γ(H+ )
S
C(HCO − ) =99.77* (4.17)
3 C (Ca+2 ) ∗γ(Ca+2 )∗γ(HCO− )
3
 Silicate
The molarity of Si(OH)4 C(Si(OH)4 ) is fixed by the saturation concentration of

amorphous silicate (Equation 4.18). Amorphous silicate precipitation reaction is given
by the chemical reaction (4.b).
Si(OH)4 =SiO2(a) +2H2 O (4.b)
C(Si(OH)4 ) = 1.932*10(−3) *(aw )(2) (4.18)

 Copper
The molarity of Cu+2 C(Cu+2 ) is fixed by the total molarity of soluble Cu (C(CuT) )
(Equation 4.19).
C(CuT) =C(Cu+2 ) +C(CuSO4) +C(CuH2 PO+4 ) +C(CuHCO+3 ) (4.19)
 Cobalt
The molarity of Co+2 C(Co+2 ) is fixed by the total molarity of soluble Co (C(CoT))
(Equation 4.20).
C(CoT) =C(Co+2 )+C(CoSO4) +C(CoHCO+3 ) (4.20)
 Zinc
The molarity of Zn+2 C(Zn+2 ) is fixed by the total molarity of soluble Zn (C(ZnT) )
(Equation 4.21).
C(ZnT) =C(Zn+2 )+C(ZnSO4 )+C(ZnH2PO+4 ) +C(ZnHCO+3 ) (4.21)
 Nickel
The molarity of Ni+2 C(Ni+2 ) is fixed by the total molarity of soluble Ni (C(NiT) )
(Equation 4.22).
C(NiT) =C(Ni+2 ) +C(NiSO4 ) +C(NiHCO+3 ) (4.22)
 Manganese
The molarity of Mn+2 C(Mn+2 ) is fixed by the total molarity of soluble Mn

(C(MnT) ) (Equation 4.23).
C(MnT) =C(Mn+2 ) +C(MnSO4 )+C(MnH2PO+4 ) +C(MnHCO+3 ) (4.23)

 Magnesium
The molarity of Mg +2 C(Mg+2 ) is fixed by the total molarity of soluble Mg (C(MgT) )

(Equation 4.24).
C(MgT) =C(Mg+2 ) +C(MgSO4 )+C(MgH2 PO+4 ) +C(MgHCO+3 ) (4.24)
 Sodium
The molarity of Na+ C(Na+) is fixed by the total molarity of soluble Na (C(NaT) )
(Equation 4.25).
C(NaT) =C(Na+) +C(NaSO−4 ) (4.25)
 Aluminum
The molarity of Al+3 C(Al+3 ) is fixed by the total molarity of soluble Al (C(AlT) )
(Equation 4.26).
C(AlT) =C(Al+3 )+C(AlSO+4 ) +C(AlHPO+4 ) +C(AlH2 PO+2

4 )
(4.26)
 Iron (II)
The molarity of Fe+2 C(Fe+2 ) is fixed by the total molarity of soluble Fe(II)
(C(Fe(II)T) ) (Equation 4.27).
C(Fe(II)T) =C(Fe+2 ) +C(FeHSO+4 ) +C(FeSO4 ) +C(FeH2 PO+4 ) +C(FeHCO+3 )

(4.27)
 Iron (III)
First - the molarity of Fe+3 C(Fe+3 ) is fixed by the total molarity of soluble Fe(III)
(C(Fe(III)T) ) (Equation 4.28).
C(Fe(III)T) =C(Fe+3 ) +C(FeSO+4 ) +C(Fe(SO4 )−2 ) +C(FeHSO+2

4 )
+C(FeH(SO4 )2 ) +C(FeHPO+4 )
+C(FeH2 PO+2
4 )
(4.28)
Second - in the case where the value of Eh is a known value the molarity of Fe+3
C(Fe+3 ) is fixed by the molarity of Fe+2 C(Fe+2 ) and Eh (Equation 4.29).
log(C(Fe+3 ) *γ3 )=log(C(Fe+2 ) *γ2 )+(Eh-0.769)*16.901 (4.29)

 Calcium
First - the molarity of Ca+2 C(Ca+2 ) is fixed by the total molarity of soluble Ca
(C(CaT) ) (Equation 4.30).
C(CaT) =C(Ca+2 ) +C(CaSO4) +C(CaH2 PO+4 ) +C(CaHCO+3 ) (4.30)
Second - in presence of gypsum in the solid, the molarity of Ca+2 C(Ca+2 ) is fixed
by the saturation concentration of gypsum (Equation 4.31).
2.624∗10(−5)
C(Ca+2 ) =C 2 (4.31)
−2 ) ∗γ(SO−2 ) ∗(aw ) ∗γ(Ca+2 )
(SO4 4
 Total concentration of soluble compounds
Equation (4.32) gives the total concentration of soluble compounds (g/L)(GT ).
GT =G(H) +G(SO4 )+G(PO4 ) +G(CO3 ) +G(Si(OH)2 ) +G(S2 O6 ) +G(Cu) +G(Co) +G(Zn)+G(Ni) +

G(Mn) +G(Mg) +G(Na) +G(Al) +G(Fe2) +G(Fe3) +G(Ca) (4.32)
G(H) =(C(H+ ) +C(HSO−4 ) +2*C(H2 SO4 )+2*C(H2 PO−4 ) +3*C(H3 PO4 ) +C(HCO−3 ) +2*C(H2 CO3 )
+4*C(Si(OH)4 ) +2*C(CuH2 PO+4 )+C(CuHCO+3 )+C(CoHCO+3 ) +2*C(ZnH2 PO+4 ) +
C(ZnHCO+3 ) +C(NiHCO+3 ) +2*C(MnH2PO+4 ) +C(MnHCO+3 ) +2*C(MgH2 PO+4 ) +C(MgHCO+3 )
+C(AlHPO+4 ) +2*C(AlH2PO+2
4 )
+C(FeHSO+4 ) +2*C(FeH2 PO+4 ) +C(FeHCO+3 ) +C(FeHSO+2
4 )
+C(FeH(SO4 )2 ) +C(FeHPO+4 ) +2*C(FeH2 PO+2
4 )
+2*C(CaH2 PO+4 ) +C(CaHCO+3 ))*1.007
(g/L) (4.33)
G(SO4 ) =(C(SO−2
4 )
+C(HSO−4 ) +C(H2 SO4 ) +C(CuSO4 )+C(CoSO4) +C(ZnSO4) +C(NiSO4 ) +
C(MnSO4 )+C(MgSO4 )+C(NaSO−4 ) +C(AlSO+4 ) +C(FeHSO+4 ) +C(FeSO4 )+C(FeHSO+2
4 )
+
C(FeSO+4 ) +2*C(Fe(SO4 )−2 ) +2*C(FeH(SO4 )2 )+C(CaSO4 ))*96.061 (g/L) (4.34)
G(PO4 ) =(C(H2 PO−4 ) +C(H3 PO4 ) +C(CuH2 PO+4 )+C(ZnH2PO+4 ) +C(MnH2 PO+4 ) +C(MgH2 PO+4 ) +
C(AlHPO+4 ) +C(AlH2 PO+2
4 )
+C(FeH2 PO+4 ) +C(FeHPO+4 ) +C(FeH2 PO+2
4 )
+C(CaH2 PO+4 ) )*
94.966 (g/L) (4.35)
G(CO3 ) =(C(HCO−3 ) +C(H2 CO3 )+C(CuHCO+3 )+C(CoHCO+3 ) +C(ZnHCO+3 ) +C(NiHCO+3 ) +

C(MnHCO+3 ) +C(MgHCO+3 ) +C(FeHCO+3 ) +C(CaHCO+3 ) )*60.008(g/L) (4.36)

G(Si(OH)2 ) =C(Si(OH)2 ) *62.082(g/L) (4.37)
G(S2 O6 ) =C(S2 O6) *160.124 (g/L) (4.38)
G(Cu) =C(CuT) *63.54 (g/L) (4.39)
G(Co) =C(CoT)*58.93 (g/L) (4.40)
G(Zn) =C(ZnT)*65.38 (g/L) (4.41)
G(Ni) =C(NiT) *58.63 (g/L) (4.42)
G(Mn) =C(MnT) *54.94 (g/L) (4.43)
G(Mg) =C(MgT) *24.31 (g/L) (4.44)
G(Na) =C(MgT)*22.99 (g/L) (4.45)
G(Al) =C(AlT)*26.98 (g/L) (4.45)
G(Fe2) =C(Fe2T) *55.85 (g/L) (4.46)
G(Fe3) =C(Fe3T) *55.85 (g/L) (4.47)
G(Ca) =C(CaT) *40.08 (g/L) (4.48)
G(S) =C(S) *32.065 (g/L) (4.49)
G(P) =C(P) *30.97 (g/L) (4.50)
G(Si) =C(Si(OH)2 ) *28.086 (g/L) (4.51)
G(Ac) =(C(H+ ) +C(H2 SO4 ) )*98.075 (g/L) (4.52)

5. Estimation of Free Gibbs Energy of
solid compound
5.1. Free Gibbs Energy of formation form literature
Table (5.1) gives Free Gibbs energy of formation of the main soluble compounds
that take part in the estimation of Free Gibbs Energies of formation of solid compounds
at 25°C.
Table 5.1: Free Gibbs Energy of main soluble compounds at 25°C
Soluble Free Gibbs Energy of References

compounds formation (J/mol)
H2 O -237140,00 Thermoddem
SO−2
4 -744004,00 Thermoddem
Fe+2 -78900,00 PSI/Nagra chemical
Fe+3 -4700,00 PSI/Nagra chemical
Al+3 -487640,00 Thermoddem
Mn+2 -230538,00 Thermoddem
Cu+2 65040,00 Thermoddem
Co+2 -54392,00 Sucpcrt92
Zn+2 -147226,00 Thermoddem
Ni+2 -45371,00 Thermoddem
Mg +2 -455375,00 Thermoddem
Ca+2 -552806.00 Thermoddem
H2 PO−4 -1137152,00 Thermoddem
HCO3− -586820.00 Thermoddem
Table (5.2) gives free Gibbs energies of formation of solid estimated from log(k)
of chemical reaction of formation or from solubility products at 25°C.

Table 5.2: Free Gibbs Energy of solid compounds estimated from log (k) or pKs at 25°C
Solid compounds Free Gibbs Energy Parameter Reference

of formation
(J/mol)
CaSO4 . 2H2 O -1797241.65 Log(k)=4.581 PSI/Nagra chemical
AlPO4 . 2H2 O -2111400.00 La iglesia A., 2009
FePO4 . 2H2 O -1635695.78 Log(k)=3.427 Takacs A. et al, 2006
MnHPO4 . 3H2 O -2088480.09 Log(k)=0.24 F. W. Boyle et al, 1985
Zn3 (PO4 )2 . 4H2 O -3643271.31 Log(k)=-3.726 MINTEQ
Cu3 (PO4 )2 . 3H2 O -2767620.69 Log(k)=-4.026 MINTEQ
Co3 (PO4 )2 . 8H2 O -4309151.93 Ks=2.05 10−35
Ni3 (PO4 )2 . 8H2 O -4262884.05 Ks=4.74 10−32
Fe3 (PO4 )2 . 8H2 O -4390164.37 Log(k)=-3.146 MINTEQ
Fe(II)Fe3 (SO4 )6 (OH)2 . 20H2 O -9931433.00 Thermoddem
Fe(II)Fe2 O4 . 2H2 O -1413130.00 Log(k)=-17.18 Jacques Chivot, 2004
Cu4 (OH)6 SO4 H2 O -2044000.00 Thermoddem
Zn4 (OH)6 SO4 -2593620.34 Log(k)=-28.4 MINTEQ
Ni4 (OH)6 SO4 -2165648.95 Log(k)=-32.00 MINTEQ
CuCO3 -517776.68 Ks=5.247 10−29
CoCO3 -639379.20 Ks=1.000 10−10
ZnCO3 -731274.96 Ks=1.46 10−10
NiCO3 -612362.67 Ks=1.42 10−7
MnCO3 -819234.46 Ks=2.24 10−11
FeCO3 -666814.99 Ks=3.07 10−11
CaCO3 -1129079.76 Ks=3.36 10−9
Cu(OH)2 -359722.56 Log(k)=-8.674 MINTEQ
Co(OH)2 (bleu) -450198.00 S. R. Perterson, 1987
Zn(OH)2 -550295.42 Log(k)=-12.474 MINTEQ
Ni(OH)2 -446613.63 Log(k)=-12.794 MINTEQ
Mn(OH)2 -615670.79 Wenhao Sun et al, 2019
Mg(OH)2 -833497.32 Log(k)=-16.844 MINTEQ
Fe(OH)2 -475746.92 Log(k)=-13.564 MINTEQ
Fe(OH)3 (am) -687576.40 Log(k)=-5.0 PSI/Nagra chemical
CoOOH -382099.00 Tian Qinghua et al, 2015
γ-MnOOH -557683.30 Wenhao Sun et al, 2019
R-MnO2 -459934.46 Wenhao Sun et al, 2019
5.2. Estimation of Al hydroxyl sulfate

It has been observed that Al precipitation in the sulfate media forms a hydroxyl
sulfate less soluble than amorphous Al hydroxide. There are two proposal of chemical
composition of hydroxyl sulfate of Al: Al8 (SO4 )5 (OH))14 (Alan J. Rubin, 1973) and
Al4 (SO4 )(0.32) (OH))(11.36) (G. Siclet, 1966). G. Siclet observed that amorphous Al
hydroxide exchange anions and cations with aqueous solution and a quantity of sulfate
that cannot exchange with solution is in the solid.

Al forms with sulfate a soluble complex (AlSO4+ ). The increase of free sulfate
concentration in solution increases Al concentration in solution and decreases the Al
precipitation efficiency (Monica M. Jimenez Correa at al, 2016).
Figure (5.1) gives Concentration – pH solubility limit curve of Al in sulfate

media (Alan J. Rubin, 1973). The first assumption is that the Al precipitates as
Al4 (SO4 )(0.32) (OH))(11.36) . 5H2 O at any pH on Figure (5.1). 5 molecules of water is added
to chemical composition of Al hydroxyl sulfate to be close to Basaluminite. The second
assumption is for modeling purpose – the free Gibbs energy of formation of Al hydroxyl
sulfate depends on pH.
Figure 5.1; Concentration –pH solubility limits of Al in sulfate solution
The chemical reaction of formation of amorphous hydroxyl sulfate of Al is given

by chemical reaction (5.a). Equations (5.1) and (5.2) give the value of equilibrium
constant of chemical reaction (5.a) as function of pH at 25°C respectively at pH ranged
from 3.78 to 4.11 and pH ranged from 4.12 to 4.95. The value of equilibrium constant at
pH less than 3.78 is equal to the value at pH 3.78. The value of equilibrium constant at
pH greater than 4.95 is equal to the value at pH 4.95.
4.Al+3+0.32SO−2 +
4 +16.36H2 O=Al4 (SO4 )(0.32) (OH))(11.36) . 5H2 O+11.36H (5.a)
Log(K)=-7.142*pH-3.040 pH<4.12 (5.1)
Log(K)=2.835*pH 2 -28.751*pH+38.032 pH>4.12 (5.2)

5.3. Estimated Free Gibbs Energy of formation of
solid compounds form lab test results
Table (5.3) gives free Gibbs energies of formation of solid compounds at 25°C.
These free Gibbs energies are estimated from industrial, pilot and lab test Data and
computer. Aluminum and ferric co-precipitate as Alumino-copiapite
(Al(2/3) Fe4 (SO4 )6 (OH)2 . 20H2 O) in the leach solution. Other copiapite compounds are
less soluble. Co5 (OH)6 (SO4 )2 . 3H2 O is amorphous cobalt hydroxyl sulfate that
precipitate at room temperature (W. Feitnecht and G. Fisher, 1935).
Co2 Cu3 (OH)6 (SO4 )2 . 5H2 O is co-precipitation solid compound of copper and cobalt in
cobalt solution where the ratio Co/Cu is greater than 40%. Cu4 (OH)6 SO4 H2 O and
Co5 (OH)6 (SO4 )2 . 3H2 O solid compounds precipitate respectively in pure copper and
cobalt solution. ZnCo3 (OH)6 SO4 . 3H2 O is co-precipitation solid compound of zinc and
cobalt in cobalt solution (J. Gilbert et al, 1969).
There are co-precipitation of Cu and Fe(III) as mixed Cu and Fe hydroxide and

co-precipitation of Cu and Al as mixed Cu and Al hydroxide (K. G. Karthikeyan et al,
1999). But the ratio Cu/Fe and Cu/Al in the solid shows that the solids are close
respectively to CuFe2 O4 and CuAl2 O4 . This publication considers that Cu, Co, Zn, Ni, and
Fe co-precipitate as aluminate at pH greater than 4.5. This consideration helps to explain
the precipitation of Co, Ni and Fe in solution in the presence of Al in the lab test done by
Monica M. Jimenez Correa (Monica M. Jimenez Correa et al, 2016).
Table 5.3: Free Gibbs energies of formation of solid compounds estimated from
industrial, pilot or lab test Data at 25°C
Solid compound Free Gibbs energies of Comments

formation (J/mol)
Al(2/3) Fe4 (SO4 )6 (OH)2 . 20H2 O -10202027.30 Amorphous
CuFe2 O4 . 2H2 O -1287010.14 Amorphous
Co2 Cu3 (OH)6 (SO4 )2 . 5H2 O -3922431.66 Amorphous
Co5 (OH)6 (SO4 )2 . 3H2 O -3731662.55 Amorphous
ZnCo3 (OH)6 SO4 . 3H2 O -3021364.83 Amorphous
CuAl2 O4 .2H2 O -2186647.93 Amorphous
CoAl2 O4 .2H2 O -2296607.35 Amorphous
ZnAl2 O4 .2H2 O -2395707.17 Amorphous
NiAl2 O4 .2H2 O -2282763.90 Amorphous
FeAl2 O4 .2H2 O -2311117.87 Amorphous

6. Neutralization reagents
6.1. Types of neutralization
The neutralization reagent must be cheaper for free acid neutralization and
impurity precipitation. The neutralization reagents used in Fe, Al and Mn removal circuit
are: Limestone and quick lime.
6.2. Limestone
6.2.1. Active grade of Calcium carbonate

Neutralization reagents in the limestone are calcium carbonate and magnesium
carbonate. Magnesium carbonate grade in the limestone can reach 5% and total calcium
carbonate grade is ranged from 80 to 90%. Table (6.1) gives the chemical composition
of Likasi limestone. Table (6.2) gives hypothetical mineralogical composition of Likasi
limestone.
Table 6.1: Chemical composition of Likasi limestone
Elements Grade (%)

Ca 33.12
Mg 2.80
Si 2.58
Fe 1.03
Al 0.89
Table 6.2: Mineralogical composition of Likasi limestone
Elements Grade (%) Available (%)

CaCO3 80.22 100
MgCO3 9.71 100
CaSiO3 2.88 0.00
SiO2 4.03 0.00
Fe2O3 1.47 0.00
Al2O3 1.68 0.00

Available calcium carbonate grade in the limestone is the grade which reacts
with acid. Available calcium carbonate grade in the limestone ranges from 90 to 97% of
total calcium carbonate grade in the limestone. An available grade of calcium carbonate
comes from reactivity lab test of the limestone.
6.2.2. Reaction extent

When limestone is used as a neutralization reagent only 70 to 90% of the
available calcium carbonate reacts with acid because of residence time, pH and mixing
efficiency. This value is called reaction extent.
The limestone reacts with free acid and produces a residue (mixture of gypsum
and unreacted material). The chemical reaction (6.a) gives the neutralization reaction of
calcium carbonate.
CaCO3 +H2 SO4 +H2 O=CaSO4 . 2H2 O + CO2 (6.a)
The reaction extent is given by Equation (6.1) in industrial practice for CaCO3
and MgCO3 .
RE(%)=-5.00*pH+97.5 (6.1)
6.2.3. Pulp solid percent

Solid percent of limestone in the limestone slurry is 20%.
6.3. Quick lime
6.3.1. Active grade of quick lime

Neutralization reagents in the quick lime are calcium oxide and magnesium
oxide. Magnesium oxide in quick lime can reach 3% and total calcium oxide grade is
ranged from 60 to 95%. Table (6.3) gives the chemical composition of Likasi oxide lime.
Table (6.4) gives hypothetical mineralogical composition of Likasi oxide lime.

Table 6.3: Chemical composition of Likasi oxide lime
Elements Grade (%)

Ca 51.46
Mg 1.97
Si 0.64
Fe 0.20
Al 0.30
Table 6.4: Mineralogical composition of Likasi oxide lime

CaO 15.30 100
Ca(OH)2 63.97 100
CaCO3 12.50 100
CaSiO3 2.65 0.00
Mg(OH)2 4.73 100
Fe2O3 0.29 0.00
Al2O3 0.57 0.00
Available calcium oxide grade in the quick lime is the grade which reacts with
acid. Available calcium oxide grade ranges from 90 to 97% of total calcium oxide grade
in quick lime. An available grade of calcium oxpde comes from reactivity lab test of the
quick lime.

When quick lime is used as a neutralization reagent only 70 to 90% of the
available calcium oxide reacts with acid because of residence time, pH and mixing
efficiency. This value is called reaction extent.
The quick lime reacts with free acid and produces a residue (mixture of gypsum
and unreacted material). The chemical reaction (6.b) gives the neutralization reaction of
calcium hydroxide.
Ca(OH)2+H2 SO4 =CaSO4 . 2H2 O (6.b)
The reaction extent is given by Equation (6.2) for CaO, Ca(OH)2 and Mg(OH)2 in
industrial practice.
RE(%)=-2.318*pH+99.38 (6.2)

Solid percent of hydrated lime in the lime slurry is 20%.
6.4. MgO
6.4.1. Active grade of MgO

Neutralization reagents in the MgO are magnesium oxide. Magnesium oxide
grade is ranged from 90 to 98%. Table (6.5) gives the chemical composition of EMAG.
Table (6.6) gives mineralogical composition of EMAG.
Table 6.5: Chemical composition of EMAG
Elements Grade (%)

Ca 1.93
Mg 57.90
Si 0.61
Fe
Al
Other
Table 6.6: Mineralogical composition of EMAG

CaO 2.70 100
MgO 96.00 100
SiO2 1.30 0.00
Fe2O3
Al2O3
Other
Available MgO grade in EMAG is the grade which reacts with acid. Available MgO
grade ranges from 90 to 97% of total MgO grade in EMAG. An available grade of MgO
comes from reactivity lab test of EMAG.

When EMAG is used as a neutralization reagent only 70 to 90% of the available
MgO reacts with acid because of residence time, pH and mixing efficiency. This value is
called reaction extent.
MgO reacts with free acid and produces a residue (mixture of gypsum and
unreacted material). The chemical reaction (6.c) gives the neutralization reaction of
MgO.
MgO+H2 SO4 =MgSO4 +H2 O (6.c)
The reaction extent is given by Equation (6.3) for CaO and MgO industrial
practice.
RE(%)=-12.527*pH+177.28 (6.3)

EMAG is fed dry in the precipitation tank.

7. Prediction of dithionate and iron
saturation concentrations
7.1. Introduction
There is a previous publication on this topic (Kafumbila J, 2022a). This topic is
reviewed because there is a change in equilibrium constants of complexation reactions
of soluble compounds.
7.2. Observations
It has been observed during reductive leaching of Cobalt using SO2 gas as
reducing agent that the concentration of Calcium is high in the leach solution from
reductive leaching of Cobalt (around 0.7g/L) comparatively to the concentration of
Calcium into leach solution obtaining from ordinary leach (0.5g/L) (Table 7.1). The
concentration of calcium is the saturation concentration in equilibrium with gypsum.
The increase of calcium concentration is due to two possibilities:
 Calcium forms soluble complex with sulfite compound as CaSO3 (D. Rai et
al, 1991).
 There is a presence in the leach solution of soluble compounds with
negative charge which decrease the concentration of SO−2
4 to have the
electrical neutrality of leach solution.
7.3. Pilot plant description

As part of feasibility study, pilot plant has been operated during 2 months with
homogenous feed to recover Copper as full plate cathode from Copper-Cobalt ore. The
flow diagram of pilot plant is shown on Figure (7.1). Copper and Cobalt grades in the
feed are respectively 1.478 and 0.325%. Table (7.2) gives the mineralogical composition
of pilot plant feed.
The feed is leached in sulfuric acid and barren solution in the primary leach
tanks. Leaching dissolves the metals from the solids at pH 2 during 2 hours. SO 2 gas is
injected in the primary leach tanks to reduce the redox potential at 350 mV (Ag/AgCl).
The reduction of redox potential prevents the iron precipitation.

Table 7.1: Pilot plant solution composition
Data Eh pH Element concentration (g/L)

(V) Cu Co Al Mg Mn Zn Ca Fe
3-Jul 0.584 1.84 3.098 9.807 0.766 1.955 3.969 0.969 0.754 1.070
4-Jul 0.587 1.8 4.212 10.935 1.101 2.092 4.243 1.059 0.710 1.099
5-Jul 0.578 1.77 3.021 10.52 1.105 2.087 4.123 1.002 0.656 1.059
6-Jul 0.567 1.75 3.855 11.308 1.272 2.266 4.498 1.174 0.772 1.123
7-Jul 0.570 1.832 3.322 11.337 1.252 2.26 4.356 1.184 0.738 1.195
8-Jul 0.569 1.81 3.666 11.713 1.24 2.353 4.462 1.135 0.736 1.354
9-Jul 0.595 1.96 4.885 12.126 1.245 2.461 2.461 1.132 0.697 1.862
10-Jul 0.622 1.542 5.84 12.557 1.285 2.455 4.379 1.199 0.663 1.737
11-Jul 0.585 1.44 6.233 12.485 1.298 2.542 4.897 1.257 0.663 1.699
12-Jul 0.562 1.57 7.019 10.594 1.03 1.998 1.094 1.089 0.669 1.315
13-Jul 0.57 1.66 4.563 9.033 0.956 1.829 4.012 1.026 0.675 1.186
14-Jul 0.538 1.92 3.547 9.471 1.049 1.926 4.388 1.16 0.745 1.183
15-Jul 0.562 2.04 4.762 9.645 0.99 1.75 4.209 1.148 0.724 1.417
16-Jul 0.602 1.54 4.335 10.436 1.084 1.888 4.301 1.145 0.694 1.864
17-Jul 0.576 1.66 4.704 10.342 1.023 1.995 4.477 1.252 0.757 1.679
18-Jul 0.587 1.67 5.463 9.284 0.991 1.895 3.903 0.985 0.721 1.454
19-Jul 0.62 1.72 4.868 9.227 0.992 1.889 3.758 1.114 0.682 1.024
20-Jul 0.668 1.7 5.688 8.357 0.937 1.969 3.425 1.144 0.605 0.415
21-Jul 0.641 1.61 6.607 7.741 0.871 1.729 3.267 1.159 0.629 0.969
22-Jul 0.596 1.67 6.1 8.671 0.892 1.704 4.067 1.105 0.689 1.198
23-Jul 0.624 1.73 5.477 8.412 0.894 1.76 3.41 1.193 0.641 0.575
24-Jul 0.615 1.45 4.501 6.183 0.699 1.304 2.566 0.855 0.59 0.238
25-Jul 0.603 1.6 4.933 6.375 0.648 1.203 2.239 0.743 0.583 0.231
26-Jul 0.596 1.38 5.015 7.264 0.733 1.491 2.724 0.865 0.759 0.560
27-Jul 0.571 1.36 3.937 6.8 0.777 3.025 2.608 0.828 0.698 0.617
28-Jul 0.559 1.52 4.27 7.349 0.853 1.625 2.881 0.858 0.707 0.754
29-Jul 0.591 1.4 2.565 7.816 0.801 1.394 2.755 0.85 0.665 0.804
30-Jul 0.562 1.66 4.383 8.124 0.755 1.477 3.16 0.993 0.682 1.043
31-Jul 0.56 1.53 3.761 6.542 0.657 1.191 2.529 0.791 0.651 0.845
1-Aug 0.565 1.52 4.2 7.304 0.727 1.344 2.758 0.855 0.668 0.905
2-Aug 0.575 1.55 3.955 8.618 0.864 1.549 3.207 0.973 0.618 1.056
3-Aug 0.572 1.54 4.414 8.15 0.839 1.52 3.346 0.922 0.657 0.98
4-Aug 0.59 1.46 6.342 12.406 1.154 2.09 4.748 1.299 0.699 1.274
6-Aug 0.59 1.35 8.96 11.574 1.173 2.133 4.69 1.193 0.672 1.355
7-Aug 0.584 1.38 5.065 9.021 0.959 1.661 3.711 1.095 0.634 1.249
8-Aug 0.574 1.44 5.898 9.603 0.996 1.785 3.954 1.101 0.741 1.292
9-Aug 0.583 1.35 3.628 11.011 1.048 1.941 4.227 1.452 0.726 1.528
10-Aug 0.596 1.42 3.94 9.945 0.999 1.803 4.019 1.42 0.723 1.447
11-Aug 0.582 1.39 4.17 10.024 1.048 1.855 3.898 1.306 0.706 1.311
12-Aug 0.575 1.37 5.447 10.171 1.028 1.788 3.784 1.141 0.758 1.253
13-Aug 0.564 1.4 4.084 10.427 1.033 1.876 3.827 1.175 0.758 1.341
14-Aug 0.567 1.32 4.151 10.623 1.149 1.951 3.722 1.168 0.808 1.409
15-Aug 0.577 1.3 4.106 11.785 1.216 2.253 3.949 1.206 0.728 1.543
16-Aug 0.573 1.37 4.646 12.46 1.324 2.366 4.423 1.249 0.756 1.665
17-Aug 0.569 1.38 4.894 12.648 1.356 2.511 4.525 1.272 0.688 1.671
18-Aug 0.571 1.31 4.21 12.928 1.372 2.507 4.717 1.351 0.691 1.693
19-Aug 0.568 1.4 5.443 14.298 1.441 2.578 5.267 1.306 0.704 1.846
20-Aug 0.574 1.4 6.19 13.477 1.452 2.81 4.974 1.34 0.686 1.912
21-Aug 0.576 1.3 6.43 12.72 1.407 2.518 4.978 1.29 0.744 2.019
22-Aug 0.573 1.35 2.873 12.103 1.25 2.359 4.198 1.053 0.76 1.918
23-Aug 0.577 1.37 3.97 10.91 1.114 2.219 3.844 0.967 0.703 1.829

Figure 7.1: Flow diagram of copper plant of pilot plant
The purpose of the primary leach is to produce a copper rich solution having a
low concentration of free acid. The leach efficiencies of copper and cobalt are
respectively 75 and 70%. Slurry discharged from the primary leach is thickened.
Overflow solution is called the pregnant leach solution (PLS) and is fed to the
copper solvent extraction circuit. Underflow from the primary leach thickener proceeds
to the secondary leach. The underflow from the primary leach thickener is leached in
sulfuric acid and barren solution in the secondary leach tanks at pH 1.5 during 6 hours.
SO2 gas is injected in the secondary leach tank to reduce the redox potential at 350 mV
(Ag/AgCl). The purposes of the redox potential reduction and the increase of free acid
concentration are to leach the remaining cobalt. The leach efficiencies of copper and
cobalt are respectively 20 and 18%. Slurry discharged from the secondary leach is
thickened. Overflow solution from this thickener reports to the storage solution tank.
Underflow from the thickener reports to the filtration circuit.

Table 7.2: Mineralogical composition of pilot plant feed
Minerals Grade
%
Cu2(OH)2(CO3) 1.584
Cu3(PO4)2.Cu2(OH)4 0.146
2CuO.2SiO2.3H2O 0.199
CuO 0.503
CuS 0.005
Cu2S 0.005
CuFeS2 0.005
CoOOH 0.507
FeO(OH) 1.954
Ni(OH)2 0.001
CaCO3.MgCO3 0.900
MnO2 0.127
ZnS 0.007
SiO2 77.139
UO3 0.004
Mg2SiO4 5.381
Ca2SiO4 0.011
CaCl2 0.025
Al2SiO5 11.471
Cr2O3 0.026
CdO 0.001
The underflow from secondary leach thickener is pumped to the vacuum belt
filter. Vacuum is applied to the belt across two zones: The first zone, called the form
zone or dewatering zone, forms the slurry into a cake on the belt and removes the
entrained leach solution. In the second zone, called the washing zone, the filter cake on
the belt is washed using wash water to remove the remaining entrained leach solution.
The leach solution is recovered from the first zone of the belt filters as filtrate. The
filtrate is pumped back to the storage tank. The filter cake moves on the filter belt from
the form zone to the wash zone and the cake is washed with water that has been
acidified to pH 3. Wash solution is pumped to the secondary copper solvent extraction.
In the primary copper solvent extraction, Copper is thus recovered from the PLS
into an organic liquor, which contains an extractant within a diluent. The PLS aqueous
solution is stripped of copper and is now referred to as the copper raffinate. The copper
raffinate stream is returned to storage tank. The loaded organic stream (LO) from the
extraction circuit is stripped with spent copper electrolyte (SE) from the copper

electrowinning (EW) section. Stripping produces the advance electrolyte and stripped
organic, the latter being recycled to Cu SX.
Secondary Cu SX consists only of an extraction stage, designed to strip any

residual copper from the solution before it proceeds to iron precipitation. From the
stripped organic, a portion of the stripped organic stream is returned to the secondary
SX.
Copper metal is electro-deposited from the advance electrolyte onto stainless

steel blanks, known as cathodes, over a 6-day cycle. Spent copper electrolyte is returned
to the copper SX circuit.
7.4. Modeling of Calcium concentration in solution

during reductive leach solution using SO2 gas as
reducing agent
7.4.1. Leach redox potential and (Fe(III)/Fe(II)) redox

potential
During reductive leach of Cobalt (III) the redox potential of redox couple
(Fe(III)/Fe(II)) is fixed by two reactions: first the production of Fe(III) by reductive
reaction of Cobalt (III) and second the production of Fe(II) by oxidative reaction of
sulfite compounds. Therefore the assumption is that the leach redox potential is close to
the redox potential of redox couple (Fe(III)/Fe(II)).
7.4.2. Solid compounds

Calcium soluble compound in pilot plant solution is always in equilibrium with
calcium sulfate solid compounds. Calcium sulfate solid compounds are the following:
CaSO4 . 2H2 O and CaSO4 . At temperature less than 40°C, solubility of calcium sulfate
dehydrate is less than the solubility of calcium sulfate anhydrite (G. Azimi et al, 2007).
The chemical reaction (7.a) gives the precipitation reaction of CaSO4 . 2H2 O.
Ca+2 + SO−2
4 + 2H2 O =CaSO4 . 2H2 O (7.a)
Equation (7.1) gives the precipitation condition of reaction (7.a). Where

“a(Ca(+2)) ”, “a(SO−2
4 )
” and “aw ” are the activities of calcium ion, sulfate anion and water.
The value of Log(K (7.a) ) is given in Table (7.3).

Log(K (7.a) )=-log(a(Ca(+2)) )-log(a(SO−2
4 )
)-2*log(aw ) (7.1)
Table (7.3): Equilibrium constant at 25°C
Reaction Log(K (1.a) ) References

1.a 4.581 PSI/Nagra chemical
7.4.3. Soluble compounds

The procedure that allows obtaining the concentration of soluble follows the
modeling explained in the chapter (4.3.2.) by taking only the sulfate complexes.
7.4.4. Results of modeling

Figure (7.2) gives the concentration of Calcium in pilot plant and modeled
concentration of calcium versus operating day in pilot plant..
Figure 7.2: Concentration of Calcium in pilot plant and Modeled concentration of calcium
versus operating day in pilot plant

Figure (7.2) shows that the concentration of calcium in pilot plant is high than
modeled concentration of calcium from pilot plant data. The results show that there is in
leach solution species with negative electrical charge that decrease the concentration of
free sulfate in solution.
7.5. Modeling of Dithionate concentration in solution

during reductive leaching of Cobalt using SO2 as
reducing agent
7.5.1. Observations
The mechanism of oxidation of sulfite to sulfate is complex. The oxidation of
sulfite compounds in the reductive leach of Cobalt produces dithionate and sulfate
compounds (J. Kafumbila, 2020a and Peter Warneck, 2018). It has observed during
leaching of MnO2 with SO2 the presence MnS2 O6 in the solution (Bing Qu et al, 2018).
This means that the dithionate is relatively stable in acid solution (Hanne Crossland et
al, 1961).
7.5.2. Mechanism of dithionate production

The mechanisms of dithionate production are the following:
Firstly it has been observed that the transition metal ions form sulfite
complexes in their higher oxidation states with sulfite compounds. The chemical
reactions (7.b), (7.c) and (7.d) give the complexation reaction of cobalt, manganese and
iron respectively at low pH.
+
Co+3 +HSO−
3 =CoSO3 +H
+
(7.b)
+
Mn+3 +HSO−
3 =MnSO3 +H
+
(7.c)
+
Fe+3+HSO−
3 =FeSO3 +H
+
(7.d)
Sulfite complexes decompose to produce reduced metal ion and the sulfite free
radical (SÖ− 3 ). The chemical reactions (7.e), (7.f) and (7.g) give respectively the
decomposition reactions of cobalt, manganese and iron complexes. For strong oxidants
like Co(III) and Mn(III), the reactions (7.e) and (7.f) are fast and apparently irreversible.
For weaker oxidants like Fe(III), the reaction (7.g) is much slow and reversible.

CoSO+ +2 −
3 =Co +SÖ3 (7.e)
MnSO+ +2 −
3 =Mn +SÖ3 (7.f)
FeSO+ +2 −
3 =Fe +SÖ3 (7.g)
Sulfite radical reacts with sulfite complexes to produce dithionate according to

the chemical reactions (7.h), (7.i) and (7.j). Sulfite radicals react and produce also
dithionate according to the chemical reaction (2.k).
CoSO+ − +2 −2
3 +SÖ3 =Co +S2 O6 (7.h)
MnSO+ − +2 −2
3 +SÖ3 =Mn +S2 O6 (7.i)
FeSO+ − +2 −2
3 +SÖ3 =Fe +S2 O6 (7.j)
2SÖ− −2
3 =S2 O6 (2.k)
The production of dithionate with the above mechanism depends on pH

(production increases with the increase of pH where sulfite complexes are stable), the
production of dithionate increases with the increase of ratio of transition metal
concentration onto sulfite concentration and the production of dithionate decrease with
the increase of copper concentration in the solution (Peter Warneck, 2018).
7.5.3. Mechanism of oxidation of transition metals

The mechanisms of oxidation of Co+2, Mn+2 and Fe+2 are the following:
The first mechanism of production of dithionate shows that the production of

dithionate is accompanied by the reduction of The oxidation of Co+3, Mn+3 and Fe+3 into
Co+2 , Mn+2 and Fe+2. There are two mechanisms of oxidation of Co+2 , Mn+2 and Fe+2to
Co+3 , Mn+3 and Fe+3:
Firstly the oxidation of transition metals is due to the presence of soluble

oxygen, hydroxyl radical and singlet oxygen in the leach solution. Production of hydroxyl
radical can be due to excess of electron in the mineral structure (Corey A. Cohn et al,
2006), Oxygen from air adsorbed on mineral surface and oxygen vacancy in the oxide
mineral structure (Qian Peng et al, 2020). The chemical reactions (7.m), (7.n) and (7.o)
give the oxidation reactions of transition metals by hydroxyl radical (ÖH).
Co+2 +ÖH=Co+3 +OH − (7.m)

Mn+2 +ÖH=Mn+3 +OH − (7.n)
Fe+2+ÖH=Fe+3+OH − (7.o)
Secondly the oxidation of transition metal starts with one part of SÖ−
3 produced
−
by soluble oxygen reacts with mineral surface oxygen to production SÖ5 (peroxysulfate
radical) according to reaction (7.p) (J. Kafumbila, 2020a).. Where “≣XOH ° ” is surface
compound that contains the surface oxygen. The reaction (1.ag) is not the oxidation
reaction but the addition chemical reaction (J. Kafumbila, 2020a). The decrease of acid
consumption during reductive leaching of Cobalt strengthens the hypothesis.
−
SÖ− ° +
3 +2≣XOH =SÖ5 +2≣X +2H
+
(7.p)
SÖ− −
5 is a strong oxidant. SÖ5 reacts with low state transition metals according to
reactions (7.q), (7.r) and (7.s) and produces high state transition metals and HSO− 5
(caro’s acid).
Co+2 +SÖ− + +3 −
5 +H =Co +HSO5 (7.q)
Mn+2 +SÖ− + +3 −
5 +H =Mn +HSO5 (7.r)
Fe+2+SÖ− + +3 −
5 +H =Fe +HSO5 (7.s)
HSO− 5 is also a strong oxidant comparatively to low state transition metals .

−
HSO5 reacts with low state transition metals according to reactions (7.t), (7.u) and (7.v)
and produces high state transition metals and sulfate compounds.
2Co+2 +HSO− + +3 −
5 +2H =2Co +HSO4 +H2 O (7.t)
2Mn+2+HSO− + +3 −
5 +2H =2Mn +HSO4 +H2 O (7.u)
2Fe+2+HSO− + +3 −
5 +2H =2Fe +HSO4 +H2 O (7.v)
7.5.4. Oxidation reaction of sulfite to dithionate

It assumes that the chemical reaction (7.w) is the oxidation reaction of sulfite
compounds into dithionate. Oxygen comes from soluble oxygen, oxygen from air
adsorbed on minerals surface and surface oxygen of minerals and oxygen can oxidize
sulfite to dithionate (Ermakov A. N. et al, 1997).
In the case where oxygen used is surface oxygen of mineral, the chemical
reaction (7.w) is in competition leaching oxide minerals with sulfuric acid. This means

that acid consumption decreases during the reductive leaching using SO2 as reducing
agent by producing the dithionate.
4HSO− −2
3 +O2 =2S2 O6 +2H2 O (7.w)
7.5.5. Leach redox potential and redox potential of

(Fe(III)/Fe(II))
During reductive leach of Cobalt (III) the redox potential of redox couple
(Fe(III)/Fe(II)) is fixed by two reactions: first the production of Fe(III) by reductive
reaction of Cobalt (III) and oxygen (oxygen adsorbed on mineral surface, soluble oxygen
and surface oxygen of the mineral) and second the production of Fe(II) by oxidative
reaction of sulfite compound to dithionate and sulfate. Therefore the assumption is that
the leach redox potential is close to the redox potential of redox couple (Fe(III)/Fe(II)).

Same as in chapter (7.3)

Same as in chapter (7.3) with addition of dithionate in the solution.
It assumes that in the conditions of reductive leach of Cobalt using SO2 gas as
reducing agent, dithionate is as S2 O−2
6 . C(S2 O−2
6 )
is the concentration of S2 O−2
6 in leach
solution. The concentration of dithionate is fixed by Equation 7.2 where C(CaT) is given in
Table (7.1) and C(Ca+2 ) is given by Equation (7.1)
C(CaT) =C(Ca+2 ) +C(CaSO4) (7.2)

Figures (7.2), (7.3), (7.4), (7.5), (7.6), (7.7), (7.8) and (7.9) give respectively the
concentration of dithionate versus concentration of Co, concentration of Mn,
concentration of Fe(II), Concentration of Fe(III), concentration of Cu, sum of
concentrations of Co, Mn and Fe(II), Eh and pH.

Figure 7.2: concentration of dithionate versus concentration of Co
Figure 7.3: concentration of dithionate versus concentration of Mn

Figure 7.4: concentration of dithionate versus concentration of Fe(II)
Figure 7.5: concentration of dithionate versus concentration of Fe(III)

Figure 7.6: concentration of dithionate versus concentration of Cu
Figure 7.7: concentration of dithionate versus sum of concentrations of Co, Mn and

Fe(II)

Figure 7.8: concentration of dithionate versus pH
Figure 7.9: concentration of dithionate versus Eh

The results show that:
 The concentration of dithionate in solution increases with the increase of

concentration of Co, Mn and Fe(II).
 There is not relationship between concentration of dithionate and the
concentrations of Cu and Fe(III).
 The concentration of dithionate in solution decreases with the increase of
Eh.
 The concentration of dithionate in solution increases with the increase of
pH.
The observation of results shows that the concentration of dithionate depends

on the sum of concentration of Co, Mn and Fe(II), Eh and pH. This means that either
there is not accumulation of dithionate in solution due to the recycle of raffinate to the
leach process unit or there is decomposition of dithionate in solution in the process unit
operations coming after leaching unit operations.
7.5.9. Prediction of dithionate concentration in solution

during reductive leaching of Cobalt using SO2 gas as
reducing agent
Empirical Equation (7.3) gives concentration of S2 O−2

6 (G(S2 O−2
6 )
) (g/L) as
function of Eh (v), pH and sum of concentration of Co (G(Co) ), Mn (G(Mn) ) and Fe(II)
G(Fe(II)) (g/L) from pilot plant data.
MG(S2 O−2
6 )
=32.149+2.161*[G(Co) +C(Mn) +G(Fe(II)) ]-62.228*Eh +1.982*pH (7.3)
Equation (7.4) gives the difference (%) between the dithionate concentration
and modeled dithionate concentration.
MG(S −2
2 O6 )
D=absolute value of (1- )*100 (7.4)
G( S −2
2 O6 )
Where “𝐺(𝑆2 𝑂−2

6 )
” is concentration of dithionate in pilot plant solution and
“𝑀𝐺(𝑆2𝑂−2
6 )
” is the modeled concentration of dithionate.
Figure (7.10) gives MG(S2 O−2

6 )
versus G(S2 O6−2 ) .

Figure 7.10: MG(S2 O−2
6 )
versus G(S2 O6−2 )
7.6. Modeling of Iron saturation concentration in

solution during reductive leaching of Cobalt
using SO2 gas as reducing agent

Same as in chapter (7.4) for calcium in equilibrium with gypsum.
In this case, Iron is in equilibrium with Alumino -copiapite. Equation (7.5) gives
precipitation condition of chemical reaction (7.aa). Free Gibbs energies of compounds
are in Table (7.5).

(2/3)Al+3 +4Fe+3 +6SO−2
4 + 22H2 O = Al(2/3) Fe4 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.aa)
Table (7.5): Standard Free Gibbs energy at 25°C
Substance ΔG (kj/mol) Reference

Alumino-Copiapite -10202.027 Estimated
Fe+2 -78.9 NBS, Wagman et al, 1982
Fe+3 -4.6 NBS, Wagman et al, 1982
SO−2
4 -744.004 Thermoddem
H2 O -237.14 Thermoddem

Same as in chapter (7.4)

Figure (7.11) gives the modeled saturation concentration of iron and
concentration of Iron in pilot plant solution.
Figure 7.11.: Iron saturation concentration and Iron concentration into pilot plant
solution versus Date

Figure (7.11) shows the precipitation of Iron when the leach redox potential
increases and the thermodynamic Data of Alumino-copiapite and soluble compounds of
Iron give simulation results close to pilot plant Data.

8. Modeling of Zinc solvent extraction
using Cyanex 272 as extractant
8.1. Cyanex 272
Phosphinic acid that is in Cyanex 272 is selective for nickel and cobalt at certain
pH range based on cation exchange mechanism. It is extremely miscible in aliphatic and
aromatic diluents and possesses of stability properties in heat and hydrolysis reactions.
The reagent contains 85 % of bis(2,4,4-trimethylpentyl) phosphinic acid as extractant.
The main target of bis(2,4,4-trimethylpentyl) phosphinic acid application aimed on the
Ni/Co separation, which performs high selectivity of cobalt over nickel (Cytec Industries
Inc., 2008). Table (8.1) gives physico-chemical parameters of Cyanex 272.
Table 8.1: Physico-chemical parameters of Cyanex 272
Molar pKa Density Viscosity Solubility

Mass (g/cm3) (CP) in Water
Mg/dm3
290 6.37 0.91 142 16
8.2. Mechanism of metal extraction of Cyanex 272

Figure (8.1) shows the mechanism of metal extraction of Cyanex 272. There are
three steps:
- First step:
o Organic phase
o Aqueous phase containing water, hydrogen ion, metal ion and metal
sulfate complex.
o Aqueous phase containing water and sodium hydroxide used as acid
neutralization agent
- Second step: Three phases are mixed.

o Metal ion reacts with organic phase and produces organic metal
complex and hydrogen ion according to chemical reaction (8.a). (HA)y
is the organic phase (H. A. Evans et al, 2008). Equation (8.1) gives the
equilibrium condition of chemical reaction (8.a). There is in the same
time decomposition of metal sulfate complex at a certain extent.

o Sodium hydroxide reacts with hydrogen ion and produces water,
sodium metal ion and sodium sulfate complex according to chemical
reaction (8.b).
Figure (8.1): Pathway of metal extraction of Cyanex 272
(n+x)
M +n + (HA)y =MAn (HA)x +nH + (8.a)
y
C(MAn (HA)3 ) ∗γ(MAn (HA)3 ) ∗[C(H+ ) ∗γ(H+ ) ]n

K= 𝑛+𝑥 (8.1)
( )
C(M+n ) ∗γ(M+n ) ∗[C(HA) ∗γ(HA) ] 𝑦
Where k is equilibrium constant, 𝐶(𝑖) is the molar concentration of substance “i”

and 𝛾(𝑖) is the activity coefficient of substance “i”, “y” is equal to 2 and “x” is equal
to zero for Fe(III) and Al and it is equal to 3 for other elements (Bershak Andrey,
2019).
(a+b)NaOH+(a+b)H + +bSO−2 + −
4 =(a+b)H2 O+aNa +bNaSO4 (8.b)
- Third step: separation of aqueous and organic phases.

8.3. Modeling of metal extraction of Cyanex 272
Equation (8.1) gives the equilibrium constant of chemical reaction (8.a).
Equation (8.2) gives value of the variable “K ° ”. Table (8.2) gives values of variable “K ° ” at
25°C as function of pH. The values of variable “K ° ” is obtained from experimental Data.
Equation (8.3) gives molar concentration of free Cyanex 272 in organic phase.
𝑛+𝑥
( )
γ(HA) 𝑦 C(MAn (HA)3 ) ∗[C(H+ ) ∗γ(H+ ) ]n
°
K =K*γ = 𝑛+𝑥 (8.2)
(MAn (HA)3 ) ( )
C(M+n ) ∗γ(M+n ) ∗[C(HA) ] 𝑦
Table 8.2: Value of the variable “K ° ” at 25°C with Cyanex 272
Element log(K ° )
Fe+3 -1.662*pH+2.5779
Zn+2 -0.3871*pH-1.3159
Al+3 -2.0712*pH+0.5055
Cu+2 -0.7015*pH-2.8037
Mn+2 -0.7549*pH-3.1608
Co+2 -0.7082*pH-3.6277
Mg +2 -0.7188*pH-4.5768
Ca+2 -0.6202*pH-5.7242
Ni+2 -0.5086*pH-8.8711
10 𝑛+𝑥
C(HA) =(V/V%)*0.91*290 - C(MAn (HA)3 ) *( ) (8.3)
𝑦

9. Oxidation of Ferrous , Manganese
and Cobalt
9.1. Oxidation of Manganese and Cobalt hydroxides
by oxygen at high pH
9.1.1. Concept
At high pH Co and Mn precipitate as Co(OH)2 and Mn(OH)2. In presence of
oxygen from Air, Co(OH)2 and Mn(OH)2 are oxidized into CoOOH and γ-MnOOH.
Chemical reactions (9.a) and (9.b) give the oxidation reaction of Co(OH)2 and Mn(OH)2.
Co(OH)2=CoOOH+H + +e− (9.a)
Mn(OH)2=γ-MnOOH+H + +e− (9.b)
It is known that oxygen from Air cannot oxidize the dithionate into sulfate. It
assumes that CoOOH and γ-MnOOH coming from oxygen oxidation cannot oxidize
dithionate in sulfate at high pH.
9.1.2. Thermodynamic equilibrium

Solids Co(OH)2 and CoOOH form a heterogeneous solid solution. Mn(OH)2 and
γ-MnOOH form also a heterogeneous solid solution. The chemical potentials of solids in
the heterogeneous solid solutions are given by Equations (9.1), (9.2), (9.3) and (9.4).
Equation (9.5) gives the chemical potential of H + .
μ(Co(OH)2 ) =μ°(Co(OH)2 )+RTlog(X(Co(OH)2 )) (9.1)
μ(CoOOH) =μ°(CoOOH) +RTlog(X(CoOOH) ) (9.2)
μ(Mn(OH)2 ) =μ°(Mn(OH)2 ) +RTlog(X(Mn(OH)2 ) ) (9.3)
μ(MnOOH) =μ°(MnOOH) +RTlog(X(MnOOH)) (9.4)
μ(H+) =RTlog(C(H+ ) *γ(H+) ) (9.5)

Equations (9.6) and (9.7) give the sum of molar fraction in heterogeneous solid
solution.
1=X(Co(OH)2 ) +X(CoOOH) (9.6)
1=X(Mn(OH)2 )+X(MnOOH) (9.7)
Equations (9.8) and (9.9) give the thermodynamic condition.
μ(Co(OH)2 ) =μ(CoOOH) +μ(H+) -96845*Eh (9.8)
μ(Mn(OH)2 ) =μ(MnOOH) +μ(H+ ) -96845*Eh (9.9)
Equation (9.10) gives the value of redox potential in the industrial precipitation
tank as function of pH (pH ranged from 7 to 8.5).
Eh=-0.075*pH+0.939 (v) (9.10)
9.2. Oxidation of Cobalt by γ-MnOOH at high pH
9.2.1. Concept
It has been observed that there is oxidation of Cobalt adsorbed on Manganese
oxide. There are two path-ways of cobalt oxidation by manganese oxide at high pH:
 First path way
o There is precipitation of Mn(OH)2.
o There is oxidation of Mn(OH)2 into γ-MnOOH.
o γ-MnOOH adsorbs Cobalt on the surface.
o There is exchange of electron between γ-MnOOH and adsorbed
Cobalt according to chemical reaction (9.c). This chemical reaction
is thermodynamically possible because γ-MnOOH and CoOOH form
a heterogeneous solid solution.
γ-MnOOH +Co+2= CoOOH+Mn+2 (9.c)
 Second path way

o There is mixed precipitation of Mn(OH)2 and Co(OH)2.
o There is oxidation of Mn(OH)2 into MnOOH and Co(OH)2 into
CoOOH by oxygen from Air.

o The remaining Co(OH)2 exchanges electron with γ-MnOOH
according to chemical reaction (9.d). This chemical reaction is
thermodynamically possible because Co(OH)2 and γ-MnOOH form
a solid solution.
Co(OH)2+ γ-MnOOH +2H + =CoOOH+Mn+2 +2H2 O (9.d)

This publication uses the first path way. Solids γ-MnOOH and CoOOH form a
heterogeneous solid solution. Mn(OH)2. The chemical potentials of solids in the
heterogeneous solid solutions are given by Equations (9.11) and (9.12). Equations
(9.13) and (9.14) give the chemical potential of Co+2 and Mn+2.
μ(MnOOH) =μ°(MnOOH) +RTlog(X(MnOOH)) (9.12)
μ(Co+2 ) =μ°(Co+2 ) +RTlog(C(Co+2 )*γ(Co+2 ) ) (9.13)
μ(Mn+2 ) =μ°(Mn+2 ) +RTlog(C(Mn+2 ) *γ(Mn+2 ) ) (9.14)
Equation (9.15) gives the sum of molar fractions in heterogeneous solid

solution.
1=X(MnOOH)+X(CoOOH) (9.15)
Equation (9.16) gives the thermodynamic condition.
μ(MnOOH) +μ(Co+2 ) =μ(CoOOH) +μ(Mn+2 ) (9.16)
9.3. Oxidation of Fe(II), Manganese and dithionate

using the mixture Air/𝐒𝐎𝟐 at low pH
9.3.1. Concept
It has been observed that there is an increase in the Eh when the mixture
Air/SO2 is injected in the solution. The path-way of production of SÖ−5 that is the
strong oxidant need the presence of Fe, Mn or Co as catalysis in the solution. The

high state of Fe, Mn or Co forms a soluble complex with sulfite compounds.
Equations from (9.e) to (9.i) give the path way. Where M +3 is metallic ion (Fe, Co
or Mn). Chemical reaction (9.j) gives the overall reaction of SO2 oxidation into
SÖ−5 (Wensheng Zhang et al, 2000)
SO2 +H2 O=H2 SO3 (9.e)
M +3+H2 SO3 =MSO+

3 +2H
+
(9.f)
MSO+ +2 −
3 =M +SÖ3 (9.g)
−
SÖ−
3 +O2 =SÖ5 (9.h)
3M +2+SÖ− + +3 −2
5 +2H =3M +SO4 +H2 O (9.i)
M +3+SO2 +O2 +H2 O=SÖ− +

5 +2H +M
+2
(9.j)
9.3.2. Ferrous oxidation reaction

Ferrous oxidation reaction is given by the chemical reaction (9.k). Depending on
the pH and the presence of Al in solution, Ferric precipitates as Alumino-Copiapite
(Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O) at low pH and Ferrihydrite (Fe(OH)3) at high pH. There
is mixed precipitation of hydroxyl and hydroxyl-sulfate.
3Fe+2+M +3+SO2 +O2 =3Fe+3+SO−2

4 +M
+2
(9.k)
9.3.3. Dithionate oxidation reaction

Dithionate oxidation reaction is given by the chemical reaction (9.l). It has been
observed during the leaching of cobalt using SO2 as reducing agent that at high Eh
(>0.6V) the concentration of dithionate in the leach solution depends on the Value of Eh
and pH only. The saturation concentration of dithionate at high Eh is given by Equation
(9.17) (pH ranged from 1.3 to 2.0).
3S2 O−2 +3 −2 +
6 +2M +2SO2 +2O2 +6H2 O=8SO4 +12H +2M
+2
(9.l)
C(S2 O−2
6 )
=151.973-183.004*Eh-7.130*pH (9.17)

9.3.4. Manganese oxidation reaction
Manganese oxidation reaction is given by the chemical reaction (9.m). Where
+3
“A ” is metallic ion of Fe, Mn or Co. MnO2 is unsaturated MnO2 in oxygen called δ-MnO2
or R-MnO2 . There is mixed precipitation of hydroxyl and hydroxyl-sulfate.
3Mn+2 +2A+3 +2SO2 +2O2 +6H2 O=3R-MnO2 +2SO−2 +2

4 +2A +12H
+
(9.m)
9.3.5. Cobalt oxidation reaction

At oxidation potential of Manganese, Cobalt cannot be oxidized into CoOOH by
the mixture Air/SO2 . Adsorbed cobalt on the surface R-MnO2 is oxidized by R-MnO2
according to chemical reaction (9.n). The chemical reaction (9.n) is thermodynamically
possible because R-MnO2 and CoOOH form a heterogeneous solid solution.
2Co+2 +R-MnO2 +2H2 O=2CoOOH+Mn+2 +2H + (9.n)
The chemical potentials of solids in the heterogeneous solid solutions are given
by Equations (9.18) and (9.19). Equations (9.20), (9.21), (9.22) and (9.23) give the
chemical potential of Co+2, Mn+2, H + and H2 O.
μ(MnO2 ) =μ°(MnO2 )+RTlog(X(MnO2 )) (9.19)
μ(H+) =RTlog(C(H+ ) *γ(H+) ) (9.22)
μ(H2 O) =μ°(H2 O) +RTlog(𝑎𝑤 ) (9.23)

solution.
1=X(MnO2 )+X(CoOOH) (9.24)

μ(MnO2 ) +2*μ(Co+2 ) +2*μ(H2 O) =2μ(CoOOH) +μ(Mn+2 ) +2*μ(H+) (9.25)
9.3.6. Utilization conditions

The main parameters of oxidation using the mixture Air/SO2 are: volume
percentage of SO2 in mixture, the flow rate of SO2 , temperature and pH. It has
been observed that:
 Oxidation efficiency of Fe(II) or Mn increases with the increase of

temperature.
 Oxidation efficiency of Fe(II) or Mn increases with the increase of pH.
 Eh depends on the flowrate SO2 . The priority of oxidation with the
increase of SO2 flowrate is Fe(II), dithionate and Mn.
 The optimal volume percentage of SO2 is ranged from 0.45% to 0.90% to
avoid undesirable chemical reactions. In the case where Fe(II) is oxidized
alone, the undesirable reaction is the production of dithionate according
to chemical reaction (9.o) at low pH where the saturation concentration of
dithionate (Equation 9.17) is high than the concentration of dithionate in
solution (whereM +2 is metallic ion (Fe, Mn or Co)). In the case where Mn
is also oxidized the undesirable reactions are:
o First the re-leach of R-MnO2 and CoOOH by SO2 according to
chemical reactions (9.p) and (9.q).
o Second the dissolution of MnO2 according to the chemical reaction
(9.n). The combination of the oxidation of manganese according to
chemical reaction (9.m) and the dissolution of MnO2 according to
chemical reaction (9.n) produces CoOOH.
In case of Manganese oxidation the utilization of SO2 is more than 70% by
taking account the chemical reactions (9.p), (9.q) and (9.n). Considering
that the oxidation of dithionate is undesirable reaction, the utilization of
SO2 is less than 30%.
MSO+ − +2 −2
3 +SÖ3 =M +S2 O6 (9.o)
R-MnO2 +SO2 =Mn+2+SO−2

4 (9.p)
2CoOOH+SO2 +2H + =2Co+2 +SO−2

4 +2H2 O (9.q)

9.4. Disproportional reaction of MnOOH at low pH
At pH less than 6 Manganites (γ-MnOOH) disproportionate into Pyrolysite (β-
MnO2 ) and Mn(II) ions in solution according to the chemical reaction (9.r) (Madeleine
Ramstedt, 2004).
2γ-MnOOH +2H + =Mn+2+ β-MnO2 +2H2 O (9.r)
9.5. Dissolution of CoOOH by Mn(II) ion at low pH
9.5.1. Concept
It has been observed that there is dissolution of Cobalt and oxidation of
adsorbed Manganese on CoOOH at pH less than 2.0. The path-ways of cobalt dissolution
by manganese at low pH:
o CoOOH adsorbs Manganese on the surface.

o There is exchange of electron between CoOOH and adsorbed
Manganese according to chemical reaction (9.s). R-MnO2 and
CoOOH form a heterogeneous solid solution.
Mn+2 +2CoOOH+2H + =R-MnO2 +2Co+2 +2H2 O (9.s)

The chemical potentials of solids in the heterogeneous solid solutions are given
by Equations (9.18) and (9.19). Equations (9.20), (9.21), (9.22) and (9.23) give the
chemical potential of Co+2, Mn+2, H + and H2 O.
μ(MnO2 ) =μ°(MnO2 )+RTlog(X(MnO2 )) (9.19)
μ(H+) =RTlog(C(H+ ) *γ(H+) ) (9.22)

μ(H2 O) =μ°(H2 O) +RTlog(𝑎𝑤 ) (9.23)

solution.
1=X(MnO2 )+X(CoOOH) (9.24)
μ(MnO2 ) +2*μ(Co+2 ) +2*μ(H2 O) =2μ(CoOOH) +μ(Mn+2 ) +2*μ(H+) (9.25)

10. Modeling and Mass balance of copper
cathode production circuit
10.1. Configuration
10.1.1. Type of configuration

The type of copper circuit is a conventional circuit containing:
 Milling in water circuit with pre-leach thickener and pre-leach filtration –

the filtration on the feed must be done using belt filter in case of the good
filterability or Press filter. The choice of this configuration is motivated
by the desire to decrease the cobalt loss in copper circuit trough liquid
loss.
 Conventional circuit – the choice of this configuration is motived by the
low concentration of extractant in organic phase but high concentration
of copper in raffinate contrary to split circuit (Kafumbila J, 2022c).
10.1.2. Flow diagram

Figure (10.1) gives the flow diagram of conventional circuit having Milling in
water with pre-leach filter unit operations.
Abbreviations of unit operations:
 BM: Ball Mill.

 CY: Hydrocyclone.
 PRLTK: Pre-leach thickener.
 PRLFL: Pre-leach filtration.
 LC: Leach circuit.
 PTK: Primary thickener.
 KTn: Thickener of rank “n” in CCD train.
 SX En: Stage of rank “n” in CuSX - extraction train.

Figure 10.1: Flow diagram of conventional circuit

 ACT: Aqueous coalescing Tank.
 SX Sn: Stage of rank “n” in CuSX - stripping train.
 EW: .Copper electrowinning.
Abbreviations of lines between unit operations:
 Feed: Ores.
 BMW: Ball Mill water.
 UFCY: Hydrocyclone underflow.
 OBM: Outlet Ball Mill.
 SW: Sump water.
 FeCY: Feed hydrocyclone.
 UFCY: Hydrocyclone underflow.
 OFCY: Hydrocyclone overflow.
 PRLTFC: Pre-leach thickener flocculants.
 PRLTOF: Pre-leach thickener overflow.
 PRLTUF: Pre-leach thickener underflow.
 PRLFFC: Pre-leach filter flocculants.
 PRLFFL: Pre-leach filter filtrate.
 PRLFCa: Pre-leach filter cake.
 LCA: Leach concentrated acid.
 RE2L: Raffinate of stage 2 of CuSX - extraction train to leach.
 WBB: Water balance bleed.
 OLC: Outlet leach circuit.
 PTKFC: Flocculants of primary thickener.
 PTKUF: Underflow of primary thickener.
 PTKOF: Overflow of primary thickener.
 TKFCn: Flocculants of thickener of rank “n” in CCD train.
 TKnUF: Underflow of thickener of rank “n” in CCD train.
 TKnOF: Overflow of thickener of rank “n” in CCD train.
 WW: Wash water of CCD train.
 PLS: Pregnant leach solution.
 REn: Raffinate of stage of rank “n” in CuSX - extraction train.
 LOEn: Loaded organic of stage of rank “n” in CuSX - extraction train.
 ALOEn: Aqueous entrainment in loaded organic of stage of rank “n” in
CuSX - extraction train.
 LOAC: Loaded organic from aqueous coalescing tank.
 ALOAC: Aqueous entrainment in loaded organic from aqueous coalescing
tank.
 ACTD: Drain of aqueous coalescing tank.
 SOS: Stripping organic.

 SOAS: Aqueous entrainment in stripping organic.
 ADS: Advance electrolyte.
 RADS: Recirculated advance electrolyte.
 SPE: Spent electrolyte.
 EWO: Oxygen produced in Copper electrowinning circuit.
 EWCC: Copper cathode produced in Copper electrowinning circuit.
 EWS: Sulfur produced in Copper electrowinning circuit.
 EWW: Water for Copper electrowinning circuit.
 EWCA: Concentrated acid for Copper electrowinning circuit.
 OEW: Outlet of Copper electrowinning circuit.
 EWB: Bleed of Copper electrowinning circuit.
10.1.3. Plant description

Feed material from crusher is fed in Ball Mill together with water and
hydrocyclone underflow. Outlet of Ball Mill is discharged in the sump. Water is also
added to the sump to reach the requirement of Feed hydrocyclone pulp density. The
hydrocyclone overflow is fed in the pre-leach thickener and underflow of pre-leach
thickener is fed to pre-leach filter. The pre-leach filter cake is fed in leach circuit with
one part of raffinate from raffinate pond. Concentrated acid and sulfur dioxide gas are
also added in the leach circuit for pH and redox potential control. Slurry discharged from
the leach circuit is thickened in primary thickener. Underflow of primary thickener is
fed to counter current decantation circuit where leach residue is washed with acidulated
water.
Overflow of primary thickener is called pregnant leach solution and is fed to the
copper solvent extraction circuit. One part of raffinate of solvent extraction step is sent
back to leach and the remaining is sent to cobalt circuit.
The loaded organic from organic CuSX – extraction train is sent to aqueous
coalescing tank to remove a maximum volume of aqueous entrainment solution. Loaded
organic from aqueous coalescing tank is sent to CuSX - stripping train.
Spent electrolyte from copper electrowinning circuit is sent to CuSX - stripping

train. Advance electrolyte from CuSX - stripping train is sent back to Copper
electrowinning circuit. Concentrated acid and water are also added in Copper
electrowinning circuit. Copper cathode, Oxygen gas and sulfur are produced in Copper
electrowinning circuit. Iron bleed solution from Copper electrowinning circuit is sent
back to PLS pond.

10.2. Mass balance
10.2.1. Design criteria
10.2.1.1.Ball Mill (in water)
Design criteria of Ball Mill mass balance are the following:
 Feed moisture content: 20%.

 Specific gravity of feed solid: 2.7t/m3.
 Solid percent in outlet Ball Mill: 70%.
10.2.1.2.Hydrocyclone
Design criteria of hydrocyclone mass balance are the following:
 Specific gravity of feed solid: 2.7t/m3.

 Volume percent of solid in overflow: 20%.
 Volume percent of solid in underflow: 52%
10.2.1.3.Pre-leach thickener
Design criteria of pre-leach thickener mass balance are the following:
 Flocculants dosage: 40 g/ton.

 Flocculants concentration: 0.25%.
 Solid percent in underflow: 58%.
10.2.1.4.Pre-leach filter
Design criteria of pre-leach filter mass balance are the following:

 Solid percent in filter cake: 78%.
10.2.1.5.Leach circuit
Design criteria of leach circuit mass balance are the following:

 Specific gravity of residue solid: 2.5t/m3.
 Solid percent in outlet leach circuit: 30% (maximum for reductive
leaching of Cobalt).
 Leach redox potential (LRP): 350 mV (Ag/AgCl).
 Leach pH: 1.7.
 Leach test (Kafumbila J., 2021):
o Gangue acid consumption (GAC): 43.260 kg/ton.
o SO2 consumption (SO2C): 14.850 kg/ton.
o CO2 production (CO2P): 7.510 kg/ton.
o Leach weight lost (LWL): 32.5 kg/ton.
o Leaching efficiency of sulfide minerals: 0% (assumption).
o Solubility:
 Cu: 14.041 kg/ton.
 P: 0.300 kg/ton.
 Fe: 0.861 kg/ton.
 Al: 0.688 kg/ton.
 Co: 4.500 kg/ton.
 Zn: 0.500 kg/ton.
 Ni: 0.068 kg/ton.
 Mn: 0.788 kg/ton.
 Mg: 1.002 kg/ton.
 Sulfur percentage in solid:

o Percentage of sulfur in the feed:0.1%.
o Sulfur percentage in the leach residue: 1.5%.
 SO2 consumption: Equation (7.3) gives empirical Equation giving
6 (G(S2 O−2
saturation concentration of S2 O−2 6 )
) (g/L) as function of Eh (v)
(leach redox potential), pH and sum of concentration of Co (G(Co) ), Mn
(G(Mn) ) and Fe(II) (G(Fe(II)) ) in leach solution. The production of
dithionate uses the surface oxygen of minerals. The chemical reactions
(10.a), (10.b), (10.c) and (10.d) give the consumption of SO2 due
respectively to production of dithionate and leaching of Co(III), Mn(IV)
and Fe(III) minerals. “≣O” is surface oxygen of minerals. The chemical
reaction (10.e) gives the consumption of SO2 due to reduction of ferric to
ferrous in the raffinate in case there is reductive leaching in the CCD
using Ferrous and dithionate as reducing agent.
MG(S2 O−2
6 )
=32.149+2.161*[G(Co) +G(Mn) +G(Fe(II)) ]-62.228*Eh +1.982*pH (7.3)
2SO2 +≣O+H2 O=S2 O−2

6 +2H
+
(10.a)
Co2 O3 +SO2 +2H + =2Co+2+SO−2

4 +H2 O (10.b)
MnO2 +SO2 =Mn+2+SO−2
4 (10.c)
Fe2 O3 +SO2 +2H + =2Fe+2+SO−2

4 +H2 O (10.d)
2Fe+3+SO2 +2H2 O=2Fe+2+SO−2

4 +4H
+
(10.e)
o Percent of sulfur in SO2 gas: 50.052%.
 Acid consumption is by sulfur mass balance. The acid decrease with the
increase of dithionate production.
o Percent of acid in concentrated acid: 98%

o Specific gravity of concentrated acid: 1.80.
 Chemical reaction (7.a) gives gypsum precipitation reaction. Equation

(10.1) gives the precipitation condition of reaction (7.a). Where “μ” is the
chemical potential.
Ca+2 + SO−2
4 + 2H2 O =CaSO4 . 2H2 O (7.a)
μ(CaSO4 .2H2O) =μ(Ca+2 )+μ(SO−2

4 )
+2μ(H2 O) (10.1)
 Chemical reaction (7.aa) gives Alumino-Copiapite precipitation reaction.

Equation (10.2) gives precipitation condition of chemical reaction (7.aa).
In this simulation is that the iron dissolution stops when the
concentration of Iron in leach solution reaches the saturation
concentration. Where “μ” is the chemical potential.
(2/3)Al+3 +4Fe+3 +6SO−2

4 + 22H2 O = Al(2/3) Fe4 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.aa)
μ(Al(2/3)Fe4 (SO4)6 (OH)2 .20H2O)+2μ(H+ ) =(2/3)μ(Al+3 ) +4μ(Fe+3 ) +6μ(SO−2

4 )
+22μ(H2 O) (10.2)
 Release of CO2 :
o Figure (10.2) shows the bubbles of CO2 and SO2 in the leach pulp.
There is a transfer of CO2 from leach pulp to the bubble and there
is a transfer of SO2 from bubble to the leach pulp. It assumes for
simulation purpose that at half of tank depth bubble contains
equal volume of CO2 and SO2 .
o The partial pressure of CO2 (atm) in the bubble is given by
Equation (10.3). For modeling purpose, the value of depth “h” is
equal to Hp /2. Equation (10.4) gives the pressure of bubble at “h”

depth. Equation (10.5) gives the concentration of H2 CO3 in the
pulp in equilibrium with CO2 in the bubble.
Figure 10.1: Leach tank containing a bubble of CO2
P(CO2) =(1/2)*Ph (10.3)
ρ∗g∗h
Ph=P0+101325 (atm) (10.4)
Where “𝑃0 ” is pressure at level of pulp (1 atm), “ρ” is specific gravity of pulp
(kg/m3), “g” is equal to 9.81 N/kg and “h” is depth (m).
C(H2 CO3 )=4.571*10−2 *P(CO2) (M) (10.5)
 Leach tank sizing:

o Residence time per leach tank: 1hour
o Ratio D/H=0.9
o Freeboard: 10% of total volume.
 Solution is saturated in silica. The chemical reaction (10.f) gives the

precipitation reaction silica gel (SiO2 ).

SiO2 +2H2 O=Si(OH)4 (10.f)
10.2.1.6.Primary thickener
Design criteria of primary thickener mass balance are the following:

 Solid percent in underflow of primary thickener: 58%.
(10.1) gives the precipitation condition of reaction (7.a).
 Release of CO2 –It assumes that CO2 in bubble is pure. For modeling
purpose, the partial pressure of CO2 (atm) is partial pressure in the
atmosphere. The atmosphere contains 0.03% of CO2 .
10.2.1.7.CCD circuit
Design criteria of CCD circuit mass balance are the following:
 The number of thickener in the CCD train: 7 that is a maximum number

in Copper industrial practice.
 Solid percent in thickener underflow: 54%.
 Flocculants dosage for the first thickener: 60% of flocculants dosage of
primary thickener.
 Flocculants dosage for other thickeners: 40% of flocculants dosage of
primary thickener.
 Mixing efficiency: 100%
 Wash efficiency: concentration of Co in the liquid of the last thickener in
the CCD train must be between 0.08 to 0.1g/L.
 pH of wash solution: 2.5.
 Solution is saturated in silica
10.2.1.8.CuSX – extraction train
Design criteria of CuSX - extraction circuit mass balance are the following:
 Type of extractant: Lix984N.

 Saturation ratio (LO/ML): 80%
 O/A ratio (Loaded organic of stage of rank “2” on extraction train onto
overflow of primary thickener): 1.25.
 Number of stage: 2.
 Volume percent of extractant in organic phase: depends on saturation
ratio.
 Mixing efficiency for Copper:
o Stage E1: 95%.
o Stage E2: 97%.
 Aqueous entrainment in organic:
o Stage E1: 1000ppm.
o Stage E2: 1000ppm.
 Equilibrium copper concentration: Equation (10.6) gives equilibrium
condition of chemical reaction (10.g) (Kafumbila J., 2022b).
Cu+2 +2HR=CuR 2 +2H + (10.g)
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (10.6)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
 Equilibrium Fe(III) concentration: Data of Lix984 (Kafumbila J., 2022b)

on extraction train. Equation (10.7) gives equilibrium condition of
chemical reaction (10.h).
Fe+3+3HR=FeR 3 +3H + (10.h)
[FeR ]∗([H+ ])3

10(−3.431) =[Fe+33]∗([HR])3 (10.7)
 Mixing efficiency for Fe(III) (assuming the same as for Copper):

o Stage E1: 95%.
o Stage E2: 97%.
10.2.1.9.Aqueous coalescing tank
Design criterion of aqueous coalescing tank is:
 Aqueous entrainment in organic: 400 ppm
10.2.1.10. CuSX – stripping train
Design criteria of CuSX - stripping circuit mass balance are the following:

 O/A (internal): 1.25
 Concentration of copper in advance electrolyse: 49-50 g/L.
 Spent electrolyte composition:
o Copper concentration: 35 g/L.
o Acid concentration: 180 g/L.
o Fe(II) concentration: 1.0 g/L.
o Fe(III) concentration: 1.0 g/L.
 Mixing efficiency:
o Stage S: 95%.
o Aqueous entrainment in organic:
o Stage S: 300ppm.
o Equilibrium copper concentration: Equation (10.8) gives equilibrium
condition of chemical reaction (10.i) (Kafumbila J., 2022b).
CuR 2 +2H + =Cu+2 +2HR (10.i)
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (10.8)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
 Equilibrium Fe(III) concentration: Data of Lix984 (Kafumbila J., 2022b)

on extraction train. Equation (10.8) gives equilibrium condition of
chemical reaction (10.j).
FeR 3 +3H + =Fe+3+3HR (10.j)
 Mixing efficiency for Fe(III) (assuming the same as for Copper):

o Stage S: 95%.
10.2.1.11. Copper electrowinning
Design criteria of Copper electrowinning circuit mass balance are the following:
 Spent electrolyte and iron bleed composition:

o Copper concentration: 35 g/L.
o Acid concentration: 180 g/L.
o Fe(II) concentration: 1.0 g/L.
o Fe(III) concentration: 1.0 g/L.
 Percent of acid in concentrated acid: 98%
 Specific gravity of concentrated acid: 1.80.

 Chemical reaction (10.k). Equation (10.9) gives the production of
oxygen.
2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (10.k)
O2P=0.252CCP (10.9)
Where “O2P” is the quantity of oxygen produced in copper electrowinning

and “CCP” is copper cathode produced in copper electrowinning.
 Dithionate decomposition:
o Half of dithionate is oxidized to sulfate by oxygen on anode

according to the chemical (10.l). Equation (10.10) gives mass of
oxygen gas (CM(O2 ) ) used to oxidize M(S O(−2)) mass of dithionate
2 6
to sulfate. Equation (10.11) gives the mass of sulfate produced

during the oxidation of M(S O(−2)) mass of dithionate
2 6
(−2) (−2)
2S2 O6 +O2 +2H2 O=4SO4 +4H + (10.l)
CM(O2 ) =0.100*M(S (−2) (10.10)

2 O6 )
PM(SO(−2)) =1.200*M(S (−2) (10.11)

4 2 O6 )
o Half of dithionate is reduce to elementary sulfur on cathode

according to the chemical reaction (10.m). Equation (10.12) gives
mass of oxygen gas produced (PM(O2 ) ) during the production of
elementary sulfur from M(S O(−2)) mass of dithionate. Equation
2 6
(10.13) gives mass of elementary sulfur produced from M(S (−2)

2 O6 )
mass of dithionate
(−2)
S2 O6 +2H + =O2 +2S ° +H2 O (10.m)
PM(O2 ) =0.200*M(S (−2) (10.12)

2 O6 )
PM(S° ) =0.401*M(S (−2) (10.13)

2 O6 )
 Flowrate of concentrated acid: sulfur mass balance on CuEW.

 Solution is saturated in silica.

10.2.2. Mass balance results
Table (10.1) gives the summary of simulation results and Tables (10.2) to
(10.9) give copper cathode production mass balance obtained by using the realistic
simulation model. Table (10.10) gives reagents, CuEW power and Cu cathode transport
costs.
Table 10.1: Result summary
Description
Number of thickener in CCD train 7
Water balance bleed flow rate 664.18 m3/hr
Water balance bleed copper concentration 0.327 g/L
Water balance bleed cobalt concentration 5.346 g/L
Water balance bleed acid concentration 11.106 g/L
Lost acid (free acid and acid associated with Copper) – CCD TK7 UF 0.345 Kg/t feed
Lost acid (free acid and acid associated with Copper) – WBB 9.638 Kg/t feed
Acid consumption – Leach circuit 56.235 Kg/t feed
Acid consumption – CuEW circuit 2.175 Kg/t feed
Acid consumption – wash CCD circuit 0.420 Kg/t feed
Total acid consumption 58.830 Kg/t feed
SO2 consumption – Leach circuit 14.451 Kg/t feed
Leach - Percent of SO2 converted to SO4 26.701 %
Leach – Percent of incoming SO4 from SO2 9.681 %
Leach – percent of SO2 converted into S2O6 by Oxygen of Minerals 73.299 %
Leach S2O6 concentration 19.575 g/L
Leach Cobalt 6.661 g/L
Leach Manganese 1.166 g/L
Leach Iron (II) 1.209 g/L
Flocculants consumption 194.799 g/t feed
Extractant percent in organic phase (v/v%) 18.17 %
PLS copper concentration 5.573 g/L
PLS S2O6 concentration 15.739 g/L
Cu/Fe in LOE1 1770
SX Copper extraction E1 efficiency 69.855 %
SX Fe(III) extraction E1 efficiency -0.041 %
SX Fe(III) extraction E2 efficiency 9.126 %
SX Copper stripping recovery 55.801 %
Copper Net transfer 0.236 g/L/(v/v%)
Copper production 13.705 Kg/t feed
Ratio Copper in EWB onto Copper production 1.761 %
Lost copper in CCD-TK7 UF 0.065 Kg/t feed
Lost cobalt in CCD-TK7 UF 0.063 Kg/t feed
Lost copper in WBB 0.271 Kg/t feed
Cobalt in WBB 4.438 Kg/t feed
Soluble copper recovery 97.603 %
Soluble cobalt recovery 98.622 %
CCD wash ratio 1.298 m3/ton

Table 10.2: Copper cathode production circuit – Mass balance
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Feed BMW UFCY OBM SW FCY OFCY PRLTFC
Solid/gas
mass t/h 800.00 2000.00 2800.00 2800.00 800.00 0.032
volume m3/h 296.30 740.74 1037.04 1037.04 296.30 0.012
SG solid t/m3 2.70 2.70 2.70 2.70 2.70 2.65
S % 0.100 0.100
Pulp
mass t/h 1000.00 2683.76 4000.00 4668.95 1985.19 12.80
volume m3/h 496.30 1424.50 2237.04 2905.98 1481.48
SG solid t/m3 2.01 1.88 1.79 1.61 1.34
%solid 80.00 74.52 70.00 40.30 0.25
Liquid
mass t/h 200.00 316.24 683.76 1200.00 668.95 1868.95 1185.19 12.77
volume m3/h 200.00 316.24 683.76 1200.00 668.95 1868.95 1185.19 12.77
SG liquid t/m3 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
S2O6 g/l
Cu g/l
Co g/l
Zn g/l
Ni g/l
Mn g/l
Mg g/l
Al g/l
Fe(II) g/l
Fe(III) g/l
Ca g/l
S g/l
P g/l
Si g/l
C g/l
Ac g/l

9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00

PRLTUF PRLTOF PRLFCa PRLFFl LCA SO2 Raf2L CO2
Solid/gas
mass t/h 800.03 800.03 11.56 5.38
volume m3/h 296.31 296.31
SG solid t/m3 2.70 2.70
S % 0.10 0.10 50.05
Pulp
mass t/h 1379.37 1025.68
volume m3/h 875.64 521.96
SG solid t/m3 1.58 1.97
%solid 58.00 78.00
Liquid
mass t/h 579.33 972.30 225.65 353.68 44.988 1503.26
volume m3/h 579.33 972.30 225.65 353.68 24.993 1429.62
SG liquid t/m3 1.00 1.00 1.00 1.00 1.800 1.05
S2O6 g/l 15.702
Cu g/l 0.327
Co g/l 5.346
Zn g/l 0.594
Ni g/l 0.080
Mn g/l 0.936
Mg g/l 1.190
Al g/l 0.817
Fe(II) g/l 0.973
Fe(III) g/l 0.051
Ca g/l 0.671
S g/l 576.73 15.161
P g/l 0.356
Si g/l 0.024
C g/l 0.000
Ac g/l 1764.00 11.106

17.00 18.00 19.00 20.00 21.00 22.00 23.00 24.00

OLC PTKFC PTKUF PTKOF CO2 TK1FC TK1UF TK1OF
Solid/gas
mass t/h 774.03 0.031 774.01 0.627 0.019 773.98
volume m3/h 309.61 0.012 309.62 0.007 309.63
SG solid t/m3 2.50 2.650 2.50 2.65 2.50
S % 1.500 1.499 1.498
Pulp
mass t/h 2580.11 12.385 1334.50 7.43 1433.30
volume m3/h 1997.47 840.67 947.80
SG solid t/m3 1.29 1.59 1.51
%solid 30.00 0.250 58.00 0.25 54.00
Liquid
mass t/h 1806.07 12.354 560.49 2205.85 7.412 659.32 948.48
volume m3/h 1687.86 12.354 531.04 2089.95 7.412 638.17 918.06
SG liquid t/m3 1.070 1.000 1.055 1.055 1.000 1.033 1.033
S2O6 g/l 19.575 15.739 15.739 8.944 8.944
Cu g/l 6.932 5.573 5.573 3.167 3.167
Co g/l 6.661 5.355 5.355 3.043 3.043
Zn g/l 0.740 0.595 0.595 0.338 0.338
Ni g/l 0.100 0.080 0.080 0.046 0.046
Mn g/l 1.166 0.938 0.938 0.533 0.533
Mg g/l 1.483 1.192 1.192 0.678 0.678
Al g/l 1.018 0.819 0.819 0.465 0.465
Fe(II) g/l 1.209 0.972 0.972 0.552 0.552
Fe(III) g/l 0.066 0.053 0.053 0.030 0.030
Ca g/l 0.659 0.672 0.672 0.691 0.691
S g/l 18.406 14.923 14.923 8.752 8.752
P g/l 0.444 0.357 0.357 0.203 0.203
Si g/l 0.024 0.024 0.024 0.024 0.024
C g/l 0.102 0.000 0.000 0.000 0.000
Ac g/l 2.907 2.532 2.532 1.753 1.753

18.00 19.00 20.00 21.00 22.00 23.00 24.00 25.00

TK2FC TK2UF TK2OF TK3FC TK3UF TK3OF TK4FC TK4UF
Solid/gas
mass t/h 0.012 773.96 0.012 773.94 0.012 773.92
volume m3/h 0.005 309.64 0.005 309.64 0.005 309.65
SG solid t/m3 2.65 2.50 2.65 2.50 2.65 2.50
S % 1.497 1.496 1.495
Pulp
mass t/h 4.95 1433.25 4.95 1433.21 4.95 1433.18
volume m3/h 955.12 959.79 962.78
SG solid t/m3 1.50 1.49 1.49
%solid 0.25 54.00 0.25 54.00 0.25 54.00
Liquid
mass t/h 4.941 659.30 1039.85 4.941 659.28 1034.85 4.941 659.26
volume m3/h 4.941 645.48 1018.06 4.941 650.15 1020.52 4.941 653.13
SG liquid t/m3 1.000 1.021 1.021 1.000 1.014 1.014 1.000 1.009
S2O6 g/l 5.461 5.461 3.310 3.310 1.964
Cu g/l 1.934 1.934 1.172 1.172 0.695
Co g/l 1.858 1.858 1.126 1.126 0.668
Zn g/l 0.206 0.206 0.125 0.125 0.074
Ni g/l 0.028 0.028 0.017 0.017 0.010
Mn g/l 0.325 0.325 0.197 0.197 0.117
Mg g/l 0.414 0.414 0.251 0.251 0.149
Al g/l 0.284 0.284 0.172 0.172 0.102
Fe(II) g/l 0.337 0.337 0.204 0.204 0.121
Fe(III) g/l 0.019 0.019 0.011 0.011 0.007
Ca g/l 0.696 0.696 0.694 0.694 0.688
S g/l 5.585 5.585 3.625 3.625 2.396
P g/l 0.124 0.124 0.075 0.075 0.045
Si g/l 0.024 0.024 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 1.265 1.265 0.915 0.915 0.668

26.00 27.00 28.00 29.00 30.00 31.00 32.00 33.00

TK4OF TK5FC TK5UF TK5OF TK6FC TK6UF TK6OF TK7FC
Solid/gas
mass t/h 0.012 773.90 0.012 773.88 0.012
volume m3/h 0.005 309.65 0.005 309.65 0.005
SG solid t/m3 2.65 2.50 2.65 2.50 2.65
S % 1.495 1.494
Pulp
mass t/h 4.95 1433.15 4.95 1433.12 4.95
volume m3/h 964.69 965.93
SG solid t/m3 1.49 1.48
%solid 0.25 54.00 0.25 54.00 0.25
Liquid
mass t/h 1029.86 4.941 659.25 1024.87 4.941 659.24 1019.89 4.941
volume m3/h 1020.28 4.941 655.04 1018.33 4.941 656.27 1015.30 4.941
SG liquid t/m3 1.009 1.000 1.006 1.006 1.000 1.005 1.005 1.000
S2O6 g/l 1.964 1.115 1.115 0.573 0.573
Cu g/l 0.695 0.395 0.395 0.203 0.203
Co g/l 0.668 0.379 0.379 0.195 0.195
Zn g/l 0.074 0.042 0.042 0.022 0.022
Ni g/l 0.010 0.006 0.006 0.003 0.003
Mn g/l 0.117 0.066 0.066 0.034 0.034
Mg g/l 0.149 0.084 0.084 0.043 0.043
Al g/l 0.102 0.058 0.058 0.030 0.030
Fe(II) g/l 0.121 0.069 0.069 0.035 0.035
Fe(III) g/l 0.007 0.004 0.004 0.002 0.002
Ca g/l 0.688 0.681 0.681 0.673 0.673
S g/l 2.396 1.618 1.618 1.119 1.119
P g/l 0.045 0.025 0.025 0.013 0.013
Si g/l 0.024 0.024 0.024 0.025 0.025
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.668 0.496 0.496 0.378 0.378

34.00 35.00 36.00 37.00 38.00 39.00 40.00 41.00

TK7UF TK7OF WW RE1 LOE1 ALOE1 RE2 LOE2
Solid/gas
mass t/h 771.04
volume m3/h 309.66
SG solid t/m3 2.490
S % 1.430
Pulp
mass t/h 1427.85
volume m3/h 964.32
SG solid t/m3 1.48
%solid 54.00
Liquid
mass t/h 656.81 1014.90 1004.68 2206.30 2.612 2201.65
volume m3/h 654.66 1011.59 1004.50 2095.95 2612.44 2.482 2093.80 2612.44
SG liquid t/m3 1.003 1.003 1.000 1.053 1.053 1.052
S2O6 g/l 0.226 0.226 0.000 15.705 15.705 15.702
Cu g/l 0.080 0.080 0.000 1.701 7.673 1.701 0.327 4.506
Co g/l 0.077 0.077 0.000 5.346 5.346 5.346
Zn g/l 0.009 0.009 0.000 0.594 0.594 0.594
Ni g/l 0.001 0.001 0.000 0.080 0.080 0.080
Mn g/l 0.013 0.013 0.000 0.936 0.936 0.936
Mg g/l 0.017 0.017 0.000 1.190 1.190 1.190
Al g/l 0.012 0.012 0.000 0.817 0.817 0.817
Fe(II) g/l 0.014 0.014 0.000 0.972 0.972 0.973
Fe(III) g/l 0.001 0.001 0.000 0.056 0.0043 0.056 0.051 0.0044
Ca g/l 0.664 0.664 0.000 0.671 0.671 0.671
S g/l 0.797 0.797 0.061 15.136 15.136 15.161
P g/l 0.005 0.005 0.000 0.356 0.356 0.356
Si g/l 0.025 0.025 0.000 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.298 0.298 0.334 8.650 8.650 11.106

42.00 43.00 44.00 45.00 46.00 47.00 48.00 49.00

ALOE2 ACTD LOAC ALOAC RADS ADS SOS ASOS
Solid/gas
mass t/h
volume m3/h
SG solid t/m3
S %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 2.612 1.567 1.045 1691.88 2633.22 0.784
volume m3/h 2.484 1.489 2612.44 0.993 1345.25 2093.73 2612.44 0.623
SG liquid t/m3 1.052 1.053 1.053 1.258 1.258 1.258
S2O6 g/l 15.702 15.705 15.705 0.021 0.021 0.021
Cu g/l 0.327 1.701 7.673 1.701 49.687 49.687 3.392 49.687
Co g/l 5.346 5.346 5.346 0.865 0.865 0.865
Zn g/l 0.594 0.594 0.594 0.096 0.096 0.096
Ni g/l 0.080 0.080 0.080 0.013 0.013 0.013
Mn g/l 0.936 0.936 0.936 0.152 0.152 0.152
Mg g/l 1.190 1.190 1.190 0.193 0.193 0.193
Al g/l 0.817 0.817 0.817 0.132 0.132 0.132
Fe(II) g/l 0.973 0.972 0.972 0.994 0.994 0.994
Fe(III) g/l 0.051 0.056 0.0043 0.056 1.007 1.007 0.0002 1.007
Ca g/l 0.671 0.671 0.671 0.109 0.109 0.109
S g/l 15.161 15.136 15.136 92.713 92.713 92.713
P g/l 0.356 0.356 0.356 0.058 0.058 0.058
Si g/l 0.024 0.024 0.024 0.020 0.020 0.020
C g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ac g/l 11.106 8.650 8.650 153.358 153.358 153.358

50.00 51.00 52.00 53.00 54.00 55.00 56.00 57.00

EWCA EWW EWCC EWO EWS SP EWB WBB
Solid/gas
mass t/h 10.96 2.764 0.0031
volume m3/h
SG solid t/m3
S %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 1.740 7.795 930.25 6.897 698.39
volume m3/h 0.967 7.795 743.79 5.515 664.18
SG liquid t/m3 1.800 1.000 1.251 1.251 1.052
S2O6 g/l 0.000 0.000 15.702
Cu g/l 35.000 35.000 0.327
Co g/l 0.865 0.865 5.346
Zn g/l 0.096 0.096 0.594
Ni g/l 0.013 0.013 0.080
Mn g/l 0.151 0.151 0.936
Mg g/l 0.193 0.193 1.190
Al g/l 0.132 0.132 0.817
Fe(II) g/l 1.000 1.000 0.973
Fe(III) g/l 1.000 1.000 0.051
Ca g/l 0.108 0.108 0.671
S g/l 576.73 93.36 93.36 15.16
P g/l 0.058 0.058 0.356
Si g/l 0.020 0.020 0.024
C g/l 0.000 0.000 0.000
Ac g/l 1764.00 190.00 190.00 11.106

Table 10.10: Reagent, CuEW power and Cu cathode transport costs
Consumption $/t or $/Mw $/tCu

Acid 4.262 t/tCu 120.00 511.45
Sulfur for SO2 0.539 t/tCu 245.00 131.95
flocculants 10.166 kg/tCu 3900.00 39.65
Lix 984N 1.946 kg/tCu 9240.00 17.98
Diluent 7.810 kg/tCu 1590.00 12.42
Guar 0.200 kg/tCu 2800.000 0.56
CuEWpower 2.351 Mw/tCu 24.500 57.60
Transport Cu DRC-SA 240.00 240.00
Total 1011.60

11. Mass balance of Cobalt circuit –A
11.1. Configuration

Figure (11.1) gives the flow diagram of Cobalt circuit having two steps: Fe and
Al precipitation and Cobalt precipitation.
Figure 11.1. : Flow diagram of cobalt circuit: two steps – Fe and Al precipitation and Co
precipitation
 FAP: Fe and Al precipitation.

 FAPTK: Thickener of Fe and Al precipitation.
 FAPFL: Filtration of Fe and Al precipitation.
 CP: Co precipitation.
 CPTK: Thickener of Co precipitation.
 CPFL: Filtration of Co precipitation
 EN: Effluent neutralization

 WBB: Water balance bleed

 LS: Limestone.
 FAPCO2: CO2 releases from Fe and Al precipitation.
 OFAP: Outlet of Fe and Al precipitation.
 FAPTKFc: Flocculants of thickener of Fe and Al precipitation.
 FAPTKOF: Overflow of thickener of Fe and Al precipitation.
 FAPTKUF: Underflow of thickener of Fe and Al precipitation
 FAPTKCO2: CO2 releases from thickener of Fe and Al precipitation
 FAPFLF: Filtrate of filter of Fe and Al precipitation
 FAPFLWW: Wash water of filter of Fe and Al precipitation
 FAPFLCa: Cake of filter of Fe and Al precipitation
 CPMG: MgO of cobalt precipitation.
 CPAO2: Oxygen from Air absorbed by solid.
 OCP: Outlet of cobalt precipitation.
 CPTKFc: Flocculants of thickener of cobalt precipitation.
 CPTKOF: Overflow of thickener of cobalt precipitation.
 CPTKUF: Underflow of thickener of cobalt precipitation
 CPFLF: Filtrate of filter of cobalt precipitation
 CPFLWW: Wash water of filter of cobalt precipitation
 CPFLCa: Cake of filter of cobalt precipitation.
 ENQL: Quick lime for effluent neutralization.
 ENAO2: Oxygen from Air absorbed by solid.
 OEN: Outlet of effluent neutralization.

Water balance bleed is fed to Fe and Al precipitation tank with limestone using
as neutralization agent at pH obtained on the constraint that Co/Al concentration is
equal to 200. Pulp after precipitation is fed in the tickener and underflow of thickener is
fed to the filter. Filtrate is fed to the tickener and overflow of thickener is fed to surge
tank.
Overflow of Fe and Al precipitation thickener is fed to Co precipitation tank with

MgO using as netralization agent at pH 8.3 because of low reaction extent of MgO and Co
concentration must be around 0.10g/L. Pulp after precipitation is fed in the tickener and
underflow of thickener is fed to the filter. Fe and Al filtration cake, cobalt precipitation
Filtrate of filter and cobalt precipitation overflow of thickener are fed to effluent
neutralization tank at pH 9.0.

11.2. Mass balance
11.2.1.1.Fe and Al precipitation
 Precipitation pH: the ratio Co/Al in the solution after precipitation must be
equal to 200. In same time the ratio Co/Fe must be less than 200 and the
Cobalt loss must be less the 1% of cobalt in WBB.
 Eh: Ratio of concentrations of Ferric and ferrous.
 Limestone is used as neutralization agent in Fe and Al precipitation. Tables
(6.1) and (6.2) give chemical and mineralogical compositions of Likasi
limestone. The reaction extent is given by Equation (6.1) in industrial
practice for CaCO3 and MgCO3 .
RE(%)=-5.00*pH+97.5 (6.1)
 Solid percent in limestone pulp: 20%.

 Table (5.1) gives the standard free Gibbs energies of reference ions and
water at 25°C. Equation (11.1) gives the chemical potential of reference
ions at 25°C. Equation (11.2) gives the chemical potential of water. Where
“μ(p) ” is the chemical potential of reference ion “p” at 25°C, “μ°(p) ” is the
standard chemical potential of reference ion “p” at 25°C, “R” is equal to
8.314, “T” is equal to 298.15, “C(p) ” is the molarity of reference ions, “γp ” is
the activity coefficient of reference ions “p” and “a(w) ” is water activity.
μ(p) =μ°(p) +R*T*2.303*log(C(p) ∗ γp ) (11.1)
μ(H2 O) =μ°(H2 O) +R*T*2.303*log(a(w) ) (11.2)
 Precipitation of phosphate. Chemical reactions from (11.a) to (11.h) give

the precipitation reactions of phosphates. Equation (11.3) gives
precipitation condition of chemical reaction (11.a), (11.b), (11.c), (11.d)
and (11.g). Equation (11.4) gives precipitation condition of chemical
reaction (11.e). Equation (11.5) gives precipitation condition of chemical
reactions (11.f) and (11.h). Where “μ°(SP) ” is the standard chemical
potential of amorphous phosphates, “μ(H+) ” is the chemical potential of H + ,
“μ(H2 PO−4 ) ” is chemical potential of H2 PO−
4 , “μ(H2 O) ” is chemical potential of
water, “μ(M+2 ) ” is chemical potential of Cu+2 , Co+2 , Zn+2, Ni+2 and Fe+2,

“μ(M+2 ) ” is chemical potential of Mn+2, “μ(A+3 ) ” is chemical potential of
Fe+3 and Al+3 and “n” is Number of hydrated molecule of water.
3Cu+2+2H2 PO−
4 +3H2 O =Cu3 (PO4 )2 . 3H2 O+4H
+
(11.a)
3Co+2+2H2 PO−
4 +8H2 O =Co3 (PO4 )2 . 8H2 O+4H
+
(11.b)
3Zn+2+2H2 PO−
4 +4H2 O =Zn3 (PO4 )2 . 4H2 O+4H
+
(11.c)
3Ni+2 +2H2 PO−

4 +8H2 O =Ni3 (PO4 )2 . 8H2 O+4H
+
(11.d)
Mn+2+H2 PO−
4 +3H2 O=MnHPO4 . 3H2 O+H
+
(11.e)
Al+3 +H2 PO−

4 +2H2 O=AlPO4 . 2H2 O+2H
+
(11.f)
3Fe+2+2H2 PO−
4 +8H2 O =Fe3 (PO4 )2 . 8H2 O+4H
+
(11.g)
Fe+3+H2 PO−
4 +2H2 O=FePO4 . 2H2 O+2H
+
(11.h)
(μ°(SP) +4∗μ(H+ ) )
>1 (11.3)
(3∗μ(M+2 ) +2∗μ(H PO− ) +n∗μ(H2 O) )
2 4
(μ°(s) +μ(H+ ) )
>1 (11.4)
(μ(Mn+2 ) +μ(H PO−) +3∗μ(H2 O) )
2 4
(μ°(s) +2∗μ(H+ ) )
>1 (11.5)
(μ(A+3 ) +μ(H PO− ) +2∗μ(H2 O) )
2 4
 Precipitation of aluminate. Chemical reactions from (11.i) to (11.m) give

the precipitation reaction of amorphous aluminates. Equation (11.6) gives
precipitation condition of amorphous aluminates. Where “μ°(SA) ” is the
standard chemical potential of amorphous aluminates, “μ(M+2 ) ” is chemical
potential of Cu+2 , Co+2 , Zn+2, Ni+2 and Fe+2, and “μ(Al+3 ) ” is chemical
potential of Al+3
Cu+2 +2Al+3+6H2 O =CuAl2 O4 . 2H2 O+8H + (11.i)
Co+2 +2Al+3 +6H2 O =CoAl2 O4 . 2H2 O+8H + (11.j)
Zn+2+2Al+3+6H2 O =ZnAl2 O4 . 2H2 O+8H + (11.k)
Ni+2 +2Al+3 +6H2 O =NiAl2 O4 . 2H2 O+8H + (11.l)

Fe+2+2Al+3 +6H2 O =FeAl2 O4 . 2H2 O+8H + (11.m)
(μ°(SA) +8∗μ(H+ ) )
>1 (11.6)
(μ(M+2 ) +2∗μ(Al+3 ) +6∗μ(H2 O) )
 Precipitation of carbonates. Chemical reactions from (11.n) to (11.s) give

precipitation reaction of carbonates. Equation (11.7) gives precipitation
condition of carbonates. Where “μ°(SC) ” is the standard chemical potential
of carbonate, “μ(M+2 ) ” is chemical potential of Cu+2, Co+2 , Zn+2, Ni+2 , Mn+2
and Fe+2, and “μ(HCO−3 ) ” is chemical potential of HCO−
3.
Cu+2 +HCO−
3 =CuCO3 +H
+
(11.n)
Co+2 +HCO−
3 =CoCO3 +H
+
(11.o)
Zn+2+HCO−
3 =ZnCO3 +H
+
(11.p)
Ni+2 +HCO−
3 =NiCO3 +H
+
(11.q)
Mn+2+HCO−
3 =MnCO3 +H
+
(11.r)
Fe+2+HCO−
3 =FeCO3 +H
+
(11.s)
(μ°(SC) +μ(H+ ) )
>1 (11.7)
(μ(M+2 ) +μ(HCO− ) )
3
 Precipitation of ferrites. Chemical reaction (11.t) and (11.u) give the

precipitation reactions of ferrites. Equation (11.8) gives precipitation
condition of ferrites. Where “μ°(SF) ” is the standard chemical potential of
ferrites, “μ(M+2 ) ” is chemical potential of Cu+2 , and Fe+2, and “μ(Fe+3 ) ” is
chemical potential of Fe+3.
Cu+2 +2Fe+3+6H2 O =CuFe2 O4 . 2H2 O+8H + (11.t)
Fe+2+2Fe+3+6H2 O =FeFe2 O4 . 2H2 O+8H + (11.u)
(μ°(SF) +8∗μ(H+ ) )
>1 (11.8)
(μ(M+2 ) +2∗μ(Fe+3 ) +6∗μ(H2 O) )
 Precipitation of hydroxyls and hydroxyl-sulfates. Chemical reactions from

(11.v) to (11.al) give precipitation reaction of hydroxyls and hydroxyl-
sulfates. There is mixed precipitation of hydroxyls and hydroxyl-sulfates.
Therefore Equation (11.9) gives chemical potential of hydroxyls and
hydroxyl-sulfates. Where “μ(SH/p) ” is the chemical potential of hydroxyl or
hydroxyl-sulfate of chemical reaction “p”, “μ°(SH/p) ” is the standard
chemical potential of hydroxyl or hydroxyl-sulfate of chemical reaction “p”
and “X(SH/p) ” is molar fraction of hydroxyl or hydroxyl-sulfate of chemical
reaction “p” in the mixture. Equations from (11.10) to (11.26) give
chemical potential of OH − from chemical reaction “p”. Equations from
(11.27) to (11.43) give the Equations that allow obtaining molar fractions
“X(SH/p) ”. Equation (11.44) gives precipitation condition of mixture
according to chemical reaction (11.m).
Fe+3+3OH − =Fe(OH)3 (11.v)
Fe+2+4Fe+3+6SO−2 −
4 +2OH +20H2 O =Fe(II)Fe3 (SO4 )6 (OH)2 . 20H2 O (11.w)
(2/3)Al+3 +4Fe+3+6SO−2 −
4 +2OH +20H2 O =Al(2/3) Fe3 (SO4 )6 (OH)2 . 20H2 O (11.x)
4Al+3+0.32SO−2 −
4 +11.36OH +5H2 O =Al4 (SO4 )(0.32) (OH))(11.36) . 5H2 O (11.y)
4Cu+2+SO−2 −
4 +6OH +H2 O =Cu4 (OH)6 SO4 H2 O (11.z)
2Co+2+3Cu+2+2SO−2 −
4 +6OH +5H2 O =Co2 Cu3 (OH)6 (SO4 )2 . 5H2 O (11.aa)
Cu+2 +2OH − =Cu(OH)2 (11.ab)
4Zn+2+SO−2 −
4 +6OH =Zn4 (OH)6 SO4 (11.ac)
Zn+2+3Co+2 +SO−2 −
4 +6OH +3H2 O =ZnCo3 (OH)6 SO4 . 3H2 O (11.ad)
Zn+2+2OH − =Zn(OH)2 (11.ae)
5Co+2+2SO−2 −
4 +6OH +3H2 O =Co5 (OH)6 (SO4 )2 . 3H2 O (11.af)
Co+2 +2OH − =Co(OH)2 (11.ag)
4Ni+2 +SO−2 −
4 +6OH =Ni4 (OH)6 SO4 (11.ah)
Ni+2 +2OH − =Ni(OH)2 (11.ai)
Mn+2+2OH − =Mn(OH)2 (11.aj)

Mg +2 +2OH − =Mg(OH)2 (11.ak)
Fe+2+2OH − =Fe(OH)2 (11.al)
μ(SH/p) =μ°(SH/p) +R*T*2.303*log(X(SH/p) ) (11.9)
μ(OH−/v) =(μ(SH/v) -μ(Fe+3 ) )/3 (11.10)
μ(OH−/w) =(μ(SH/w)-μ(Fe+2 ) -4μ(Fe+3 ) -6μ(SO−2

4 )
-20μ(H2 O) )/2 (11.11)
μ(OH−/x) =(μ(SH/x) -(2/3)μ(Al+3 ) -4μ(Fe+3 ) -6μ(SO−2

4 )
-20μ(H2 O) )/2 (11.12)
μ(OH−/y) =(μ(SH/y) -4μ(Al+3 ) -0.32μ(SO−2

4 )
-5μ(H2 O) )/11.36 (11.13)
μ(OH−/z) =(μ(SH/z)-4μ(Cu+2 ) -μ(SO−2

4 )
-μ(H2 O) )/6 (11.14)
μ(OH−/aa) =(μ(SH/aa) -2μ(Co+2 ) -3μ(Cu+2 )-2μ(SO−2

4 )
-5μ(H2 O) )/6 (11.15)
μ(OH−/ab) =(μ(SH/ab) -μ(Cu+2 ) )/2 (11.16)
μ(OH−/ac) =(μ(SH/ac)-4μ(Zn+2 ) -μ(SO−2

4 )
)/6 (11.17)
μ(OH−/ad) =(μ(SH/ad) -μ(Zn+2 ) -3μ(Co+2 ) -μ(SO−2

4 )
-3μ(H2 O) )/6 (11.18)
μ(OH−/ae) =(μ(SH/ae) -μ(Zn+2 ) )/2 (11.19)
μ(OH−/af) =(μ(SH/af) -5μ(Co+2 ) -2μ(SO−2

4 )
-3μ(H2 O) )/6 (11.20)
μ(OH−/ag) =(μ(SH/af) -μ(Co+2 ) )/2 (11.21)
μ(OH−/ah) =(μ(SH/ah) -4μ(Ni+2 ) -μ(SO−2

4 )
)/6 (11.22)
μ(OH−/ai) =(μ(SH/ai) -μ(Ni+2 ) )/2 (11.23)
μ(OH−/aj) =(μ(SH/aj) -μ(Mn+2 ) )/2 (11.24)
μ(OH−/ak) =(μ(SH/ak) -μ(Mg+2 ) )/2 (11.25)
μ(OH−/al) =(μ(SH/al)-μ(Fe+2 ) )/2 (11.26)

μ(OH−/v) =μ(OH−/w) (11.27)
μ(OH−/v) =μ(OH−/x) (11.28)
μ(OH−/v) =μ(OH−/y) (11.29)
μ(OH−/v) =μ(OH−/z) (11.30)
μ(OH−/v) =μ(OH−/aa) (11.31)
μ(OH−/v) =μ(OH−/ab) (11.32)
μ(OH−/v) =μ(OH−/ac) (11.33)
μ(OH−/v) =μ(OH−/ad) (11.34)
μ(OH−/v) =μ(OH−/ae) (11.35)
μ(OH−/v) =μ(OH−/af) (11.36)
μ(OH−/v) =μ(OH−/ag) (11.37)
μ(OH−/v) =μ(OH−/ah) (11.38)
μ(OH−/v) =μ(OH−/ai) (11.39)
μ(OH−/v) =μ(OH−/aj) (11.40)
μ(OH−/v) =μ(OH−/ak) (11.41)
μ(OH−/v) =μ(OH−/al) (11.42)
X(v) +X(w) +X(x) +X(y) +X(z) +X(aa) +X(ab) +X(ac) +X(ad) +X(ae) +X(af)
+X(ag) +X(ah) +X(ai) +X(aj) +X(ak) +X(al) =1 (11.43)
Fe+3+3H2 O =Fe(OH)3 +3H + (11.am)
(μ°(SH/m) +3∗μ(H+ ) )
>1 (11.44)
(μ(Fe+3 ) +3∗μ(H2 O) )

 Release of CO2 – Figure (11.2) shows the bubble of CO2 in the
precipitation pulp. It assumes that CO2 in bubble is pure. The pressure of
CO2 (atm) in the bubble is given by Equation (11.45). For modeling
purpose, the value of depth “h” is equal to Hp /2. Equation (11.46) gives
the concentration of H2 CO3 in the pulp in equilibrium with CO2 in the
bubble.
Figure 11.2: Precipitation tank with CO2 bubble
ρ∗g∗h
Ph=P0+101325 (atm) (11.45)
C(H2 CO3 )=4.571*10−2 *Ph (M) (11.46)
 Precipitation tank sizing:

o Residence time per precipitation tank: 30minutes
o Ratio D/H=0.9

 Solution is saturated in silica. The chemical reaction (11.n) gives the

precipitation reaction silica gel (SiO2 ). Equation (11.47) gives molarity of
soluble silica.
SiO2 +2H2 O=Si(OH)4 (11.an)
C(Si(OH)4 ) =1.932*10−3*(aw )2 (11.47)
11.2.1.2.Thickener
Design criteria of thickener mass balance are the following:

 Release of CO2 –It assumes that CO2 in bubble is pure. For modeling
purpose, the partial pressure of CO2 (atm) is partial pressure in the
atmosphere. The atmosphere contains 0.03% of CO2 .
11.2.1.3.Press filter
Design criteria of press filter mass balance are the following:
 Wash ratio: 1.5m3/ton.

 Wash efficiency: 98%.
11.2.1.4.Co precipitation
 Precipitation pH: 8.3 to have around 0.1g/L of Co.

 Equation (11.48) gives the value of Eh(v) obtained from cobalt open
precipitation tank in cobalt production plant.
Eh=-0.101*pH+1.116 (v) (11.48)

 MgO is used as neutralization agent in cobalt precipitation. Tables (6.5)
and (6.6) give chemical and mineralogical compositions of EMAG. The
reaction extent is given by Equation (6.3) in industrial practice for MgO
and CaO.
RE(%)=-12.527*pH+177.28 (6.3)
 Table (5.1) gives the standard free Gibbs energies of reference ions and
water at 25°C. Equation (11.1) gives the chemical potential of reference
ions at 25°C. Equation (11.2) gives the chemical potential of water.
 Precipitation of phosphate. Chapter 11.2.1.1.
 Precipitation of aluminate. Chapter 11.2.1.1.
 Precipitation of carbonates. Chapter 11.2.1.1.
 Precipitation of ferrites. Chapter 11.2.1.1.
 Precipitation of hydroxyls and hydroxyl-sulfates. Chapter 11.2.1.1.
 Solution is saturated in silica. Chapter 11.2.1.1.
 Oxidation of Mn(OH)2 into MnOOH. Mn(OH)2 absorbs oxygen from Air
and is oxidized into MnOOH according to chemical reaction (11.ao).
Mn(OH)2 and MnOOH are mixed into heterogeneous solid solution.
Equations (11.49) and (11.50) give the chemical potentials of Mn(OH)2
and MnOOH respectively. Equations (11.51) and (11.52) allow obtaining
molar fraction of Mn(OH)2 and MnOOH. The quantity of absorbed oxygen
is obtained from chemical reaction (11.ap).
Mn(OH)2=MnOOH+H + +e− (11.ao)
μ(Mn(OH)2 ) =μ(SH/aj) +R*T*2.303*log(X(Mn(OH)2 )) (11.49)
μ(MnOOH/a) =μ°(MnOOH) +R*T*2.303*log(X(MnOOH)) (11.50)
μ(Mn(OH)2 ) =μ(MnOOH) +μ(H+ ) -96485*Eh (11.51)
X(Mn(OH)2 ) +X(MnOOH)=1 (11.52)
4Mn(OH)2+O2 =4MnOOH+2H2 O (11.ap)
 Oxidation of Co(OH)2 into CoOOH. Co(OH)2 absorbs oxygen from Air and
is oxidized into CoOOH according to chemical reaction (11.aq). Co(OH)2
and CoOOH are mixed into heterogeneous solid solution. Equations
(11.53) and (11.54) give the chemical potentials of Co(OH)2 and CoOOH
respectively. Equations (11.55) and (11.56) allow obtaining molar fraction

of Co(OH)2 and CoOOH. The quantity of absorbed oxygen is obtained from
chemical reaction (11.ar).
Co(OH)2=CoOOH+H + +e− (11.aq)
μ(Co(OH)2 ) =μ(SH/ag)+R*T*2.303*log(X(Co(OH)2 ) ) (11.53)
μ(CoOOH) =μ°(CoOOH) +R*T*2.303*log(X(CoOOH)) (11.54)
μ(Co(OH)2 ) =μ(CoOOH) +μ(H+) -96485*Eh (11.55)
X(Co(OH)2 ) +X(CoOOH)=1 (11.56)
4Co(OH)2+O2 =4CoOOH+2H2 O (11.ar)
 Oxidation of adsorbed Co on surface of MnOOH into CoOOH. MnOOH

adsorbs cobalt ion on the surface and oxidizes Co ion into CoOOH
according to chemical reaction (11.as). MnOOH and CoOOH are mixed into
heterogeneous solid solution. Equations (11.57) and (11.58) give the
chemical potentials of MnOOH and CoOOH respectively. Equations (11.59)
and (11.60) allow obtaining molar fraction of MnOOH and CoOOH.
MnOOH+Co+2 =CoOOH+Mn+2 (11.as)
μ(MnOOH/b) =μ(MnOOH/a) +R*T*2.303*log(X(MnOOH) ) (11.57)
μ(CoOOH) =μ°(CoOOH) +R*T*2.303*log(X(CoOOH)) (11.58)
μ(MnOOH/b) +μ(Co+2 ) =μ(CoOOH) +μ(Mn+2 ) (11.59)
X(MnOOH) +X(CoOOH) =1 (11.60)
 Oxidation of Ferrous into ferric. Ferrous precipitate as Fe(OH)2 according

to the chemical reaction (11.al). Fe(OH)2 absorbs oxygen from Air and is
oxidized into Fe(OH)3 according to chemical reaction (11.at). There is a
complete oxidation of Fe(OH)2 into Fe(OH)3 . In presence of Copper Cu+2
reacts with Fe(OH)3 and produces amorphous copper ferrite according to
chemical reaction (11.au). In this publication, for modeling purpose, the
following path way is used - ferrous is oxidized by oxygen according to
chemical reaction (11.av). Fe+3 precipitates as Fe(OH)3 and
CuFe2 O4 . 2H2 O. Quantity of absorbed oxygen is obtained from chemical

reaction (11.aw). Equation (11.61) gives reaction extent of ferrous
oxidation by oxygen from Air.
Fe+2+2OH − =Fe(OH)2 (11.al)
Fe(OH)2 +H2 O=Fe(OH)3 +H + +e− (11.at)
Fe+2+2Fe(OH)3 =CuFe2 O4 . 2H2 O+2H + (11.au)
Fe+2=Fe+3+e− (11.av)
4Fe+2+O2 +4H + =4Fe+3+2H2 O (11.aw)
μ(Fe+3 ) -96485*Eh=μ(Fe+2 ) (11.60)
11.2.1.5.Thickener

Design criteria of press filter mass balance are the following:
 Wash ratio: 3.0m3/ton.

 Wash efficiency: 98%.
11.2.1.7.Effluent neutralization
 Precipitation pH: 9.0

Eh=-0.101*pH+1.116 (v) (11.48)
 Dissolution of CaCO3 from inlet solid: 0.0%.

 Dissolution of MgCO3 from inlet solid: 0.0%.
 Dissolution of other minerals from inlet solid: 100%
 Quick lime is used as neutralization agent in effluent neutralization. Tables
(6.3) and (6.4) give chemical and mineralogical compositions of Likasi
limestone. The reaction extent is given by Equation (6.2) for CaO, Ca(OH)2
and Mg(OH)2 in industrial practice.
RE(%)=-2.318*pH+99.38 (6.2)
 Solid percent in quick lime pulp: 20%.

 Oxidation of Ferrous into ferric: chapter 11.2.1.4.
 Oxidation of Mn(OH)2 into MnOOH: chapter 11.2.1.4.
 Oxidation of Co(OH)2 into CoOOH: chapter 11.2.1.4.
 Oxidation of adsorbed Co on surface of MnOOH into CoOOH: chapter
11.2.1.4.

Tables from (11.1) to (11.3) give the mass balance of cobalt hydroxide
production circuit (A) obtained by using the realistic simulation model. Table (11.4)
gives the mineralogical composition of Fe and Al precipitation and Co precipitation.
Tables (11.5) and (11.6) give the distribution of elements in inlet and outlet of cobalt
production circuit. Table (11.7) gives Cobalt production and Cobalt recovery. Table
(11.8) gives the reaction extent and the reagent consumption. Table (11.9) gives reagent
costs and cobalt hydroxide transport cost.

Table 11.1: Mass balance of cobalt hydroxide precipitation circuit - A
1 2 3 4 5 6 7 8
WBB LS FAPCO2 OFAP FAPTKFc FAPFLF FAPFKCO2 FAPTKOF
Solid/gas
mass t/h 16.997 4.537 24.867 0.0010 0.419
volume m3/h 0.0004
SG solid t/m3 2.650
Cu % 0.217
Co % 0.000
Zn % 0.000
Ni % 0.000
Mn % 0.000
Mg % 2.800 0.516
Al % 0.889 2.719
Fe(II) % 0.000
Fe(III) % 1.028 0.839
Ca % 33.118 22.029
S % 12.452
P % 0.952
Si % 2.580 1.764
C % 11.010 2.029
Pulp
mass t/h 84.986 778.840 0.398
volume m3/h
SG solid t/m3
%solid 20.00 3.193 0.250
Liquid
mass t/h 698.391 67.989 753.973 0.397 57.839 774.608
volume m3/h 664.181 67.989 726.073 0.397 56.642 749.385
SG liquid t/m3 1.052 1.000 1.038 1.000 1.021 1.034
S2O6 g/l 15.702 14.364 8.653 13.904
Cu g/l 0.327 0.224 0.135 0.217
Co g/l 5.346 4.890 2.946 4.733
Zn g/l 0.594 0.543 0.327 0.526
Ni g/l 0.080 0.073 0.044 0.071
Mn g/l 0.936 0.856 0.516 0.829
Mg g/l 1.190 1.567 0.944 1.517
Al g/l 0.817 0.024 0.015 0.024
Fe(II) g/l 0.973 0.890 0.536 0.861
Fe(III) g/l 0.051 0.000 0.000 0.000
Ca g/l 0.671 0.821 0.510 0.820
S g/l 15.161 9.604 5.798 9.316
P g/l 0.356 0.000 0.000 0.000
Si g/l 0.024 0.024 0.015 0.024
C g/l 0.000 0.177 0.012 0.019
Ac g/l 11.106 0.002 0.000 0.000

9 10 11 12 13 14 15 16
FAPTKUF FAPFLW FAPFLCa CPMG CPAO2 OCP CPTKFc CPFKOF
Solid/gas
mass t/h 24.788 24.788 3.682 0.1926 11.596 0.0005
volume m3/h 0.0002
SG solid t/m3 2.650
Cu % 0.218 0.218 1.404
Co % 0.000 0.000 29.818
Zn % 0.000 0.000 3.399
Ni % 0.000 0.000 0.441
Mn % 0.000 0.000 1.888
Mg % 0.518 0.518 57.897 4.962
Al % 2.728 2.728 0.000 0.153
Fe(II) % 0.000 0.000 0.000
Fe(III) % 0.842 0.842 0.000 5.566
Ca % 22.100 22.100 1.930 0.164
S % 12.432 12.432 4.528
P % 0.955 0.955 0.000
Si % 1.769 1.769 0.608 0.193
C % 2.036 2.036 0.123
Pulp
mass t/h 61.970 41.313 778.482 0.186
volume m3/h
SG solid t/m3
%solid 40.000 60.000 1.490 0.250
Liquid
mass t/h 37.182 37.182 16.525 766.887 0.185 701.360
volume m3/h 35.971 37.182 16.501 746.598 0.185 682.810
SG liquid t/m3 1.034 1.000 1.001 1.027 1.000 1.027
S2O6 g/l 13.904 0.606 13.956 13.952
Cu g/l 0.217 0.009 0.000 0.000
Co g/l 4.733 0.206 0.120 0.120
Zn g/l 0.526 0.023 0.000 0.000
Ni g/l 0.071 0.003 0.003 0.003
Mn g/l 0.829 0.036 0.539 0.538
Mg g/l 1.517 0.066 3.607 3.607
Al g/l 0.024 0.001 0.000 0.000
Fe(II) g/l 0.861 0.038 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000
Ca g/l 0.820 0.036 0.893 0.893
S g/l 9.316 0.406 8.648 8.646
P g/l 0.000 0.000 0.000 0.000
Si g/l 0.024 0.001 0.024 0.024
C g/l 0.019 0.001 0.000 0.000
Ac g/l 0.000 0.000 0.000 0.000

17 18 19 20 21 22 23 24
CPTKUF CPFLW CPFLF CPFLCa ENQL ENAO2 OEN
Solid/gas
mass t/h 11.596 11.596 1.0429 0.000 27.7304
volume m3/h
SG solid t/m3
Cu % 1.404 1.404 0.195
Co % 29.817 29.817 0.334
Zn % 3.399 3.399 0.001
Ni % 0.441 0.441 0.008
Mn % 1.888 1.888 1.446
Mg % 4.962 4.962 1.972 0.623
Al % 0.153 0.153 0.300 2.450
Fe(II) % 0.000 0.000 0.000
Fe(III) % 5.565 5.565 0.200 0.762
Ca % 0.164 0.164 51.458 21.418
S % 4.528 4.528 12.062
P % 0.000 0.000 0.814
Si % 0.193 0.193 0.640 1.606
C % 0.123 0.123 1.500 1.876
Pulp
mass t/h 77.308 28.990 5.215 830.994
volume m3/h
SG solid t/m3
%solid 15.000 40.000 20.000 3.337
Liquid
mass t/h 65.711 34.788 83.106 17.394 4.172 803.264
volume m3/h 63.973 34.788 81.395 17.359 4.172 784.092
SG liquid t/m3 1.027 1.000 1.021 1.002 1.000 1.024
S2O6 g/l 13.952 10.746 1.028 13.278
Cu g/l 0.000 0.000 0.000 0.000
Co g/l 0.120 0.092 0.009 0.000
Zn g/l 0.000 0.000 0.000 0.000
Ni g/l 0.003 0.002 0.000 0.000
Mn g/l 0.538 0.415 0.040 0.001
Mg g/l 3.607 2.778 0.266 3.400
Al g/l 0.000 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000
Ca g/l 0.893 0.687 0.066 0.946
S g/l 8.646 6.659 0.637 7.893
P g/l 0.000 0.000 0.000 0.014
Si g/l 0.024 0.019 0.002 0.024
C g/l 0.000 0.000 0.000 0.000
Ac g/l 0.000 0.000 0.000 0.000

Table 11.4: Mineralogical composition of precipitates.
FAP CP EN
Mass (kg/hrs) % Mass (kg/hrs) % Mass (kg/hrs) %
CaCO3 (unreacted) 3677.16 14.79 0.00 0.00 3739.08 13.48
Ca(OH)2 0.000 0.00 35.061 0.30 188.604 0.68
CaSiO3 489.519 1.97 0.000 0.00 517.125 1.86
MgCO3 445.091 1.79 0.000 0.00 445.091 1.61
Mg(OH)2 (unreacted) 0.000 0.00 1365.179 11.77 10.597 0.04
Al2O3 285.553 1.15 0.000 0.00 291.466 1.05
Fe2O3 249.859 1.00 0.000 0.00 252.841 0.91
SiO2 684.987 2.75 47.865 0.41 684.987 2.47
CaSO4.2H2O 16480.69 66.27 0.00 0.00 17759.38 64.04
Co3(PO4)2.8H2O 0.000 0.00 0.123 0.00 0.000 0.00
MnHPO4.3H2O 0.00 0.00 0.00 0.00 1494.08 5.39
AlPO4.2H2O 1207.24 4.85 0.00 0.00 0.00 0.00
Fe(OH)3 37.455 0.15 1261.508 10.88 120.929 0.44
Al4(OH)(11.36).(SO4)(0.32).5H2O 1114.96 4.48 0.00 0.00 1533.23 5.53
Cu4(OH)6SO4.H2O 0.272 0.00 0.000 0.00 0.000 0.00
Co2Cu3(OH)6(SO4)2.5H2O 0.123 0.00 0.000 0.00 0.000 0.00
Cu(OH)2 1.433 0.01 0.707 0.01 0.157 0.00
ZnCo3(OH)6(SO4).3H2O 0.00 0.00 2978.86 25.69 0.00 0.00
Zn(OH)2 0.001 0.00 0.157 0.00 0.000 0.00
Co5(OH)6(SO4)2.3H2O 0.00 0.00 3326.15 28.68 0.00 0.00
Co(OH)2 0.000 0.00 406.322 3.50 0.000 0.00
Ni4(OH)6SO4 0.000 0.00 0.068 0.00 0.000 0.00
Ni(OH)2 0.000 0.00 80.763 0.70 0.004 0.00
Mn(OH)2 0.000 0.00 26.035 0.22 0.484 0.00
Mg(OH)2 (precipitated) 0.000 0.00 15.206 0.13 95.905 0.35
CuFe2O4.2H2O 57.171 0.23 703.297 6.07 0.000 0.00
CuAl2O4.2H2O 135.783 0.55 0.000 0.00 184.963 0.67
CoAl2O4.2H2O 0.000 0.00 69.977 0.60 334.543 1.21
ZnAl2O4.2H2O 0.000 0.00 0.000 0.00 1.277 0.00
NiAl2O4.2H2O 0.000 0.00 0.000 0.00 7.543 0.03
MnCO3 0.000 0.00 136.817 1.18 0.000 0.00
CaCO3 (precipitated) 0.000 0.00 0.000 0.00 67.971 0.25
CoOOH 0.000 0.00 921.451 7.95 0.000 0.00
MnOOH 0.000 0.00 220.116 1.90 0.097 0.00
Total 24867.31 11595.67 27730.36

Table 11.5: Distribution of elements in Inlet (%)
Inlet
WBB FAPLS CPMG
Cu 100.000 0.000 0.000
Co 100.000 0.000 0.000
Zn 100.000 0.000 0.000
Ni 100.000 0.000 0.000
Mn 100.000 0.000 0.000
Mg 23.265 14.003 62.732
Al 78.222 21.778 0.000
Ca 7.247 91.597 1.156
S 100.000 0.000 0.000
P 100.000 0.000 0.000
Si 3.350 91.958 4.692
C 0.001 99.999 0.000
Fe 79.551 20.449 0.000
Table 11.6: Distribution of elements in outlet (%)
Outlet
FAPFLCa CO2 CPFLCa CPTKOf/CPFLF
Cu 24.953 0.000 75.047 0.000
Co 0.097 0.000 97.392 2.512
Zn 0.096 0.000 99.903 0.001
Ni 0.096 0.000 96.087 3.817
Mn 0.096 0.000 35.333 64.571
Mg 3.809 0.000 17.068 79.123
Al 97.444 0.000 2.556 0.000
Ca 88.879 0.000 0.326 10.794
S 30.669 0.000 5.324 64.007
P 99.994 0.000 0.006 0.000
Si 91.544 0.000 4.677 3.779
C 26.969 72.267 0.764 0.000
Fe 24.486 0.000 75.514 0.000

Table 11.7: Coblat production and recovery
Cobalt production 3.458 t/hrs

Cobalt grade in hydroxide 29.817 %
Cobalt recovery from water balance bleed 97.392 %
Cobalt recovery from copper circuit feed 96.050 %
Table 11.8: Reaction extent and reagent consumption
Reaction extent (%)

FAP Limestone 73.032 4.916 T/tCo
CP MgO 73.306 1.065 T/tCo
EN quick lime 78.518 0.302 T/tCo
Flocculants 0.422 kg/tCo
Table 11.9: Reagent cost and cobalt hydroxide transport cost
Consumption Cost ($/t) (DRC) Cost ($/tCo)

Limestone 4.916 t/tCo 70.00 344.09
CP MgO 1.065 t/tCo 700.00 745.37
EN quick lime 0.302 t/tCo 150.00 45.24
Flocculants 0.422 t/tCo 3900.00 1.65
Transport Cobalt (DRC-SA) 8.384 t/tCo 240.00 2012.18
Total 3148.53
The grade of cobalt in the cobalt precipitation cake is 29.82% because:
 1.404% of Cu grade and 75% of Cu is in cobalt hydroxide cake as

CuFe2O4,2H2O.
 3.399% of Zn grade and 99.9% of Zn is in cobalt hydroxide cake as
ZnCo3(OH)6(SO4),3H2O.
 5.565% of Fe grade and 75% of Fe is in cobalt hydroxide cake as Fe(OH)3
and CuFe2O4,2H2O.
 4.962% of Mg grade and Mg is in cobalt hydroxide cake as unreacted
Mg(OH)2.
 35% of Mn is in the cake as MnCO3. Carbonate comes from Fe and Al
precipitation.

The target is to have the cobalt grade more than 40%. The grades of Copper,
Zinc, Iron, and Magnesium must decrease to increase the grade of Cobalt by using the
following procedure:
 Oxidation of Fe(II) by oxygen in Fe and Al precipitation step and Fe and

Cu will co-precipitate as CuFe2O4,2H2O.
 Solvent extraction of Zn using Cyanex 272 as extractant. The solvent
extraction of Zn is done without neutralization.
 Leach Mg in cobalt hydroxide cake at pH 7.

12. Mass balance of Cobalt circuit –B
12.1. Configuration

Figure (12.1) gives the flow diagram of Cobalt circuit (B). The purpose of the
flow diagram is to remove Copper, Zinc, Iron and Mg from Cobalt hydroxide cake. Cobalt
grade in the cobalt hydroxide cake must be greater than 40%.
 FALSP: Fe and Al precipitation with limestone.

 FAQLP: Fe and Al precipitation with quick lime.
 ZSXE: Zinc solvent extraction-Extraction step.
 ZSXS: Zinc solvent extraction – Stripping step
 CP: Co precipitation.
 CPTK: Thickener of Co precipitation.
 MGD: Magnesium dissolution.
 MGDFL: Filtration of Co precipitation.
 EN: Effluent neutralization
 WBB: Water balance bleed

 FAPLS: Limestone.
 FALSPCO2: CO2 releases from Fe and Al precipitation using limestone.
 OFALSP: Outlet of Fe and Al precipitation using limestone.
 FAPQL: Quick lime.
 FAQLPO2: Oxygen from Air
 FAQLPCO2: CO2 releases from Fe and Al precipitation using quick lime.
 OFQLAP: Outlet of Fe and Al precipitation using quick lime.
 FAPTKUF: Underflow of thickener of Fe and Al precipitation.

Figure 12.1. : Flow diagram of cobalt circuit - B
 FAPFLF: Filtrate of filter of Fe and Al precipitation.

 FAPFLWW: Wash water of filter of Fe and Al precipitation.
 FAPFLCa: Cake of filter of Fe and Al precipitation.
 ZSXER: Zinc solvent extraction – raffinate.
 ZSXLO: Zinc solvent extraction – loaded organic.
 ZSXALO: Zinc solvent extraction – aqueous entrainment in LO.
 ZSXSO: Zinc solvent extraction – stripped organic.
 ZSXASO: Zinc solvent extraction – aqueous entrainment in SO.
 ZSXAS: Zinc solvent extraction – acid solution.
 ZSXSR: Zinc solvent extraction – recycled stripping solution.
 ZSXSTS: Zinc solvent extraction – stripping solution.

 CPMG: MgO of cobalt precipitation.
 CPAO2: Oxygen from Air absorbed by solid.
 OCP: Outlet of cobalt precipitation.
 CPTKFc: Flocculants of thickener of cobalt precipitation.
 CPTKOF: Overflow of thickener of cobalt precipitation.
 CPTKUF: Underflow of thickener of cobalt precipitation.
 MGDAc: Acid for magnesium dissolution.
 OMGD: outlet of magnesium dissolution.
 MGDFLF: Filtrate of filter of magnesium dissolution
 MGDFLW: Wash water of filter of magnesium dissolution.
 MGDFLCa: Cake of filter of magnesium dissolution.
 ENQL: Quick lime of effluent neutralization.
 ENAO2: Oxygen from Air absorbed by solid.

Water balance bleed is fed to Fe and Al precipitation tank with limestone using
as neutralization agent at pH 3.0. The outlet is fed to Fe and Al precipitation tank with
quick lime using as neutralization agent at pH 5.0. Air is injected to oxidize ferrous into
ferric and to remove carbanate is solution. Pulp after precipitation is fed in the tickener
and underflow of thickener is fed to the filter. Filtrate is fed to the thickener and
overflow of thickener is fed to surge tank.
Overflow of Fe and Al precipitation thickener is fed to Zin solvent extraction

using Cyanex 272 as extractant. The load organic is stripped with acid solution and the
stripping solution is fed to neutralization step where quick lime is used as neutralization
agent.
The raffinate of Zinc solvent extraction is fed Co precipitation tank with MgO
using as neutralization agent at pH 8.3 to Co concentration around 0.1g/L. Pulp after
precipitation is fed in the thickener and underflow of thickener is fed to Magensium
dissolution step at pH 7. Outlet of Magnesium dissolution step is fed to the filter. Cobalt
precipitation overflow of thickener, Zn solvent extraction stripping solution and Fe and
Al filter cake are fed to effluent neutralization tank. Magnesium dissolution filter filtrate
is fed to Fe and Al precipitation using limestone as neutralisation agent.

12.2. Mass balance
12.2.1.1.Fe and Al precipitation using limestone

 Limestone: chapter 11.2.1.1.
12.2.1.2.Fe and Al precipitation using quick lime

 Dissolution of CaCO3 , MgCO3 , CaSiO3 , Al2 O3 and Fe2 O3 from inlet solid:
0.0%.
 Dissolution of other minerals from inlet solid: 100%
 Quick lime is used as neutralization agent in Fe and Al precipitation.
Tables (6.3) and (6.4) give chemical and mineralogical compositions of
Likasi limestone. The reaction extent is given by Equation (6.2) for CaO,
Ca(OH)2 and Mg(OH)2 in industrial practice.
RE(%)=-2.318*pH+99.38 (6.2)
 Solid percent in limestone pulp: 20%.

 Oxidation of Ferrous into ferric:
o Ferrous is oxidized by oxygen according to chemical reaction
(11.av). Fe+3 precipitates as Fe(OH)3 and CuFe2 O4 . 2H2 O. Quantity
of reacted oxygen is obtained from chemical reaction (11.aw). The

quantity of injected oxygen in the precipitation tank must be 10
times greater than quantity of required oxygen. The residence
time depends on the quantity of ferrous in solution.
Fe+2=Fe+3+e− (11.av)
4Fe+2+O2 +4H + =4Fe+3+2H2 O (11.aw)
o The target is 0.05g/L of ferrous in solution after oxidation

because the kinetic of ferrous oxidation by oxygen from Air is
proportional to concentration of ferrous in solution (first order
reaction).
 Release of CO2 :
o Figure (12.2) shows the bubble of CO2 in the precipitation pulp.
There is a dilution of CO2 by Air in the Bubble. It assumes that CO2
concentration in the bubble is 0.03%.
Figure 12.2: Precipitation tank with CO2 bubble

o The pressure of Air (atm) in the bubble is given by Equation
(12.3). For modeling purpose, the value of depth “h” is equal to
Hp /2.
o Equation (12.4) gives partial pressure of CO2 in the bubble.
Equation (12.5) gives the concentration of H2 CO3 in the pulp in
equilibrium with CO2 in the bubble.
ρ∗g∗h
Ph=P0+101325 (atm) (12.3)
P(CO2) =Ph*0.03/100 (12.4)
C(H2 CO3 )=4.571*10−2 *Ph (M) (11.46)
 Precipitation tank sizing:

o Residence time per precipitation tank: 30minutes
o Ratio D/H=0.9
12.2.1.3.Thickener
Design criteria of thickener mass balance are the following: chapter 11.2.1.2.
Design criteria of press filter mass balance are the following: chapter 11.2.1.3.
12.2.1.5.Zinc solvent extraction – Extraction train
Design criteria of ZnSX - extraction circuit mass balance are the following:
 Type of extractant: Cyanex 272.

 O/A advance ratio: 1.25.
 Feed solution pH: pH of overflow of thickener (around 5.0).
 Raffinate pH: depends on the quantity of extracted elements.

 Volume percent of extractant in organic phase: depends on quantity of
extracted elements and raffinate pH.
 Quantity of extracted zinc is equal to 80% of quantity of zinc in the water
balance bleed (WBB).
 Aqueous entrainment in organic: 1000ppm.
 Organic entrainment in aqueous: 50ppm.
 Organic entrainment recovery from dial filter: 70%.
 Equilibrium element concentrations: Equation (8.1) gives equilibrium
condition of chemical reaction (8.a)
(n+x)
M +n + (HA)y =MAn (HA)x +nH + (8.a)
y
C(MAn (HA)3 ) ∗γ(MAn (HA)3 ) ∗[C(H+ ) ∗γ(H+ ) ]n

K= 𝑛+𝑥
( )
C(M+n ) ∗γ(M+n ) ∗[C(HA) ∗γ(HA) ] 𝑦
(8.1)
12.2.1.6.Zinc solvent extraction – Stripping train
Design criteria of ZnSX - stripping circuit mass balance are the following:
 O/A advance ratio: 30.

 O/A internal ratio: 1.25
 Acid concentration in acid solution: 150g/L.
 Organic entrainment in organic: 100ppm.
(n+x)
MAn (HA)x +nH + =M +n + y
(HA)y (12.a)
12.2.1.7.Co precipitation
Design criteria of cobalt precipiation: Chapter 11.2.1.4.
12.2.1.8.Thickener
Design criteria of thickener: Chapter 11.2.1.5.

12.2.1.9. Magnesium dissolution
 Dissolution pH: 7.0.

 Dissolution of CoOOH and MnOOH from inlet solid: 0.0%.
 Dissolution of unreacted CaO and MgO from inlet solid to reach the
unreacted CaO and MgO of the reaction extent of MgO at pH 7.0.
 Dissolution of other minerals: 100.0%.
 Oxidation of Mn(OH)2 into MnOOH. Chapter 11.2.1.4.
 Oxidation of Co(OH)2 into CoOOH. Chapter 11.2.1.4.
 Oxidation of adsorbed Co on surface of MnOOH into CoOOH. Chapter
11.2.1.4.
12.2.1.10. Press filter
Design criteria of press filter: Chapter 11.2.1.6.
12.2.1.11. Effluent neutralization
Design criteria of press filter: Chapter 11.2.1.7.

production circuit (B) obtained by using the realistic simulation model. Tables (12.6)
and (12.7) give the mineralogical composition of solids. Tables (12.8) and (12.9) give
the distribution of elements in the inlet and the outlet of cobalt circuit.
Table (12.10) gives cobalt production and cobalt recovery. Table (12.11) gives
the reaction extent and reagent consumptions. Table (12.12) gives volume percent of
Cyanex 272 and consumption of extractant and diluent. Table (12.13) gives reagent

Table 12.1: Mass balance of cobalt hydroxide precipitation circuit - B
1 2 3 4 5 6 7 8
WBB FAPLS FALSPCO2 OFALSP FAPQL FAQLPO2 FAQLPCO2 OFAQLP
Solid/gas
mass t/h 11.980 3.536 17.585 2.934 0.0869 0.568 26.475
volume m3/h
SG solid t/m3
Cu % 0.000 0.814
Co % 0.000 0.000
Zn % 0.000 0.000
Ni % 0.000 0.000
Mn % 0.000 0.000
Mg % 2.800 0.334 1.972 0.248
Al % 0.889 1.740 0.300 2.455
Fe(II) % 0.000 0.000
Fe(III) % 1.028 0.719 0.200 2.907
Ca % 33.118 22.127 51.458 20.149
S % 14.113 13.147
P % 1.300 0.894
Si % 2.580 1.758 0.640 1.238
C % 11.010 1.313 1.500 0.918
Pulp
mass t/h 59.899 826.028 14.669 840.216
volume m3/h
SG solid t/m3
%solid 20.00 2.129 20.000 3.151
Liquid
mass t/h 698.391 47.919 808.443 11.735 813.742
volume m3/h 664.181 47.919 774.778 11.735 786.775
SG liquid t/m3 1.052 1.000 1.043 1.000 1.034
S2O6 g/l 15.702 14.400 14.180
Cu g/l 0.327 0.280 0.002
Co g/l 5.346 5.026 4.949
Zn g/l 0.594 0.509 0.502
Ni g/l 0.080 0.204 0.201
Mn g/l 0.936 0.863 0.850
Mg g/l 1.190 2.030 2.063
Al g/l 0.817 0.443 0.011
Fe(II) g/l 0.973 0.834 0.050
Fe(III) g/l 0.051 0.039 0.000
Ca g/l 0.671 0.708 0.782
S g/l 15.161 11.221 9.780
P g/l 0.356 0.010 0.000
Si g/l 0.024 0.024 0.024
C g/l 0.000 0.159 0.000
Ac g/l 11.106 0.146 0.001

9 10 11 12 13 14 15 16
FAPTKFc FAPFLF FAPTKOF FAPTKUF FAPFLW FAPFLCa ZSXASO ZSXER
Solid/gas
mass t/h 0.0011 26.396 26.396
volume m3/h 0.0004
SG solid t/m3 2.650
Cu % 0.817 0.817
Co % 0.000 0.000
Zn % 0.000 0.000
Ni % 0.000 0.000
Mn % 0.000 0.000
Mg % 0.249 0.249
Al % 2.462 2.462
Fe(II) % 0.000 0.000
Fe(III) % 2.915 2.915
Ca % 20.209 20.209
S % 13.130 13.130
P % 0.897 0.897
Si % 1.242 1.242
C % 0.920 0.920
Pulp
mass t/h 0.424 65.991 43.994
volume m3/h
SG solid t/m3
%solid 0.250 40.000 60.000
Liquid
mass t/h 0.423 61.591 836.161 39.594 39.594 17.597 1.011 836.161
volume m3/h 0.423 60.327 809.141 38.315 39.594 17.571 0.890 809.352
SG liquid t/m3 1.000 1.021 1.033 1.033 1.000 1.001 1.136 1.033
S2O6 g/l 8.574 13.775 13.775 0.601 0.403 13.755
Cu g/l 0.001 0.002 0.002 0.000 0.000 0.002
Co g/l 2.992 4.808 4.808 0.210 0.577 4.783
Zn g/l 0.303 0.487 0.487 0.021 9.444 0.107
Ni g/l 0.122 0.195 0.195 0.009 0.006 0.195
Mn g/l 0.514 0.826 0.826 0.036 0.200 0.818
Mg g/l 1.248 2.005 2.005 0.087 0.079 2.001
Al g/l 0.006 0.010 0.010 0.000 0.140 0.005
Fe(II) g/l 0.030 0.049 0.049 0.002 0.001 0.049
Fe(III) g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ca g/l 0.487 0.782 0.782 0.034 0.023 0.781
S g/l 5.925 9.519 9.519 0.415 47.253 9.557
P g/l 0.000 0.000 0.000 0.000 0.000 0.000
Si g/l 0.015 0.024 0.024 0.001 0.001 0.024
C g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.001 0.001 0.001 0.000 124.466 0.780

17 18 19 20 21 22 23 24
ZSXSO ZSXLO ZSXALO ZSXAS ZSXSTR ZSXSTS CPMG CPAO2
Solid/gas
mass t/h 3.289 0.1076
volume m3/h
SG solid t/m3
Cu %
Co %
Zn %
Ni %
Mn %
Mg % 57.897
Al % 0.000
Fe(II) %
Fe(III) % 0.000
Ca % 1.930
S %
P %
Si % 0.608
C %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 1.011 37.973 879.724 36.962
volume m3/h 1011.43 1011.426 0.979 33.714 774.459 32.539
SG liquid t/m3 1.033 1.126 1.136 1.136
S2O6 g/l 13.755 0.000 0.403 0.403
Cu g/l 0.0000 0.0000 0.002 0.000 0.000 0.000
Co g/l 0.0000 0.0144 4.783 0.000 0.577 0.577
Zn g/l 0.0065 0.3185 0.107 0.000 9.444 9.444
Ni g/l 0.195 0.000 0.006 0.006
Mn g/l 0.0000 0.0058 0.818 0.000 0.200 0.200
Mg g/l 0.0000 0.0007 2.001 0.000 0.079 0.079
Al g/l 0.0008 0.0054 0.005 0.000 0.140 0.140
Fe(II) g/l 0.049 0.000 0.001 0.001
Fe(III) g/l 0.0000 0.0000 0.000 0.000 0.000 0.000
Ca g/l 0.781 0.000 0.023 0.023
S g/l 9.557 46.576 47.253 47.253
P g/l 0.000 0.000 0.000 0.000
Si g/l 0.024 0.000 0.001 0.001
C g/l 0.000 0.000 0.000 0.000
Ac g/l 0.780 150.000 124.466 124.466

25 26 27 28 29 30 31 32
OCP CPTKFc CPFKOF CPTKUF MGDAc OMGD MGDFLW MGDFLF
Solid/gas
mass t/h 9.764 0.0004 9.765 8.300
volume m3/h 0.0001
SG solid t/m3 2.650
Cu % 0.014 0.014 0.016
Co % 38.484 38.482 41.144
Zn % 0.890 0.890 1.046
Ni % 1.532 1.532 0.519
Mn % 1.566 1.566 1.671
Mg % 5.257 5.257 2.389
Al % 0.038 0.038 0.045
Fe(II) % 0.000 0.000 0.000
Fe(III) % 0.402 0.402 0.473
Ca % 0.174 0.174 0.420
S % 6.437 6.437 7.512
P % 0.000 0.000 0.000
Si % 0.205 0.205 0.241
C % 0.000 0.000 0.000
Pulp
mass t/h 839.558 0.156 65.098 67.124
volume m3/h
SG solid t/m3
%solid 1.163 0.250 15.000 12.364
Liquid
mass t/h 829.794 0.156 774.616 55.333 2.026 58.825 24.899 71.274
volume m3/h 807.335 0.156 753.654 53.836 1.126 54.854 24.899 67.342
SG liquid t/m3 1.028 1.000 1.028 1.028 1.800 1.072 1.000 1.058
S2O6 g/l 13.790 13.787 13.787 13.531 10.802
Cu g/l 0.000 0.000 0.000 0.000 0.000
Co g/l 0.141 0.141 0.141 6.389 5.101
Zn g/l 0.000 0.000 0.000 0.002 0.002
Ni g/l 0.010 0.010 0.010 1.952 1.558
Mn g/l 0.630 0.630 0.630 0.878 0.701
Mg g/l 3.729 3.728 3.728 9.403 7.506
Al g/l 0.000 0.000 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000 0.000
Ca g/l 0.841 0.840 0.840 0.498 0.398
S g/l 8.803 8.801 8.801 576.729 20.566 16.417
P g/l 0.000 0.000 0.000 0.000 0.000
Si g/l 0.024 0.024 0.024 0.024 0.019
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.000 0.000 0.000 1764.000 0.000 0.000

33 34 35 36 37 38 39 40
MGDFLCa ENQL ENAO2 OEN
Solid/gas
mass t/h 8.300 6.255 0.000 39.376
volume m3/h
SG solid t/m3
Cu % 0.016 0.548
Co % 41.144 0.327
Zn % 1.046 0.781
Ni % 0.519 0.020
Mn % 1.671 1.208
Mg % 2.389 1.972 0.383
Al % 0.045 0.300 1.710
Fe(II) % 0.000 0.000
Fe(III) % 0.473 0.200 1.986
Ca % 0.420 51.458 21.456
S % 7.512 13.212
P % 0.000 0.596
Si % 0.241 0.640 0.934
C % 0.000 1.500 0.855
Pulp
mass t/h 20.749 31.273 886.845
volume m3/h
SG solid t/m3
%solid 40.000 20.000 4.440
Liquid
mass t/h 12.449 25.018 847.470
volume m3/h 12.366 25.018 827.410
SG liquid t/m3 1.007 1.000 1.024
S2O6 g/l 1.200 12.587
Cu g/l 0.000 0.000
Co g/l 0.567 0.000
Zn g/l 0.000 0.000
Ni g/l 0.173 0.000
Mn g/l 0.078 0.008
Mg g/l 0.834 3.447
Al g/l 0.000 0.000
Fe(II) g/l 0.000 0.000
Fe(III) g/l 0.000 0.000
Ca g/l 0.044 0.894
S g/l 1.825 7.785
P g/l 0.000 0.003
Si g/l 0.002 0.024
C g/l 0.000 0.000
Ac g/l 0.000 0.000

OFALSP OFAQLP OCP

CaCO3 1681.793 9.564 1782.642 6.733 0.000 0.000
Ca(OH)2 0.000 0.000 301.562 1.139 31.324 0.321
CaSiO3 345.020 1.962 422.678 1.597 0.000 0.000
MgCO3 203.568 1.158 203.568 0.769 0.000 0.000
Mg(OH)2 0.000 0.000 1094.309 4.133 1219.676 12.491
Al2O3 201.262 1.145 217.896 0.823 0.000 0.000
Fe2O3 176.104 1.001 184.495 0.697 0.000 0.000
SiO2 482.789 2.745 482.789 1.824 42.763 0.438
CaSO4.2H2O 13310.292 75.691 18520.642 69.956 0.000 0.000
Co3(PO4)2.8H2O 0.000 0.000 0.000 0.000 0.125 0.001
AlPO4.2H2O 1166.148 6.631 1207.243 4.560 0.000 0.000
Fe(OH)3 0.045 0.000 916.611 3.462 137.571 1.409
FeFe4(SO4)6(OH)2.20H2O 0.001 0.000 0.000 0.000 0.000 0.000
(Al)(2/3)Fe4(SO4)6(OH)2.20H2O 18.084 0.103 0.000 0.000 0.000 0.000
Al4(OH)(11.36).(SO4)(0.32).5H2O 0.000 0.000 1283.649 4.849 0.000 0.000
Cu(OH)2 0.000 0.000 0.048 0.000 2.032 0.021
ZnCo3(OH)6(SO4).3H2O 0.000 0.000 0.000 0.000 657.179 6.730
Zn(OH)2 0.000 0.000 0.002 0.000 0.021 0.000
Co5(OH)6(SO4)2.3H2O 0.000 0.000 0.000 0.000 5865.592 60.072
Co(OH)2 0.000 0.000 0.001 0.000 359.188 3.679
Ni4(OH)6SO4 0.000 0.000 0.000 0.000 10.140 0.104
Ni(OH)2 0.000 0.000 0.000 0.000 227.569 2.331
Mn(OH)2 0.000 0.000 0.000 0.000 22.894 0.234
Mg(OH)2 0.000 0.000 0.000 0.000 11.810 0.121
CuFe2O4.2H2O 0.000 0.000 933.918 3.528 0.000 0.000
CoAl2O4.2H2O 0.000 0.000 0.000 0.000 14.635 0.150
MnCO3 0.000 0.000 0.000 0.000 0.241 0.002
CoOOH 0.000 0.000 0.000 0.000 939.590 9.623
MnOOH 0.000 0.000 0.000 0.000 221.982 2.273
Total 17585.105 26474.688 9764.334

OMGD OEN
Mass (kg/hrs) % Mass (kg/hrs) %
CaCO3 (unreated) 0.000 0.000 2154.010 5.470
Ca(OH)2 12.214 0.147 1432.680 3.639
CaSiO3 0.000 0.000 588.237 1.494
MgCO3 0.000 0.000 203.568 0.517
Mg(OH)2 (unreacted) 475.596 5.730 80.497 0.204
Al2O3 0.000 0.000 253.360 0.643
Fe2O3 0.000 0.000 202.383 0.514
SiO2 42.763 0.515 482.789 1.226
CaSO4.2H2O 121.311 1.462 27850.829 70.731
Co3(PO4)2.8H2O 0.125 0.002 0.000 0.000
MnHPO4.3H2O 0.000 0.000 1551.807 3.941
Fe(OH)3 137.571 1.658 916.961 2.329
Al4(OH)(11.36).(SO4)(0.32).5H2O 0.000 0.000 625.550 1.589
Co2Cu3(OH)6(SO4)2.5H2O 0.104 0.001 0.000 0.000
Cu(OH)2 1.987 0.024 0.067 0.000
ZnCo3(OH)6(SO4).3H2O 656.083 7.905 0.000 0.000
Zn(OH)2 0.070 0.001 0.000 0.000
Co5(OH)6(SO4)2.3H2O 5569.476 67.106 0.000 0.000
Co(OH)2 14.291 0.172 0.000 0.000
Ni4(OH)6SO4 35.930 0.433 0.000 0.000
Ni(OH)2 37.214 0.448 0.010 0.000
Mn(OH)2 0.029 0.000 3.719 0.009
Mg(OH)2 (precipitated) 0.027 0.000 140.541 0.357
CuFe2O4.2H2O 0.000 0.000 933.877 2.372
CoAl2O4.2H2O 14.635 0.176 464.695 1.180
ZnAl2O4.2H2O 0.000 0.000 1032.261 2.622
NiAl2O4.2H2O 0.000 0.000 29.181 0.074
CoCO3 0.110 0.001 0.000 0.000
MnCO3 0.000 0.000 114.549 0.291
CaCO3 (precipitated) 0.000 0.000 310.048 0.787
CoOOH 958.035 11.543 0.000 0.000
MnOOH 221.987 2.675 3.910 0.010
Total 8299.559 39375.529

Inlet
WBB FAPLS FAPQL CPMG ZSXS/MGDAc
Cu 100.000 0.000 0.000 0.000 0.000
Co 100.000 0.000 0.000 0.000 0.000
Zn 100.000 0.000 0.000 0.000 0.000
Ni 100.000 0.000 0.000 0.000 0.000
Mn 100.000 0.000 0.000 0.000 0.000
Mg 25.598 10.860 1.873 61.669 0.000
Al 82.478 16.185 1.338 0.000 0.000
Ca 7.440 66.279 25.220 1.060 0.000
S 81.940 0.000 0.000 0.000 18.060
P 100.000 0.000 0.000 0.000 0.000
Si 4.391 84.954 5.161 5.494 0.000
C 0.002 96.770 3.229 0.000 0.000
Fe 84.047 15.227 0.726 0.000 0.000
Table 12.9: Distribution of elements in oulet (%)
Outlet
FAPFLCa CO2 ZSXSTS MGDFLCa CPTKOf
Cu 99.389 0.000 0.001 0.610 0.000
Co 0.104 0.000 0.529 96.377 2.990
Zn 0.095 0.000 77.895 22.010 0.000
Ni 0.282 0.000 0.349 84.864 14.505
Mn 0.102 0.000 1.049 22.463 76.386
Mg 2.179 0.000 0.083 6.753 90.985
Al 98.742 0.000 0.695 0.564 0.000
Ca 88.850 0.000 0.012 0.589 10.548
S 28.261 0.000 12.511 5.257 53.972
P 99.994 0.000 0.000 0.006 0.000
Si 89.532 0.000 0.006 5.465 4.996
C 17.823 82.176 0.000 0.001 0.000
Fe 95.141 0.000 0.006 4.853 0.000

Table 12.10: Cobalt production and recovery

Table 12.11: Reaction extent and Reagent consumption
Reaction extent (%)

FAP limestone 82.500 3.501 T/tCo
FAP Quick lime 87.790 0.857 T/tCo
FAP stechiometria Oxygen 25.395 kg/tCo
ZSXS Acid 1.508 T/tCo
CP MgO 73.306 0.961 T/tCo
MGD Acid 0.592 T/tCo
Table 12.12: Cyanex 272 v/v% and consumption of Extractant and diluent
V/V% Cyanex 272 14.220 %

Cyanex 272 consumption 0.706 kg/tCo
Diluent consumption 3.793 kg/tCo
pH of raffinate 2.269
Table 12.13: Reagent costs and cobalt hydroxide transport cost

Limestone 3.501 t/tCo 70.00 245.08
Quick lime 2.685 t/tCo 150.00 402.79
Acid 2.100 t/tCo 120.00 252.03
MgO 0.961 t/tCo 700.00 672.94
flocclants 0.424 kg/tCo 3900.00 1.65
Cyanex 272 0.706 kg/tCo 41990.00 29.63
Diluent 3.793 kg/tCo 1590.00 6.03
Transport Cobalt DRC-SA 6.064 t/tCo 240.00 1455.31
Total 3065.46

The cobalt grade is 41.144% and it reaches the target of 40%.
 Cu grade decreases from 1.404% to 0.016% and 0.61% of Cu is in cobalt

hydroxide cake as Cu(OH)2.
 Zn grade decreases from 3.399% to 1.046% and 22.01% of Zn is in cobalt
hydroxide cake as ZnCo3(OH)6(SO4),3H2O.
 Fe grade decreases from 5.565% to 0.473% and 4.853% of Fe is in cobalt
hydroxide cake as Fe(OH)3.
 Mg grade decreases from 4.962% to 2.389% and Mg is in cobalt
hydroxide cake as unreacted Mg(OH)2.
 C grade decreases from 0.123% to 0.0% in the Cake.
The next step is to increase the reaction extent of MgO and Cobalt recovery.by
using the following precedure:
 Cobalt precipitation step is done in two stages. The frist stage uses MgO
as neutralization agent and it is done at pH 7.7 where MgO reaction
extent is high than 80%. After decantation, the overflow is sent to second
stage of Cobalt precipitation.
 The second stage use quick lime as neutralization agent and it is done at
pH pH 8.5 to decrease the cobalt loss in the overflow. After decantation,
the underflow is sent to cobalt and manganese dissolution step.

13. Mass balance of Cobalt circuit –C
13.1. Configuration

Figure (13.1) gives the flow diagram of Cobalt circuit (C). The purpose of the
flow diagram is to increase the reaction extent of MgO and to decrease the cobalt loss in
the cobalt precipitation thickener overflow.
 FALSP: Fe and Al precipitation with limestone.

 FAQLP: Fe and Al precipitation with quick lime.
 ZSXE: Zinc solvent extraction-Extraction step.
 ZSXS: Zinc solvent extraction – Stripping step
 CP1: Co precipitation stage 1.
 CP1TK: Thickener of Co precipitation stage 1.
 MGD: Magnesium dissolution.
 MGDFL: Filtration of Mg dissolution.
 CP2: Co precipitation stage 2.
 CP2TK: Thickener of Co precipitation stage 2.
 CMD: Cobalt and Manganese dissolution.
 EN: Effluent neutralization.
 WBB: Water balance bleed.

 OCMD: Out of cobalt and Manganese dissolution.
 FAPLS: Limestone.
 FALSPCO2: CO2 releases from Fe and Al precipitation using limestone.
 OFALSP: Outlet of Fe and Al precipitation using limestone.
 FAPQL: Quick lime.
 FAQLPO2: Oxygen from Air

Figure 13.1. : Flow diagram of cobalt circuit - C
 FAQLPCO2: CO2 releases from Fe and Al precipitation using quick lime.

 OFQLAP: Outlet of Fe and Al precipitation using quick lime.
 FAPTKUF: Underflow of thickener of Fe and Al precipitation.
 FAPFLF: Filtrate of filter of Fe and Al precipitation.
 FAPFLW: Wash water of filter of Fe and Al precipitation.
 FAPFLCa: Cake of filter of Fe and Al precipitation.
 ZSXER: Zinc solvent extraction – raffinate.
 ZSXLO: Zinc solvent extraction – loaded organic.

 ZSXALO: Zinc solvent extraction – aqueous entrainment in LO.
 ZSXSO: Zinc solvent extraction – stripped organic.
 ZSXASO: Zinc solvent extraction – aqueous entrainment in SO.
 ZSXAS: Zinc solvent extraction – acid solution.
 ZSXSR: Zinc solvent extraction – recycled stripping solution.
 ZSXSTS: Zinc solvent extraction – stripping solution.
 CP1MG: MgO of cobalt precipitation stage 1.
 CP1AO2: Oxygen from Air absorbed by solid – stage 1.
 OCP1: Outlet of cobalt precipitation stage 1.
 CP1TKFc: Flocculants of thickener of cobalt precipitation stage 1.
 CP1TKOF: Overflow of thickener of cobalt precipitation stage 1.
 CP1TKUF: Underflow of thickener of cobalt precipitation stage 1.
 MGDAc: Acid for magnesium dissolution.
 OMGD: outlet of magnesium dissolution.
 MGDFLF: Filtrate of filter of magnesium dissolution
 MGDFLW: Wash water of filter of magnesium dissolution.
 MGDFLCa: Cake of filter of magnesium dissolution.
 CP2AO2: Oxygen from Air absorbed by solid – stage 2.
 CP2QL: Quick lime of cobalt precipitation stage 2.
 OCP2: Outlet of cobalt precipitation stage 2.
 CP2TKFc: Flocculants of thickener of cobalt precipitation stage 2.
 CP2TKOF: Overflow of thickener of cobalt precipitation stage 2.
 CP2TKUF: Underflow of thickener of cobalt precipitation stage 2.
 ENQL: Quick lime used to Effluent neutralization.
 ENAO2: Oxygen from Air absorbed by solid – EN.

Water balance bleed is fed to Cobalt and Manganese dissolution tank. The out let
is fed to Fe and Al precipitation tank with limestone using as neutralization agent at pH
3. The outlet is fed to Fe and Al precipitation tank with quick lime using as neutralization
agent at pH 5.0. Air is injected to oxidize ferrous into ferric and to remove carbonate.
Pulp after precipitation is fed in the tickener and underflow of thickener is fed to the
filter. Filtrate is fed to the thickener and overflow of thickener is fed to surge tank.
Overflow of Fe and Al precipitation thickener is fed to Zin solvent extraction

using Cyanex 272 as extractant. The load organic is stripped with acid solution. The
raffinate of Zinc solvent extraction is fed to Co precipitation stage 1 tank with MgO using
as netralization agent at pH 7.7. Pulp after precipitation is fed in the thickener and
underflow of thickener is fed to Magensium dissolution step at pH 7. Outlet of

Magnesium dissolution step is fed to the filter. Overflow of Co precipitation stage 1
thickener and filtrate from Magnesium dissolution filter are fed to cobalt precipitation
stage 2 tank using quick lime as neutralisation agent at pH 8.5. Outlet to cobalt
precipitation stage 2 is fed to the thickener. Underflow of the thickener is fed to Co and
Mn dissolution tank. Cobalt precipitation stage 2 thickener overflow, the stripping
solution and Fe and Al filter cake are fed to effluent neutralization step where quick lime
is used as neutralization agent at pH 9.0.
13.2. Mass balance
13.2.1.1.Fe and Al precipitation using limestone
Design criteria: chapter 12.2.1.1.
13.2.1.2.Fe and Al precipitation using quick lime
13.2.1.3.Thickener
13.2.1.5.Zinc solvent extraction – Extraction train
Design criteria of ZnSX - extraction circuit: chapter 12.2.1.5.
13.2.1.6.Zinc solvent extraction – Stripping train
Design criteria of ZnSX - stripping circuit: chapter 12.2.1.6.
13.2.1.7.Co precipitation stage 1
 Precipitation pH: 7.7 to have MgO reaction extent greater than 80%.

 MgO : chapter 11.2.1.4.
11.2.1.1.
 Oxidation of Ferrous into ferric. Chapter 11.2.1.1.
13.2.1.8.Thickener of cobalt precipitation stage 1
Design criteria: Chapter 11.2.1.5.
13.2.1.9. Magnesium dissolution
13.2.1.10. Press filter
13.2.1.11. Co precipitation stage 2
 Precipitation pH: 8.5.

 Quick lime: Chapter 12.2.1.2.
11.2.1.1.
 Oxidation of Ferrous into ferric. Chapter 11.2.1.1.
13.2.1.12. Thickener of cobalt precipitation stage 2
13.2.1.13. Cobalt and Manganese dissolution
 Dissolution pH: less than 2.

 MnOOH reacts with acid according to the chemical reaction (9.r).
 CoOOH and MnO2 react with ferrous according to chemical reactions

(13.b) and (13.c).
CoOOH+Fe+2+3H + =Co+2+Fe+3+2H2 O (13.b)
MnO2 +2Fe+2+4H + =Mn+2+2Fe+3+2H2 O (13.c)
 The oxidation of ferrous into ferric increases the Eh of solution. If the

value of Eh is high to make that the saturation concentration of dithionate
(Equation 9.17) becomes less than the concentration of dithionate in
solution, the excess of dithionate reacts with CoOOH and MnO2 according
to the chemical reaction (13.d) and (13.e) in competition with reactions
(13.b) and (13.c).
C(S2 O−2
6 )
=151.973-183.004*Eh-7.130*pH (9.17)
S2 O−2 + −2 +2
6 +2CoOOH+2H =2SO4 +2Co +2H2 O (13.d)
S2 O−2 −2
6 +MnO2 =2SO4 +Mn
+2
(13.e)
 Dissolution of unreacted Ca(OH)2 and Mg(OH)2 from inlet solid to reach

the unreacted Ca(OH)2 and Mg(OH)2 of the reaction extent of quick lime
at pH of Co and Mn dissolution.
 Dissolution of CaSiO3, Al2O3 and Fe2O3 from inlet solid: 0.%.
 Dissolution of other minerals: 100%.

 Oxidation of adsorbed Co on surface of MnO2 into CoOOH. In the case it
remains MnO2 is the solid there is not enough ferrous in solution. Chapter
11.2.1.4.
13.2.1.14. Effluent neutralization

production circuit (C) obtained by using the realistic simulation model. Tables (13.7),
(13.8) and (13.9) give the mineralogical composition of solid. Tables (13.10) and
(13.11) give the distribution of elements in the inlet and the outlet of cobalt circuit.

Table 13.1: Mass balance of cobalt hydroxide precipitation circuit - C
1 2 3 4 5 6 7 8
WBB OCMD FAPLS FALSPCO2 OFALSP FAPQL FAQLPO2 FAQLPCO2
Solid/gas
mass t/h 3.948 8.149 2.387 19.539 3.051 0.0079 0.542
volume m3/h
SG solid t/m3
Cu % 0.000 0.000
Co % 0.000 0.000
Zn % 0.000 0.000
Ni % 0.000 0.000
Mn % 0.000 0.000
Mg % 0.042 2.800 0.213 1.972
Al % 0.164 0.889 1.658 0.300
Fe(II) % 0.000 0.000
Fe(III) % 0.109 1.028 3.307 0.200
Ca % 23.969 33.118 18.674 51.458
S % 17.797 14.903
P % 0.000 1.177
Si % 0.349 2.580 1.147 0.640
C % 0.078 11.010 0.819 1.500
Pulp
mass t/h 740.730 40.744 779.088 15.256
volume m3/h
SG solid t/m3
%solid 0.533 20.00 2.508 20.000
Liquid
mass t/h 698.391 736.783 32.595 759.549 12.205
volume m3/h 664.181 699.665 32.595 727.714 12.205
SG liquid t/m3 1.052 1.053 1.000 1.044 1.000
S2O6 g/l 15.702 15.391 14.798
Cu g/l 0.327 0.310 0.298
Co g/l 5.346 6.240 5.999
Zn g/l 0.594 0.564 0.542
Ni g/l 0.080 0.307 0.295
Mn g/l 0.936 1.615 1.553
Mg g/l 1.190 1.307 1.515
Al g/l 0.817 0.776 0.409
Fe(II) g/l 0.973 0.132 0.127
Fe(III) g/l 0.051 0.840 0.041
Ca g/l 0.671 0.758 0.724
S g/l 15.161 14.781 11.175
P g/l 0.356 0.338 0.009
Si g/l 0.024 0.024 0.024
C g/l 0.000 0.042 0.158
Ac g/l 11.106 5.682 0.146

9 10 11 12 13 14 15 16
OFAQLP FAPTKFc FAPFLF FAPTKOF FAPTKUF FAPFLW FAPFLCa ZSXASO
Solid/gas
mass t/h 25.852 0.0010 25.776 25.776
volume m3/h 0.0004
SG solid t/m3 2.650
Cu % 0.834 0.837 0.837
Co % 0.000 0.000 0.000
Zn % 0.000 0.000 0.000
Ni % 0.000 0.000 0.000
Mn % 0.000 0.000 0.000
Mg % 0.183 0.183 0.183
Al % 2.409 2.416 2.416
Fe(II) % 0.000 0.000 0.000
Fe(III) % 2.851 2.859 2.859
Ca % 20.017 20.076 20.076
S % 13.633 13.617 13.617
P % 0.916 0.918 0.918
Si % 0.942 0.945 0.945
C % 0.668 0.670 0.670
Pulp
mass t/h 793.809 0.414 64.440 42.960
volume m3/h
SG solid t/m3
%solid 3.257 0.250 40.000 60.000
Liquid
mass t/h 767.957 0.413 60.144 789.850 38.664 38.664 17.184 0.954
volume m3/h 741.009 0.413 58.837 762.849 37.342 38.664 17.157 0.842
SG liquid t/m3 1.036 1.000 1.022 1.035 1.035 1.000 1.002 1.133
S2O6 g/l 14.532 8.771 14.102 14.102 0.614 0.400
Cu g/l 0.002 0.001 0.002 0.002 0.000 0.000
Co g/l 5.892 3.556 5.718 5.718 0.249 0.677
Zn g/l 0.532 0.321 0.517 0.517 0.022 9.733
Ni g/l 0.290 0.175 0.281 0.281 0.012 0.008
Mn g/l 1.525 0.921 1.480 1.480 0.064 0.356
Mg g/l 1.559 0.941 1.513 1.513 0.066 0.058
Al g/l 0.011 0.007 0.011 0.011 0.000 0.139
Fe(II) g/l 0.050 0.030 0.049 0.049 0.002 0.001
Fe(III) g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ca g/l 0.770 0.480 0.771 0.771 0.034 0.022
S g/l 10.148 6.137 9.867 9.867 0.429 45.923
P g/l 0.000 0.000 0.000 0.000 0.000 0.000
Si g/l 0.024 0.015 0.024 0.024 0.001 0.001
C g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.001 0.001 0.001 0.001 0.000 119.107

17 18 19 20 21 22 23 24
ZSXER ZSXSO ZSXLO ZSXALO ZSXAS ZSXSTR ZSXSTS CP1MG
Solid/gas
mass t/h 2.596
volume m3/h
SG solid t/m3
Cu %
Co %
Zn %
Ni %
Mn %
Mg % 57.897
Al % 0.000
Fe(II) %
Fe(III) % 0.000
Ca % 1.930
S %
P %
Si % 0.608
C %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 789.850 0.954 35.801 827.348 35.801
volume m3/h 763.075 953.56 953.562 0.921 31.785 730.151 31.595
SG liquid t/m3 1.035 1.035 1.126 1.133 1.133
S2O6 g/l 14.081 14.081 0.000 0.400 0.400
Cu g/l 0.002 0.0000 0.0000 0.002 0.000 0.000 0.000
Co g/l 5.688 0.0000 0.0175 5.688 0.000 0.677 0.677
Zn g/l 0.114 0.0079 0.3389 0.114 0.000 9.733 9.733
Ni g/l 0.281 0.281 0.000 0.008 0.008
Mn g/l 1.465 0.0000 0.0107 1.465 0.000 0.356 0.356
Mg g/l 1.510 0.0000 0.0005 1.510 0.000 0.058 0.058
Al g/l 0.005 0.0008 0.0056 0.005 0.000 0.139 0.139
Fe(II) g/l 0.048 0.048 0.000 0.001 0.001
Fe(III) g/l 0.000 0.0000 0.0000 0.000 0.000 0.000 0.000
Ca g/l 0.770 0.770 0.000 0.022 0.022
S g/l 9.902 9.902 46.576 45.923 45.923
P g/l 0.000 0.000 0.000 0.000 0.000
Si g/l 0.024 0.024 0.000 0.001 0.001
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.812 0.812 150.000 119.107 119.107

25 26 27 28 29 30 31 32
CP1AO2 OCP1 CP1TKFc CP1TKOF CP1TKUF MGDAc OMGD MGDFLW
Solid/gas
mass t/h 0.0296 9.244 0.0004 9.245 8.298
volume m3/h 0.0001
SG solid t/m3 2.650
Cu % 0.014 0.014 0.015
Co % 40.446 40.445 41.773
Zn % 0.937 0.937 1.044
Ni % 1.311 1.311 0.523
Mn % 0.096 0.096 0.085
Mg % 3.121 3.121 1.886
Al % 0.040 0.040 0.044
Fe(II) % 0.000 0.000 0.000
Fe(III) % 0.400 0.400 0.446
Ca % 0.104 0.104 0.276
S % 8.164 8.164 8.650
P % 0.000 0.000 0.000
Si % 0.171 0.171 0.190
C % 0.000 0.000 0.000
Pulp
mass t/h 792.476 0.148 61.632 62.626
volume m3/h
SG solid t/m3
%solid 1.167 0.250 15.000 13.250
Liquid
mass t/h 783.231 0.148 730.992 52.387 0.994 54.328 24.893
volume m3/h 761.138 0.148 710.376 50.910 0.552 51.438 24.893
SG liquid t/m3 1.029 1.000 1.029 1.029 1.800 1.056 1.000
S2O6 g/l 14.117 14.115 14.115 13.969
Cu g/l 0.000 0.000 0.000 0.000
Co g/l 0.790 0.790 0.790 6.085
Zn g/l 0.000 0.000 0.000 0.001
Ni g/l 0.122 0.122 0.122 1.633
Mn g/l 1.457 1.457 1.457 1.478
Mg g/l 3.110 3.109 3.109 5.644
Al g/l 0.000 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000
Ca g/l 0.825 0.825 0.825 0.558
S g/l 8.936 8.934 8.934 576.729 15.754
P g/l 0.000 0.000 0.000 0.000
Si g/l 0.024 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000
Ac g/l 0.000 0.000 0.000 1764.000 0.000

33 34 35 36 37 38 39 40
MGDFLF MGDFLCa CP2QL CP2O2 OCP2 CP2TKFc CP2TKOF CP2TKUF
Solid/gas
mass t/h 8.298 2.151 0.094 6.351 0.0003 6.351
volume m3/h 0.0001
SG solid t/m3 2.650
Cu % 0.015 0.000 0.000
Co % 41.773 12.802 12.802
Zn % 1.044 0.001 0.001
Ni % 0.523 2.536 2.536
Mn % 0.085 7.563 7.563
Mg % 1.886 1.972 0.195 0.195
Al % 0.044 0.300 0.102 0.102
Fe(II) % 0.000 0.000 0.000
Fe(III) % 0.446 0.200 0.068 0.068
Ca % 0.276 51.458 15.733 15.732
S % 8.650 10.780 10.780
P % 0.000 0.000 0.000
Si % 0.190 0.640 0.217 0.217
C % 0.000 1.500 0.508 0.508
Pulp
mass t/h 20.744 10.757 808.617 0.102 42.340
volume m3/h
SG solid t/m3
%solid 40.000 20.000 0.785 0.250 15.000
Liquid
mass t/h 66.775 12.447 8.606 802.267 0.101 766.380 35.989
volume m3/h 63.919 12.387 8.606 781.938 0.101 746.962 35.077
SG liquid t/m3 1.045 1.005 1.000 1.026 1.000 1.026 1.026
S2O6 g/l 11.017 1.160 13.723 13.722 13.722
Cu g/l 0.000 0.000 0.000 0.000 0.000
Co g/l 4.799 0.505 0.070 0.070 0.070
Zn g/l 0.001 0.000 0.000 0.000 0.000
Ni g/l 1.288 0.136 0.010 0.010 0.010
Mn g/l 1.166 0.123 0.804 0.804 0.804
Mg g/l 4.451 0.469 3.227 3.227 3.227
Al g/l 0.000 0.000 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000 0.000
Ca g/l 0.440 0.046 0.924 0.923 0.923
S g/l 12.424 1.308 8.257 8.256 8.256
P g/l 0.000 0.000 0.000 0.000 0.000
Si g/l 0.019 0.002 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.000 0.000 0.000 0.000 0.000

41 42 43 44 45 46 47 48
ENQL ENAO2 OEN
Solid/gas
mass t/h 5.854 0.001 38.350
volume m3/h
SG solid t/m3
Cu % 0.562
Co % 0.203
Zn % 0.803
Ni % 0.021
Mn % 1.580
Mg % 1.972 0.335
Al % 0.300 1.681
Fe(II) % 0.000
Fe(III) % 0.200 1.953
Ca % 51.458 21.027
S % 13.547
P % 0.613
Si % 0.640 0.733
C % 1.500 0.679
Pulp
mass t/h 29.270 874.411
volume m3/h
SG solid t/m3
%solid 20.000 4.386
Liquid
mass t/h 23.416 836.060
volume m3/h 23.416 817.711
SG liquid t/m3 1.000 1.022
S2O6 g/l 12.563
Cu g/l 0.000
Co g/l 0.000
Zn g/l 0.000
Ni g/l 0.000
Mn g/l 0.009
Mg g/l 2.993
Al g/l 0.000
Fe(II) g/l 0.000
Fe(III) g/l 0.000
Ca g/l 0.996
S g/l 7.263
P g/l 0.002
Si g/l 0.024
C g/l 0.000
Ac g/l 0.000

OCMD OFALSP OFAQLP

CaCO3 25.688 0.651 1169.654 5.986 1274.543 4.930
Ca(OH)2 70.442 1.784 70.442 0.361 313.641 1.213
CaSiO3 56.948 1.443 291.633 1.493 372.401 1.441
MgCO3 0.000 0.000 138.468 0.709 138.468 0.536
Mg(OH)2 3.958 0.100 3.958 0.020 17.622 0.068
Al2O3 12.199 0.309 149.098 0.763 166.399 0.644
Fe2O3 6.153 0.156 125.940 0.645 134.667 0.521
SiO2 0.000 0.000 328.396 1.681 328.396 1.270
CaSO4.2H2O 3772.339 95.557 13065.433 66.869 18755.622 72.550
AlPO4.2H2O 0.000 0.000 1172.899 6.003 1207.250 4.670
Fe(OH)3 0.000 0.000 7.936 0.041 924.265 3.575
FeFe4(SO4)6(OH)2.20H2O 0.000 0.000 0.015 0.000 0.000 0.000
(Al)(2/3)Fe4(SO4)6(OH)2.20H2O 0.000 0.000 3014.885 15.430 0.000 0.000
Al4(OH)(11.36).(SO4)(0.32).5H2O 0.000 0.000 0.000 0.000 1284.526 4.969
Cu(OH)2 0.000 0.000 0.000 0.000 0.048 0.000
Co(OH)2 0.000 0.000 0.000 0.000 0.001 0.000
Ni(OH)2 0.000 0.000 0.000 0.000 0.001 0.000
CuFe2O4.2H2O 0.000 0.000 0.000 0.000 934.175 3.614
Total 3947.726 19538.758 25852.026

OCP1 OMGD OCP2

CaCO3 0.000 0.000 0.000 0.000 121.040 1.906
Ca(OH)2 17.761 0.192 9.640 0.116 368.154 5.797
CaSiO3 0.000 0.000 0.000 0.000 56.948 0.897
Mg(OH)2(unreacted) 691.571 7.481 375.357 4.524 20.685 0.326
Al2O3 0.000 0.000 0.000 0.000 12.199 0.192
Fe2O3 0.000 0.000 0.000 0.000 6.153 0.097
SiO2 33.750 0.365 33.750 0.407 0.000 0.000
CaSO4.2H2O 0.000 0.000 75.923 0.915 3143.733 49.502
Co3(PO4)2.8H2O 0.113 0.001 0.113 0.001 0.000 0.000
Fe(OH)3 129.564 1.402 129.564 1.561 0.000 0.000
Co2Cu3(OH)6(SO4)2.5H2O 0.000 0.000 0.051 0.001 0.000 0.000
Cu(OH)2 1.941 0.021 1.919 0.023 0.001 0.000
ZnCo3(OH)6(SO4).3H2O 655.073 7.086 654.380 7.886 0.591 0.009
Zn(OH)2 0.031 0.000 0.064 0.001 0.000 0.000
Co5(OH)6(SO4)2.3H2O 7106.090 76.869 6604.936 79.599 948.369 14.933
Co(OH)2 113.364 1.226 18.479 0.223 157.843 2.485
Ni4(OH)6SO4 45.237 0.489 30.428 0.367 60.457 0.952
Ni(OH)2 152.708 1.652 42.516 0.512 202.575 3.190
Mn(OH)2 2.979 0.032 0.065 0.001 25.783 0.406
Mg(OH)2 (precipiated) 0.554 0.006 0.022 0.000 9.022 0.142
CoAl2O4.2H2O 14.453 0.156 14.453 0.174 0.000 0.000
MnCO3 0.175 0.002 0.000 0.000 170.038 2.677
CoOOH 267.879 2.898 294.810 3.553 433.777 6.830
MnOOH 11.162 0.121 11.183 0.135 613.305 9.657
Total 9244.404 8297.718 6350.674

OEN
Mass (kg/hrs) %
CaCO3 (unreated) 1622.134 4.230
Ca(OH)2 1372.338 3.578
CaSiO3 527.361 1.375
MgCO3 138.468 0.361
Mg(OH)2 77.106 0.201
Al2O3 199.592 0.520
Fe2O3 151.410 0.395
SiO2 328.396 0.856
CaSO4.2H2O 27791.176 72.466
MnHPO4.3H2O 1554.658 4.054
Fe(OH)3 924.636 2.411
Al4(OH)(11.36).(SO4)(0.32).5H2O 806.118 2.102
Cu(OH)2 0.075 0.000
Ni(OH)2 0.009 0.000
Mn(OH)2 4.617 0.012
Mg(OH)2 135.601 0.354
CuFe2O4.2H2O 934.111 2.436
CoAl2O4.2H2O 281.560 0.734
ZnAl2O4.2H2O 1033.033 2.694
NiAl2O4.2H2O 29.506 0.077
MnCO3 382.159 0.996
CaCO3 (precipitated) 50.854 0.133
MnOOH 5.762 0.015
Total 38350.679

Inlet
WBB FAPLS FAP/CP2QL CP1MG ZSXS/MGDAc
Cu 100.000 0.000 0.000 0.000 0.000
Co 100.000 0.000 0.000 0.000 0.000
Zn 100.000 0.000 0.000 0.000 0.000
Ni 100.000 0.000 0.000 0.000 0.000
Mn 100.000 0.000 0.000 0.000 0.000
Mg 30.124 8.693 3.909 57.275 0.000
Al 86.041 11.484 2.475 0.000 0.000
Ca 7.585 45.963 45.598 0.853 0.000
S 84.843 0.000 0.000 0.000 15.157
P 100.000 0.000 0.000 0.000 0.000
Si 5.804 76.371 12.095 5.731 0.000
C 0.002 91.995 8.003 0.000 0.000
Fe 87.831 10.824 1.345 0.000 0.000
Table 13.11: Distribution of elements in oulet (%)
Outlet
FAPFLCa CO2 ZSXSTS MGDFLCa CPTKOf
Cu 99.417 0.000 0.001 0.583 0.000
Co 0.120 0.000 0.602 97.805 1.473
Zn 0.098 0.000 77.950 21.951 0.000
Ni 0.395 0.000 0.473 84.697 14.435
Mn 0.178 0.000 1.808 1.375 96.639
Mg 1.845 0.000 0.070 6.187 91.898
Al 98.723 0.000 0.696 0.581 0.000
Ca 87.878 0.000 0.012 0.398 11.712
S 29.635 0.000 12.225 6.184 51.956
P 99.994 0.000 0.000 0.006 0.000
Si 87.759 0.000 0.008 5.693 6.540
C 17.762 82.237 0.000 0.001 0.000
Fe 95.218 0.000 0.006 4.776 0.000


Reaction extent (%)

FAP limestone 82.500 2.347 T/tCo
FAP Quick lime 87.790 0.879 T/tCo
FAP stechiometria oxygen 2.274 kg/tCo
CP1 MgO 80.822 0.748 T/tCo
CP2 Quick lime 79.673 0.620 T/tCo
EN Quick lime 78.518 1.686 T/tCo
V/V% Cyanex 272 14.761 %

Cyanex 272 consumtion 0.684 kg/tCo
Dilluent consumption 3.522 kg/tCo
pH of raffinate 2.252

Limestone 2.347 t/tCo 70.00 164.27
Quick lime 3.184 t/tCo 150.00 477.63
Acid 1.687 t/tCo 120.00 202.48
MgO 0.748 t/tCo 700.00 523.35
Cyanex 272 0.684 kg/tCo 41990.00 28.73
Diluent 3.522 kg/tCo 1590.00 5.60
Total 2837.67

The two stages of cobalt precipitation:
 Mg grade decreases from 2.389% to 1.886%.

 Mn grade decreases from 1.671% to 0.085%.
The cobalt recovery increases because the pH of second stage of cobalt

precipitation increases from 8.3 to 8.5 and Cobalt loss in the overflow of the thickener of
second cobalt precipitation decreases from 2.99% to 1.47%.
From Table (10.1) it has been observed that the Copper loss in water balance
bleed is 1.93% of copper soluble in the feed. The next flow diagram recoves copper from
cobalt circuit. Mn is removed from the circuit by using disproportional reaction of
MnOOH at low pH and the dissolution of CoOOH by Mn(+2). The presence of the second
way of Mn removal in cobalt circuit decreases the pH of the cobalt precipitation stage 2
from 8.5 to 8.6.
Spillage tretment step is introduce to control the flow rate of PLS in copper
solvent extraction and the flow rate of PLS in zinc solvent extraction. Metal valuables are
precipitated using quick lime at pH 8.6. Spillage treatment cake contains Co and Mn as
CoOOH and MnOOH. CoOOH and MnOOH are used to oxidize ferrous to ferric in
dissolution step.

14. Mass balance of Copper circuit and
Cobalt circuit - D
14.1. Configuration

Figures (14.1) and (14.2) give the flow diagram of conventional circuit having
Milling in water with pre-leach filter unit operations and cobalt hydroxide production
circuit (D) in which copper is extracted by solvent extraction using an organic bleed
from copper circuit.
 Copper circuit:
o BM: Ball Mill.

o CY: Hydrocyclone.
o PRLTK: Pre-leach thickener.
o PRLFL: Pre-leach filtration.
o LC: Leach circuit.
o PTK: Primary thickener.
o KTn: Thickener of rank “n” in CCD train.
o SX En: Stage of rank “n” in CuSX - extraction train.
o ACT: Aqueous coalescing Tank.
o SX Sn: Stage of rank “n” in CuSX - stripping train.
o EW: .Copper electrowinning.
 Cobalt circuit:
o FALSP: Fe and Al precipitation with limestone.

o FALSPTK: Thickener of Fe and Al precipitation.
o FALSPFL: Filtration of Fe and Al precipitation.
o ZSXE1: Zinc solvent extraction-Extraction step – stage 1.
o ZSXE1: Zinc solvent extraction-Extraction step – stage 2.
o ZSXS1: Zinc solvent extraction – Stripping step –stage 1.

Figure 14.1: Flow diagram of conventional circuit

Figure 14.2. : Flow diagram of cobalt circuit - D
o ZSXS2: Zinc solvent extraction – Stripping step –stage 2.

o BCuSX1: Bleed copper solvent extraction – stage 1.
o BCuSX2: Bleed copper solvent extraction – stage 2.
o FAQLP: Fe and Al precipitation with quick lime.
o FAQLPTK: Thickener of Fe and Al precipitation.
o CP1: Co precipitation stage 1.
o CP1TK: Thickener of Co precipitation stage 1.

o MGD: Magnesium dissolution.
o MGDFL: Filtration of Mg dissolution.
o CP2: Co precipitation stage 2.
o CP2TK: Thickener of Co precipitation stage 2.
o CD: Cobalt dissolution.
o CDFL: Cobalt dissolution filter.
o ST: Spillage treatment.
o STTK: Spillage treatment thickener.
o STFL: Spillage treatment filter.
o EN: Effluent neutralization.
o DS: Dissolution.
 Copper circuit:
o Feed: Ores.
o BMW: Ball Mill water.
o UFCY: Hydrocyclone underflow.
o OBM: Outlet Ball Mill.
o SW: Sump water.
o FeCY: Feed hydrocyclone.
o UFCY: Hydrocyclone underflow.
o OFCY: Hydrocyclone overflow.
o PRLTFC: Pre-leach thickener flocculants.
o PRLTOF: Pre-leach thickener overflow.
o PRLTUF: Pre-leach thickener underflow.
o PRLFFC: Pre-leach filter flocculants.
o PRLFFL: Pre-leach filter filtrate.
o PRLFCa: Pre-leach filter cake.
o LCA: Leach concentrated acid.
o RE2L: Raffinate of stage 2 of CuSX - extraction train to leach.
o WBB: Water balance bleed.
o OLC: Outlet leach circuit.
o PTKFC: Flocculants of primary thickener.
o PTKUF: Underflow of primary thickener.
o PTKOF: Overflow of primary thickener.
o TKFCn: Flocculants of thickener of rank “n” in CCD train.
o TKnUF: Underflow of thickener of rank “n” in CCD train.
o TKnOF: Overflow of thickener of rank “n” in CCD train.
o TK1OFP: Overflow of primary thickener to PLS.
o TK1OFS: Overflow of primary thickener to spillage treatment.
o WW: Wash water of CCD train.

o PLS: Pregnant leach solution.
o REn: Raffinate of stage of rank “n” in CuSX - extraction train.
o LOEn: Loaded organic of stage of rank “n” in CuSX - extraction
train.
o ALOEn: Aqueous entrainment in loaded organic of stage of rank
“n” in CuSX - extraction train.
o LOAC: Loaded organic from aqueous coalescing tank.
o ALOAC: Aqueous entrainment in loaded organic from aqueous
coalescing tank.
o ACTD: Drain of aqueous coalescing tank.
o SO: Stripping organic.
o ASO: Aqueous entrainment in stripping organic.
o SOBL: Stripping organic to bleed copper solvent extraction.
o ASOBL: Aqueous entrainment in SOBL.
o LOBL1: Loaded organic from bleed copper solvent extraction –
stage 1.
o ALOBL1: Aqueous entrainment in LOBL1.
o SOBP: Bypass stripping organic.
o ASOBP: Aqueous entrainment in SOBP.
o ADS: Advance electrolyte.
o RADS: Recirculated advance electrolyte.
o SPE: Spent electrolyte.
o EWO: Oxygen produced in Copper electrowinning circuit.
o EWCC: Copper cathode produced in Copper electrowinning
circuit.
o EWS: Sulfur produced in Copper electrowinning circuit.
o EWW: Water for Copper electrowinning circuit.
o EWCA: Concentrated acid for Copper electrowinning circuit.
o OEW: Outlet of Copper electrowinning circuit.
o EWB: Bleed of Copper electrowinning circuit.
 Cobalt circuit:
o WBB: Water balance bleed.

o DSAc: Acid of dissolution.
o DSCO2: CO2 releases from dissolution.
o ODS: Out of dissolution.
o FAPLS: Limestone.
o FALSPCO2: CO2 releases from Fe and Al precipitation using
limestone.
o OFALSP: Outlet of Fe and Al precipitation using limestone.
o FALSPTKFc: Flocculants of thickener of Fe and Al precipitation
using limestone.

o FALSPTKCO2: CO2 releases from Fe and Al precipitation
thickener using limestone
o FALSPTKOF: Overflow of thickener of Fe and Al precipitation
using limestone.
o FALSPTKUF: Underflow of thickener of Fe and Al precipitation
using limestone.
o FALSPFLF: Filtrate of filter of Fe and Al precipitation using
limestone.
o FALSPFLW: Wash water of filter of Fe and Al precipitation using
limestone.
o FALSPFLCa: Cake of filter of Fe and Al precipitation using
limestone.
o ZSXER1: Zinc solvent extraction – raffinate – stage 1.
o ZSXER2: Zinc solvent extraction – raffinate – stage 2.
o ZSXLO2: Zinc solvent extraction – loaded organic stage 2.
o ZSXALO2: Zinc solvent extraction – aqueous entrainment in LO-
stage 2.
o ZSXLO1: Zinc solvent extraction – loaded organic stage 1.
o ZSXALO1: Zinc solvent extraction – aqueous entrainment in LO-
stage 2.
o ZSXSO1: Zinc solvent extraction – stripped organic stage 1.
o ZSXASO1: Zinc solvent extraction – aqueous entrainment in SO –
stage 1.
o ZSXSO2: Zinc solvent extraction – stripped organic stage 2.
o ZSXASO2: Zinc solvent extraction – aqueous entrainment in SO –
stage 2
o ZSXSTS2: Zinc solvent extraction – stripping solution – stage 2.
o ZSXSTS1: Zinc solvent extraction – stripping solution - stage 1.
o ZSXAS: Zinc solvent extraction – acid solution.
o ZSXSTR1: Zinc solvent extraction – recycled stripping solution –
stage 1.
o ZSXSTR2: Zinc solvent extraction – recycled stripping solution –
stage 2.
o BCuSXR1: Bleed copper solvent extraction raffinate – stage 1.
o BCuSXR2: Bleed copper solvent extraction raffinate – stage 2.
o SOBL: Stripping organic to bleed copper solvent extraction.
o ASOBL: Aqueous entrainment in SOBL.
stage 2.
stage 1.

o FAPQL: Quick lime.
o FAQLPO2: Oxygen from Air injected.
o FAQLPTKCO2: CO2 releases from Fe and Al precipitation
thickener using quick lime
o OFQLAP: Outlet of Fe and Al precipitation using quick lime.
o FAQLPTKFc: Flocculants of thickener of Fe and Al precipitation
using quick lime.
o FAQLPTKOF: Overflow of thickener of Fe and Al precipitation
using quick lime.
o FAQLPTKUF: Underflow of thickener of Fe and Al precipitation
using quick lime.
o CP1MG: MgO of cobalt precipitation - stage 1.
o CP1AO2: Oxygen from Air absorbed by solid – stage 1.
o OCP1: Outlet of cobalt precipitation - stage 1.
o CP1TKFc: Flocculants of thickener of cobalt precipitation - stage 1.
o CP1TKOF: Overflow of thickener of cobalt precipitation - stage 1.
o CP1TKUF: Underflow of thickener of cobalt precipitation - stage 1.
o MGDAc: Acid for magnesium dissolution.
o OMGD: outlet of magnesium dissolution.
o MGDFLF: Filtrate of filter of magnesium dissolution
o MGDFLW: Wash water of filter of magnesium dissolution.
o MGDFLCa: Cake of filter of magnesium dissolution.
o CP2AO2: Oxygen from Air absorbed by solid – stage 2.
o CP2QL: Quick lime of cobalt precipitation - stage 2.
o OCP2: Outlet of cobalt precipitation - stage 2.
o CP2TKFc: Flocculants of thickener of cobalt precipitation - stage 2.
o CP2TKOF: Overflow of thickener of cobalt precipitation - stage 2.
o CP2TKUF: Underflow of thickener of cobalt precipitation - stage 2.
o CDAc: Acid for cobalt dissolution.
o OCD: outlet of cobalt dissolution.
o CDFLF: Filtrate of filter of cobalt dissolution
o CDFLW: Wash water of filter of cobalt dissolution.
o CDFLCa: Cake of filter of cobalt dissolution.
o STQL: Quick lime for spillage treatment.
o STAO2: Oxygen from Air absorbed by solid – stage 1.
o OST: Outlet of spillage treatment.
o STTKFc: Flocculants of thickener of spillage treatment.
o STTKOF: Overflow of thickener of spillage treatment.
o STTKUF: Underflow of thickener of spillage treatment.
o STFLF: Filtrate of filter of spillage treatment.
o STFLCa: Cake of filter of spillage treatment.
o OEN: Out of Effluent neutralization

14.1.2.1.Copper circuit
Feed material from crusher is fed in Ball Mill together with water and
hydrocyclone underflow. Outlet of Ball Mill is discharged in the sump. Water is also
added to the sump to reach the requirement of Feed hydrocyclone pulp density. The
hydrocyclone overflow is fed in the pre-leach thickener and underflow of pre-leach
thickener is fed to pre-leach filter.
The pre-leach filter cake is fed in leach circuit with one part of raffinate from
raffinate pond. Concentrated acid and sulfur dioxide gas are also added in the leach
circuit for pH and redox potential control. Slurry discharged from the leach circuit is
thickened in primary thickener. Underflow of primary thickener is fed to counter
current decantation circuit where leach residue is washed with acidulated water.
Overflow of primary thickener is sent to the PLS Pond. Small part of CCD1OF is sent also
to PLSPond to reach the known flowrate of PLS. The mixture is the PLS. Other part of
CCD1 overflow is sent the spillage treatment.
PLS is fed to the copper solvent extraction circuit. One part of raffinate of
solvent extraction step is sent back to leach and the remaining is sent to cobalt circuit.
The loaded organic from organic CuSX – extraction train is sent to aqueous coalescing
tank to remove a maximum volume of aqueous entrainment solution. Loaded organic
from aqueous coalescing tank is sent to CuSX - stripping train.
Spent electrolyte from copper electrowinning circuit is sent to CuSX - stripping

train. Advance electrolyte from CuSX - stripping train is sent back to Copper
electrowinning circuit. Bleed of stripping organic is sent to bleed copper solvent
extraction in cobalt circuit. Loaded organic from bleed copper solvent extraction is
mixed with the remaining stripping organic called bypass stripping organic. The mixture
is sent to copper solvent extraction – extraction train - stage 2
Concentrated acid and water are also added in Copper electrowinning circuit.
Copper cathode, Oxygen gas and sulfur are produced in Copper electrowinning circuit.
Iron bleed solution from Copper electrowinning circuit is sent back to PLS pond.
14.1.2.2.Cobalt circuit
Water balance bleed is fed to Fe and Al dissolution tank. The out let is fed to Fe
and Al precipitation tank with limestone using as neutralization agent at pH 3. Pulp after
precipitation is fed in the tickener and underflow of thickener is fed to the filter. Filtrate
is fed to the thickener and overflow of thickener is fed to surge tank.

Known flowrate Overflow of Fe and Al precipitation thickener is fed to Zin
solvent extraction using Cyanex 272 as extractant in two stages. The load organic is
stripped with acid solution in two stages and the stripping solution is fed to effluent
neutralization step where quick lime is used as neutralization agent. Excess volume of
overflow of Fe and Al precipitation thickener is sent the spillage treatment.
The raffinate of Zinc solvent extraction is fed to Bleed copper solvent extraction
stage 1. Bleed stripping organic from copper circuit is fed to bleed copper solvent
extraction stage 2. Bleed loaded organic bleed copper solvent extraction stage 1 is sent
to copper circuit and raffinate of bleed copper solvent extraction stage 2 is sent to Fe
and Al precipitation tank using quick lime as neutralization agent at pH 5.1.
Air is injected in Fe and Al precipitation tank using quick lime to oxidize ferrous
into ferric and to remove carbanate gas from solution. Outlet is sent to thickener.
Underflow of the thickener is sent to dissolution step. Overflow is sent to cobalt
precipitation stage 1 tank with MgO using as netralization agent at pH 7.7.
Pulp after Cobalt precipitation is fed in the thickener and underflow of thickener
and acid are fed to Magensium dissolution step at pH 7. Outlet of Magnesium dissolution
step is fed to the filter. Filtrate of magnesium dissolution filter is fed to dissolution step.
Overflow of Co precipitation stage 1 thickener is fed to cobalt precipitation stage 2 tank
using quick lime as neutralisation agent at pH 8.6. There is partial oxidation of cobalt
and manganses into CoOOH and MnOOH. Outlet cobalt precipitation stage 2 is fed to the
thickener. Underflow of cobalt precipitation stage 2 thickener and acid are fed to Co
dissolution tank. There is first disproportional reaction of MnOOH and dissolution of
CoOOH by Mn(+2). The outlet of cobalt dissolution is fed to the filter. Filtrate is fed to
dissolution step. Cake of cobalt dissolution filter is sent to effluent neutralization.
Overflow of cobalt precipiation stage 2 thickener is sent to effluent neutralization tank.
Quick lime is added to spillage treatment for copper and cobalt precipitation at
pH 8.6. There is partial oxidation of cobalt and manganses into CoOOH and MnOOH.
Outlet of spillage treatment is sent to thickener. Overflow of thickener of spillage
treatment is sent the effluent treatment. Underflow of thickener of spillage treatment is
sent to filter. Filtrate is sent to effluent treatment and Cake of filter is sent to dissolution
step where CoOOH and MnOOH will oxidize ferrous to ferric.

14.2. Mass balance
A. Ball Mill (in water)
B. Hydrocyclone
C. Pre-leach thickener
D. Pre-leach filter
E. Leach circuit
F. Primary thickener
G. CCD circuit
H. CuSX – extraction train
Design criteria of CuSX - extraction circuit mass balance are the following:
 PLS flow rate: 2.000 m3/hrs (four trains of 500 m3/hrs).

 Other design criteria: chapter 10.2.1.8.

I. Aqueous coalescing tank
Design criterion: chapter 10.2.1.9.
J. CuSX – stripping train
K. Copper electrowinning
A. Dissolution
 pH of dissolution: less than 2.0.

 Other design criteria as design in chapter 13.2.1.13. (cobalt and
manganese dissolution)
B. Fe and Al precipitation using limestone
C. Thickener
D. Press filter
E. Zinc solvent extraction – Extraction train
Design criteria of ZnSX - extraction circuit mass balance are the following:
 ZnPLS flow rate : 600 m3/hrs ( one train).

 Type of extractant: Cyanex 272.
 O/A advance ratio: 1.25.
 Feed solution pH: pH of overflow of thickener (around 3.0).
 Raffinate pH: depends on the quantity of extracted elements.

 Volume percent of extractant in organic phase: 80% of dissolved zinc in
leach circuit.
F. Zinc solvent extraction – Stripping train
Design criteria of ZnSX - stripping circuit mass balance are the following:
 O/A advance ratio: 30.

 O/A internal ratio: 1.25
 Acid concentration in acid solution: 150g/L.
 Organic entrainment in organic: 100ppm.
G. BCuSX
Design criteria of BCuSX circuit mass balance are the following:
 Type of extractant: Lix984N.

 O/A ratio: 1.25.
 Volume percent of extractant in organic phase: Copper circuit
 Mixing efficiency for Copper: 97% stages 1 and 2.
 Equilibrium copper concentration: Equation (10.6) gives equilibrium
condition of chemical reaction (10.g).
 Equilibrium Fe(III) concentration: Data of Lix984 on extraction train.
Equation (10.7) gives equilibrium condition of chemical reaction (10.h).
 Mixing efficiency for Fe(III) (assuming the same as for Copper): 97%.
H. Fe and Al precipitation using quick lime
 Precipitation pH:5.1.

 Quick lime: chapter 12.2.1.2.
I. Thickener

J. Co precipitation stage 1
K. Thickener of cobalt precipitation stage 1
L. Magnesium dissolution
M. Press filter
N. Co precipitation stage 2
 pH of cobalt precipitation stage 2: 8.6

 Other design criteria as Chapter 13.2.1.12.

O. Thickener of cobalt precipitation stage 2
P. Cobalt dissolution
 Precipitation pH: 1.5.

 MnOOH reacts with acid according to the chemical reaction (9.r).
 CoOOH and Mn+2 react according to chemical reaction (14.a).
Mn+2 +2CoOOH+2H + =R-MnO2 +2Co+2 +2H2 O (9.s)
 Dissolution of unreacted CaCO3, Ca(OH)2 and Mg(OH)2 from inlet solid to

reach the unreacted CaCO3, Ca(OH)2 and Mg(OH)2 of the reaction extent of
limestone and quick lime at pH of Co dissolution.
 Dissolution of CaSiO3, Al2O3 and Fe2O3 from inlet solid: 0.%.
 Dissolution of other minerals: 100%.
Q. Press filter of cobalt dissolution
R. Spillage treatment
Design criteria: Cobalt precipitation stage 2.
S. Thickener of spillage treatment

T. Press filter of spillage treatment
U. Effluent neutralization
Table (14.1) gives the summary of simulation results and Tables (14.2) to
(14.11) give copper cathode production mass balance obtained by using the realistic
simulation model.

Table 14.1: Result summary
Description
Number of thickener in CCD train 7
Water balance bleed flow rate 576.82 m3/hr
TK1OFS flow rate 99.90 m3/hr
Water balance bleed copper concentration 0.356 g/L
Water balance bleed cobalt concentration 5.497 g/L
Water balance bleed acid concentration 11.245 g/L
Lost acid (free acid and acid associated with Copper) – CCD TK7 UF 0.367 Kg/t feed
Lost acid (free acid and acid associated with Copper) – WBB 8.503 Kg/t feed
Lost acid (free acid and acid associated with Copper) – TK1OFS 0.990 Kg/t feed
Acid consumption – Leach circuit 55.867 Kg/t feed
Acid consumption – CuEW circuit 2.402 Kg/t feed
Acid consumption – wash CCD circuit 0.425 Kg/t feed
Total acid consumption 58.693 Kg/t feed
SO2 consumption – Leach circuit 14.455 Kg/t feed
Leach - Percent of SO2 converted to SO4 26.687 %
Leach – Percent of incoming SO4 from SO2 9.737 %
Leach – percent of SO2 converted into S2O6 by Oxygen of Minerals 73.298 %
Leach S2O6 concentration 19.949 g/L
Leach Cobalt 6.789 g/L
Leach Manganese 1.189 g/L
Leach Iron (II) 1.231 g/L
Flocculants consumption 194.801 g/t feed
Extractant percent in organic phase (v/v%) 19.232 %
PLS copper concentration 5.648 g/L
PLS S2O6 concentration 16.183 g/L
Cu/Fe in LOE1 1615
SX Copper stripping recovery 55.954 %
Copper Net transfer 0.237 g/L/(v/v%)
Copper production 13.956 Kg/t feed
Ratio Copper in EWB onto Copper production 1.936 %
Lost copper in CCD-TK7 UF 0.075 Kg/t feed
Lost cobalt in CCD-TK7 UF 0.073 Kg/t feed
Lost copper in FAQLTKOF 0.004 Kg/t feed
Soluble copper recovery 99.434 %
CCD wash ratio 1.312 m3/ton

1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Feed BMW UFCY OBM SW FCY OFCY PRLTFC
Solid/gas
mass t/h 800.00 2000.00 2800.00 2800.00 800.00 0.032
volume m3/h 296.30 740.74 1037.04 1037.04 296.30 0.012
SG solid t/m3 2.70 2.70 2.70 2.70 2.70 2.65
S % 0.100 0.100
Pulp
mass t/h 1000.00 2683.76 4000.00 4668.95 1985.19 12.80
volume m3/h 496.30 1424.50 2237.04 2905.98 1481.48
SG solid t/m3 2.01 1.88 1.79 1.61 1.34
%solid 80.00 74.52 70.00 40.30 0.25
Liquid
mass t/h 200.00 316.24 683.76 1200.00 668.95 1868.95 1185.19 12.77
volume m3/h 200.00 316.24 683.76 1200.00 668.95 1868.95 1185.19 12.77
SG liquid t/m3 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
S2O6 g/l
Cu g/l
Co g/l
Zn g/l
Ni g/l
Mn g/l
Mg g/l
Al g/l
Fe(II) g/l
Fe(III) g/l
Ca g/l
S g/l
P g/l
Si g/l
C g/l
Ac g/l

9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00

PRLTUF PRLTOF PRLFCa PRLFFl LCA SO2 Raf2L CO2
Solid/gas
mass t/h 800.03 800.03 11.564 5.385
volume m3/h 296.31 296.31
SG solid t/m3 2.70 2.70
S % 0.10 0.10 50.05
Pulp
mass t/h 1379.37 1025.68
volume m3/h 875.64 521.96
SG solid t/m3 1.58 1.97
%solid 58.00 78.00
Liquid
mass t/h 579.33 972.30 225.65 353.68 44.693 1503.55
volume m3/h 579.33 972.30 225.65 353.68 24.830 1428.19
SG liquid t/m3 1.00 1.00 1.00 1.00 1.800 1.053
S2O6 g/l 16.140
Cu g/l 0.356
Co g/l 5.497
Zn g/l 0.610
Ni g/l 0.083
Mn g/l 0.962
Mg g/l 1.224
Al g/l 0.840
Fe(II) g/l 0.999
Fe(III) g/l 0.053
Ca g/l 0.669
S g/l 576.73 15.541
P g/l 0.366
Si g/l 0.024
C g/l 0.000
Ac g/l 1764.00 11.245

17.00 18.00 19.00 20.00 21.00 22.00 23.00 24.00

OLC PTKFC PTKUF PTKOF CO2 TK1FC TK1UF TK1OF
Solid/gas
mass t/h 774.03 0.031 774.02 0.627 0.019 773.99
volume m3/h 309.61 0.012 309.62 0.007 309.63
SG solid t/m3 2.50 2.650 2.50 2.65 2.50
S % 1.500 1.499 1.498
Pulp
mass t/h 2580.11 12.385 1334.52 7.43 1433.32
volume m3/h 1996.05 834.41 943.61
SG solid t/m3 1.29 1.60 1.52
%solid 30.00 0.250 58.00 0.25 54.00
Liquid
mass t/h 1806.07 12.354 560.50 1257.35 7.412 659.33 959.85
volume m3/h 1686.44 12.354 524.79 1177.23 7.412 633.98 922.95
SG liquid t/m3 1.071 1.000 1.068 1.068 1.000 1.040 1.040
S2O6 g/l 19.949 19.767 19.767 11.052 11.052
Cu g/l 6.962 6.898 6.898 3.857 3.857
Co g/l 6.789 6.727 6.727 3.761 3.761
Zn g/l 0.754 0.747 0.747 0.418 0.418
Ni g/l 0.102 0.101 0.101 0.057 0.057
Mn g/l 1.189 1.178 1.178 0.659 0.659
Mg g/l 1.512 1.498 1.498 0.837 0.837
Al g/l 1.037 1.028 1.028 0.575 0.575
Fe(II) g/l 1.231 1.220 1.220 0.682 0.682
Fe(III) g/l 0.068 0.067 0.067 0.038 0.038
Ca g/l 0.659 0.659 0.659 0.687 0.687
S g/l 18.674 18.508 18.508 10.628 10.628
P g/l 0.452 0.448 0.448 0.250 0.250
Si g/l 0.024 0.024 0.024 0.024 0.024
C g/l 0.102 0.000 0.000 0.000 0.000
Ac g/l 2.906 2.888 2.888 1.991 1.991

25.00 26.00 27.00 28.00 29.00 30.00 31.00 32.00

TK2FC TK2UF TK2OF TK3FC TK3UF TK3OF TK4FC TK4UF
Solid/gas
mass t/h 0.012 773.97 0.012 773.94 0.012 773.92
volume m3/h 0.005 309.64 0.005 309.64 0.005 309.65
SG solid t/m3 2.65 2.50 2.65 2.50 2.65 2.50
S % 1.497 1.496 1.495
Pulp
mass t/h 4.95 1433.27 4.95 1433.23 4.95 1433.19
volume m3/h 952.62 958.33 961.94
SG solid t/m3 1.50 1.50 1.49
%solid 0.25 54.00 0.25 54.00 0.25 54.00
Liquid
mass t/h 4.941 659.30 1051.23 4.941 659.28 1046.22 4.941 659.27
volume m3/h 4.941 642.98 1025.20 4.941 648.69 1029.40 4.941 652.30
SG liquid t/m3 1.000 1.025 1.025 1.000 1.016 1.016 1.000 1.011
S2O6 g/l 6.666 6.666 3.996 3.996 2.349
Cu g/l 2.326 2.326 1.395 1.395 0.820
Co g/l 2.269 2.269 1.360 1.360 0.799
Zn g/l 0.252 0.252 0.151 0.151 0.089
Ni g/l 0.034 0.034 0.020 0.020 0.012
Mn g/l 0.397 0.397 0.238 0.238 0.140
Mg g/l 0.505 0.505 0.303 0.303 0.178
Al g/l 0.347 0.347 0.208 0.208 0.122
Fe(II) g/l 0.411 0.411 0.247 0.247 0.145
Fe(III) g/l 0.023 0.023 0.014 0.014 0.008
Ca g/l 0.696 0.696 0.696 0.696 0.691
S g/l 6.658 6.658 4.237 4.237 2.740
P g/l 0.151 0.151 0.091 0.091 0.053
Si g/l 0.024 0.024 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 1.427 1.427 1.022 1.022 0.735

33.00 34.00 35.00 36.00 37.00 38.00 39.00 40.00

TK4OF TK5FC TK5UF TK5OF TK6FC TK6UF TK6OF TK7FC
Solid/gas
mass t/h 0.012 773.90 0.012 773.88 0.012
volume m3/h 0.005 309.65 0.005 309.65 0.005
SG solid t/m3 2.65 2.50 2.65 2.50 2.65
S % 1.495 1.494
Pulp
mass t/h 4.95 1433.15 4.95 1433.12 4.95
volume m3/h 964.24 965.70
SG solid t/m3 1.49 1.48
%solid 0.25 54.00 0.25 54.00 0.25
Liquid
mass t/h 1041.23 4.941 659.25 1036.23 4.941 659.24 1031.25 4.941
volume m3/h 1030.22 4.941 654.59 1028.90 4.941 656.04 1026.25 4.941
SG liquid t/m3 1.011 1.000 1.007 1.007 1.000 1.005 1.005 1.000
S2O6 g/l 2.349 1.321 1.321 0.674 0.674
Cu g/l 0.820 0.461 0.461 0.235 0.235
Co g/l 0.799 0.450 0.450 0.230 0.230
Zn g/l 0.089 0.050 0.050 0.025 0.025
Ni g/l 0.012 0.007 0.007 0.003 0.003
Mn g/l 0.140 0.079 0.079 0.040 0.040
Mg g/l 0.178 0.100 0.100 0.051 0.051
Al g/l 0.122 0.069 0.069 0.035 0.035
Fe(II) g/l 0.145 0.082 0.082 0.042 0.042
Fe(III) g/l 0.008 0.004 0.004 0.002 0.002
Ca g/l 0.691 0.683 0.683 0.675 0.675
S g/l 2.740 1.803 1.803 1.211 1.211
P g/l 0.053 0.030 0.030 0.015 0.015
Si g/l 0.024 0.024 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.735 0.536 0.536 0.399 0.399

41.00 42.00 43.00 44.00 45.00 46.00 47.00 48.00

TK7UF TK7OF WW TK1OFP TK1OFS PLS RE1 LOE1
Solid/gas
mass t/h 771.00
volume m3/h 309.66
SG solid t/m3 2.490
S % 1.430
Pulp
mass t/h 1427.78
volume m3/h 964.21
SG solid t/m3 1.48
%solid 54.00
Liquid
mass t/h 656.78 1026.26 1015.97 855.96 103.90 2113.30 2114.75
volume m3/h 654.55 1022.77 1015.79 823.05 99.90 2000.00 2006.58 2500.00
SG liquid t/m3 1.003 1.003 1.000 1.040 1.040 1.057 1.054
S2O6 g/l 0.264 0.264 0.000 11.052 11.052 16.183 16.141
Cu g/l 0.092 0.092 0.000 3.857 3.857 5.648 1.735 8.156
Co g/l 0.090 0.090 0.000 3.761 3.761 5.507 5.496
Zn g/l 0.010 0.010 0.000 0.418 0.418 0.611 0.610
Ni g/l 0.001 0.001 0.000 0.057 0.057 0.083 0.083
Mn g/l 0.016 0.016 0.000 0.659 0.659 0.964 0.962
Mg g/l 0.020 0.020 0.000 0.837 0.837 1.226 1.224
Al g/l 0.014 0.014 0.000 0.575 0.575 0.841 0.840
Fe(II) g/l 0.016 0.016 0.000 0.682 0.682 0.999 0.999
Fe(III) g/l 0.001 0.001 0.000 0.038 0.038 0.055 0.058 0.0050
Ca g/l 0.666 0.666 0.000 0.687 0.687 0.671 0.669
S g/l 0.832 0.832 0.061 10.628 10.628 15.267 15.515
P g/l 0.006 0.006 0.000 0.250 0.250 0.367 0.366
Si g/l 0.025 0.025 0.000 0.024 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.306 0.306 0.334 1.991 1.991 2.546 8.790

49.00 50.00 51.00 52.00 53.00 54.00 55.00 56.00

ALOE1 RE2 LOE2 ALOE2 ACTD LOAC ALOAC RADS
Solid/gas
mass t/h
volume m3/h
SG solid t/m3
S %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 2.500 2110.81 2.500 1.500 1.000 1559.46
volume m3/h 2.372 2005.01 2500.00 2.375 1.423 2500.00 1.423 1240.42
SG liquid t/m3 1.054 1.053 1.053 1.054 1.054 1.257
S2O6 g/l 16.141 16.140 16.140 16.141 16.141 0.020
Cu g/l 1.735 0.356 4.944 0.356 1.735 8.156 1.735 49.689
Co g/l 5.496 5.497 5.497 5.496 5.496 0.772
Zn g/l 0.610 0.610 0.610 0.610 0.610 0.086
Ni g/l 0.083 0.083 0.083 0.083 0.083 0.012
Mn g/l 0.962 0.962 0.962 0.962 0.962 0.135
Mg g/l 1.224 1.224 1.224 1.224 1.224 0.172
Al g/l 0.840 0.840 0.840 0.840 0.840 0.118
Fe(II) g/l 0.999 0.999 0.999 0.999 0.999 0.994
Fe(III) g/l 0.058 0.053 0.0050 0.053 0.058 0.0050 0.058 1.009
Ca g/l 0.669 0.669 0.669 0.669 0.669 0.094
S g/l 15.515 15.541 15.541 15.515 15.515 92.501
P g/l 0.366 0.366 0.366 0.366 0.366 0.051
Si g/l 0.024 0.024 0.024 0.024 0.024 0.020
C g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ac g/l 8.790 11.245 11.245 8.790 8.790 153.349

57.00 58.00 59.00 60.00 61.00 62.00 63.00 64.00

ADS SO ASO SOBL ASOBL SOBP ASOBP LOBL1
Solid/gas
mass t/h
volume m3/h
SG solid t/m3
S %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 959.82 0.750 0.225 0.525
volume m3/h 763.46 2500.00 0.597 750.620 0.179 1749.380 0.597 750.620
SG liquid t/m3 1.257 1.257 1.257 1.257
S2O6 g/l 0.020 0.020 0.020 0.020
Cu g/l 49.689 3.592 49.689 3.592 49.689 3.592 49.689 4.369
Co g/l 0.772 0.772 0.772 0.772
Zn g/l 0.086 0.086 0.086 0.086
Ni g/l 0.012 0.012 0.012 0.012
Mn g/l 0.135 0.135 0.135 0.135
Mg g/l 0.172 0.172 0.172 0.172
Al g/l 0.118 0.118 0.118 0.118
Fe(II) g/l 0.994 0.994 0.994 0.994
Fe(III) g/l 1.009 0.0003 1.009 0.0003 1.009 0.0003 1.009 0.0007
Ca g/l 0.094 0.094 0.094 0.094
S g/l 92.501 92.501 92.50 92.50
P g/l 0.051 0.051 0.051 0.051
Si g/l 0.020 0.020 0.020 0.020
C g/l 0.000 0.000 0.000 0.000
Ac g/l 153.349 153.349 153.35 153.35

65.00 66.00 67.00 68.00 69.00 70.00 71.00 72.00

ALOBL EWCA EWW EWCC EWO EWS SP EWB
Solid/gas
mass t/h 11.165 2.814 0.0031
volume m3/h
SG solid t/m3
S %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 0.751 1.921 8.483 948.53 7.720
volume m3/h 0.716 1.067 8.483 758.71 6.175
SG liquid t/m3 1.049 1.800 1.000 1.250 1.250
S2O6 g/l 14.015 0.000 0.000
Cu g/l 0.063 35.000 35.000
Co g/l 8.222 0.770 0.770
Zn g/l 0.140 0.085 0.085
Ni g/l 0.366 0.012 0.012
Mn g/l 1.399 0.135 0.135
Mg g/l 1.683 0.171 0.171
Al g/l 0.496 0.118 0.118
Fe(II) g/l 0.086 1.000 1.000
Fe(III) g/l 0.000 1.000 1.000
Ca g/l 0.606 0.094 0.094
S g/l 13.76 576.73 93.13 93.13
P g/l 0.005 0.051 0.051
Si g/l 0.024 0.020 0.020
C g/l 0.000 0.000 0.000
Ac g/l 4.237 1764.00 190.00 190.00

73.00 74.00 75.00 76.00 77.00 78.00 79.00 80.00

WBB
Solid/gas
mass t/h
volume m3/h
SG solid t/m3
S %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 607.26
volume m3/h 576.82
SG liquid t/m3 1.053
S2O6 g/l 16.140
Cu g/l 0.356
Co g/l 5.497
Zn g/l 0.610
Ni g/l 0.083
Mn g/l 0.962
Mg g/l 1.224
Al g/l 0.840
Fe(II) g/l 0.999
Fe(III) g/l 0.053
Ca g/l 0.669
S g/l 15.54
P g/l 0.366
Si g/l 0.024
C g/l 0.000
Ac g/l 11.245
From Table (10.1) and (14.1), it has been observed that the copper recovery from
soluble copper in the feed and copper metal increases from 97.60% to 99.43%.

production circuit (D) obtained by using the realistic simulation model. Tables (14.23),
(14.24) and (14.25) give the mineralogical composition of solid. Tables (14.26) and
(14.27) give the distribution of elements in the inlet and the outlet of cobalt circuit.

Table 14.12: Mass balance of cobalt hydroxide precipitation circuit - D
1 2 3 4 5 6 7
WBB ODS FAPLS FALSPCO2 OFALSP FALSPTKFc FALSPFLF
Solid/gas
mass t/h 25.506 3.207 1.027 31.928 0.0013
volume m3/h 0.0005
SG solid t/m3 2.650
Cu % 0.000 0.000
Co % 0.000 0.000
Zn % 0.000 0.000
Ni % 0.000 0.000
Mn % 0.000 0.000
Mg % 0.019 2.800 0.065
Al % 0.287 0.889 0.997
Fe(II) % 0.000 0.000
Fe(III) % 2.028 1.028 2.154
Ca % 21.166 33.118 20.233
S % 17.831 16.740
P % 0.000 0.739
Si % 0.280 2.580 0.483
C % 0.035 11.010 0.222
Pulp
mass t/h 817.935 16.037 832.946 0.511
volume m3/h
SG solid t/m3
%solid 3.118 20.00 3.833 0.250
Liquid
mass t/h 607.262 792.429 12.830 801.017 0.510 74.307
volume m3/h 576.824 746.933 12.830 758.527 0.510 72.030
SG liquid t/m3 1.053 1.061 1.000 1.056 1.000 1.032
S2O6 g/l 16.140 14.838 14.611 8.688
Cu g/l 0.356 1.060 1.044 0.621
Co g/l 5.497 8.730 8.597 5.112
Zn g/l 0.610 0.706 0.695 0.413
Ni g/l 0.083 0.388 0.382 0.227
Mn g/l 0.962 1.491 1.469 0.873
Mg g/l 1.224 1.683 1.755 1.044
Al g/l 0.840 1.310 1.004 0.597
Fe(II) g/l 0.999 0.091 0.090 0.053
Fe(III) g/l 0.053 0.216 0.031 0.019
Ca g/l 0.669 0.613 0.606 0.375
S g/l 15.541 15.557 14.270 8.498
P g/l 0.366 0.322 0.006 0.003
Si g/l 0.024 0.024 0.024 0.015
C g/l 0.000 0.159 0.159 0.000
Ac g/l 11.245 1.461 0.146 0.102

8 9 10 11 12 13 14
FALSPTKOF FALSPTKUF FALSPTKCO2 FALSPFLW FALSPFLCa FALSPTKOFZ FALSPTKOFS
Solid/gas
mass t/h 31.846 0.442 31.846
volume m3/h
SG solid t/m3
Cu % 0.000 0.000
Co % 0.000 0.000
Zn % 0.000 0.000
Ni % 0.000 0.000
Mn % 0.000 0.000
Mg % 0.065 0.065
Al % 1.000 1.000
Fe(II) % 0.000 0.000
Fe(III) % 2.160 2.160
Ca % 20.285 20.285
S % 16.734 16.734
P % 0.741 0.741
Si % 0.484 0.484
C % 0.222 0.222
Pulp
mass t/h 79.615 53.077
volume m3/h
SG solid t/m3
%solid 40.000 60.000
Liquid
mass t/h 828.065 47.769 47.769 21.231 630.255 197.810
volume m3/h 788.314 45.476 47.769 21.183 600.000 188.314
SG liquid t/m3 1.050 1.050 1.000 1.002 1.050 1.050
S2O6 g/l 14.042 14.042 0.603 14.042 14.042
Cu g/l 1.003 1.003 0.043 1.003 1.003
Co g/l 8.262 8.262 0.355 8.262 8.262
Zn g/l 0.668 0.668 0.029 0.668 0.668
Ni g/l 0.367 0.367 0.016 0.367 0.367
Mn g/l 1.412 1.412 0.061 1.412 1.412
Mg g/l 1.687 1.687 0.072 1.687 1.687
Al g/l 0.965 0.965 0.041 0.965 0.965
Fe(II) g/l 0.086 0.086 0.004 0.086 0.086
Fe(III) g/l 0.030 0.030 0.001 0.030 0.030
Ca g/l 0.607 0.607 0.026 0.607 0.607
S g/l 13.734 13.734 0.590 13.734 13.734
P g/l 0.005 0.005 0.000 0.005 0.005
Si g/l 0.024 0.024 0.001 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.138 0.138 0.013 0.138 0.138

15 16 17 18 19 20 21
ZSXER1 ZSXER2 ZSXSO2 ZSXASO2 ZSXLO2 ZSXALO2 ZSXLO1
Solid/gas
mass t/h
volume m3/h
SG solid t/m3
Cu %
Co %
Zn %
Ni %
Mn %
Mg %
Al %
Fe(II) %
Fe(III) %
Ca %
S %
P %
Si %
C %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 630.255 630.255 0.750 0.750
volume m3/h 600.38 600.496 750.000 0.660 750.000 0.715 750.000
SG liquid t/m3 1.050 1.050 1.136 1.050
S2O6 g/l 14.034 14.014 0.010 14.014
Cu g/l 0.995 0.982 0.0000 0.017 0.0089 0.982 0.0151
Co g/l 8.247 8.222 0.0000 0.022 0.0115 8.222 0.0191
Zn g/l 0.264 0.140 0.0188 5.057 0.1222 0.140 0.4454
Ni g/l 0.367 0.366 0.000 0.366
Mn g/l 1.407 1.399 0.0000 0.009 0.0049 1.399 0.0081
Mg g/l 1.686 1.683 0.0000 0.002 0.0003 1.683 0.0004
Al g/l 0.681 0.496 0.0814 6.358 0.2348 0.496 0.4616
Fe(II) g/l 0.086 0.086 0.000 0.086
Fe(III) g/l 0.001 0.001 0.0181 0.786 0.0188 0.001 0.0424
Ca g/l 0.606 0.605 0.000 0.605
S g/l 13.726 13.758 46.964 13.758
P g/l 0.005 0.005 0.000 0.005
Si g/l 0.024 0.024 0.000 0.024
C g/l 0.000 0.000 0.000 0.000
Ac g/l 1.828 2.980 77.221 2.980

22 23 24 25 26 27 28
ZSXALO1 ZSXSO1 ZSXASO1 ZSXAS ZSXSTR2 ZSXSTS2 ZSXSTR1
Solid/gas
mass t/h
volume m3/h
SG solid t/m3
Cu %
Co %
Zn %
Ni %
Mn %
Mg %
Al %
Fe(II) %
Fe(III) %
Ca %
S %
P %
Si %
C %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 0.750 0.750 28.158 652.596 28.158 658.218
volume m3/h 0.714 750.000 0.655 25.000 574.348 24.782 574.511
SG liquid t/m3 1.050 1.146 1.126 1.136 1.136 1.146
S2O6 g/l 14.034 0.408 0.000 0.010 0.010 0.408
Cu g/l 0.995 0.000 0.488 0.0000 0.017 0.017 0.488
Co g/l 8.247 0.000 0.822 0.0000 0.022 0.022 0.822
Zn g/l 0.264 0.179 12.894 0.0000 5.057 5.057 12.894
Ni g/l 0.367 0.011 0.0000 0.000 0.000 0.011
Mn g/l 1.407 0.000 0.287 0.0000 0.009 0.009 0.287
Mg g/l 1.686 0.000 0.062 0.0000 0.002 0.002 0.062
Al g/l 0.681 0.287 11.453 0.0000 6.358 6.358 11.453
Fe(II) g/l 0.086 0.002 0.0000 0.000 0.000 0.002
Fe(III) g/l 0.001 0.044 0.722 0.0000 0.786 0.786 0.722
Ca g/l 0.606 0.018 0.000 0.000 0.000 0.018
S g/l 13.726 46.515 46.576 46.964 46.964 46.515
P g/l 0.005 0.000 0.000 0.000 0.000 0.000
Si g/l 0.024 0.001 0.000 0.000 0.000 0.001
C g/l 0.000 0.000 0.000 0.000 0.000 0.000
Ac g/l 1.828 25.201 150.000 77.221 77.221 25.201

29 30 31 32 33 34 35
ZSXSTS1 SOBL ASOBL LOBL2 ALOBL2 LOBL1 ALOBL1
Solid/gas
mass t/h
volume m3/h
SG solid t/m3
Cu %
Co %
Zn %
Ni %
Mn %
Mg %
Al %
Fe(II) %
Fe(III) %
Ca %
S %
P %
Si %
C %
Pulp
mass t/h
volume m3/h
SG solid t/m3
%solid
Liquid
mass t/h 28.158 0.225 0.751 0.751
volume m3/h 24.577 750.620 0.179 750.620 0.716 750.620 0.716
SG liquid t/m3 1.146 1.257 1.049 1.049
S2O6 g/l 0.408 0.020 14.011 14.015
Cu g/l 0.488 3.592 49.689 3.634 0.026 4.369 0.063
Co g/l 0.822 0.772 8.220 8.222
Zn g/l 12.894 0.086 0.140 0.140
Ni g/l 0.011 0.012 0.366 0.366
Mn g/l 0.287 0.135 1.398 1.399
Mg g/l 0.062 0.172 1.683 1.683
Al g/l 11.453 0.118 0.496 0.496
Fe(II) g/l 0.002 0.994 0.086 0.086
Fe(III) g/l 0.722 0.0003 1.009 0.0006 0.000 0.0007 0.000
Ca g/l 0.018 0.094 0.605 0.606
S g/l 46.515 92.501 13.783 13.759
P g/l 0.000 0.051 0.005 0.005
Si g/l 0.001 0.020 0.024 0.024
C g/l 0.000 0.000 0.000 0.000
Ac g/l 25.201 153.349 4.359 4.237

36 37 38 39 40 41 42
BCuSXR1 BCuSXR2 FAPQL FAQLPO2 FAQLPCO2 OFAQLP FAQLPTKFc
Solid/gas
mass t/h 4.796 0.003 0.190 10.765 0.0004
volume m3/h 0.0002
SG solid t/m3 2.650
Cu % 0.111
Co % 2.957
Zn % 0.000
Ni % 0.000
Mn % 0.000
Mg % 1.972 0.109
Al % 0.300 2.867
Fe(II) % 0.000
Fe(III) % 0.200 0.284
Ca % 51.458 22.328
S % 15.018
P % 0.030
Si % 0.640 0.285
C % 1.500 0.187
Pulp
mass t/h 23.978 652.957 0.172
volume m3/h
SG solid t/m3
%solid 20.000 1.649 0.250
Liquid
mass t/h 629.721 629.165 19.183 642.192 0.172
volume m3/h 600.448 599.900 19.183 617.869 0.172
SG liquid t/m3 1.049 1.049 1.000 1.039 1.000
S2O6 g/l 14.015 14.011 13.604
Cu g/l 0.063 0.026 0.006
Co g/l 8.222 8.220 7.466
Zn g/l 0.140 0.140 0.136
Ni g/l 0.366 0.366 0.355
Mn g/l 1.399 1.398 1.358
Mg g/l 1.683 1.683 1.768
Al g/l 0.496 0.496 0.005
Fe(II) g/l 0.086 0.086 0.050
Fe(III) g/l 0.000 0.000 0.000
Ca g/l 0.606 0.605 0.692
S g/l 13.759 13.783 10.766
P g/l 0.005 0.005 0.000
Si g/l 0.024 0.024 0.024
C g/l 0.000 0.000 0.000
Ac g/l 4.237 4.359 0.001

43 44 45 46 47 48 49
FAQLPTKOF FAQLPTKUF CP1MG CP1AO2 OCP1 CP1TKFc CP1TKOF
Solid/gas
mass t/h 10.765 2.229 0.025 9.103 0.0004
volume m3/h 0.0001
SG solid t/m3 2.650
Cu % 0.111 0.036
Co % 2.957 41.022
Zn % 0.000 0.835
Ni % 0.000 1.380
Mn % 0.000 0.076
Mg % 0.109 57.897 2.722
Al % 2.867 0.000 0.031
Fe(II) % 0.000 0.000
Fe(III) % 0.284 0.000 0.307
Ca % 22.327 1.930 0.091
S % 15.018 8.364
P % 0.030 0.000
Si % 0.285 0.608 0.149
C % 0.187 0.000
Pulp
mass t/h 71.769 583.615 0.146
volume m3/h
SG solid t/m3
%solid 15.000 1.560 0.250
Liquid
mass t/h 581.360 61.003 574.512 0.145 523.073
volume m3/h 559.347 58.694 557.313 0.145 507.417
SG liquid t/m3 1.039 1.039 1.031 1.000 1.031
S2O6 g/l 13.600 13.600 13.650 13.646
Cu g/l 0.006 0.006 0.000 0.000
Co g/l 7.464 7.464 0.791 0.791
Zn g/l 0.136 0.136 0.000 0.000
Ni g/l 0.355 0.355 0.131 0.131
Mn g/l 1.357 1.357 1.350 1.349
Mg g/l 1.767 1.767 3.645 3.644
Al g/l 0.005 0.005 0.000 0.000
Fe(II) g/l 0.050 0.050 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000
Ca g/l 0.692 0.692 0.756 0.756
S g/l 10.763 10.763 9.436 9.434
P g/l 0.000 0.000 0.000 0.000
Si g/l 0.024 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000
Ac g/l 0.001 0.001 0.000 0.000

50 51 52 53 54 55 56
CP1TKUF MGDAc OMGD MGDFLW MGDFLF MGDFLCa CP2QL
Solid/gas
mass t/h 9.103 8.186 8.186 1.173
volume m3/h
SG solid t/m3
Cu % 0.036 0.040 0.040
Co % 41.020 42.317 42.317
Zn % 0.835 0.928 0.928
Ni % 1.380 0.564 0.564
Mn % 0.076 0.065 0.065
Mg % 2.722 1.641 1.641 1.972
Al % 0.031 0.034 0.034 0.300
Fe(II) % 0.000 0.000 0.000
Fe(III) % 0.307 0.342 0.342 0.200
Ca % 0.091 0.224 0.224 51.458
S % 8.363 8.803 8.803
P % 0.000 0.000 0.000
Si % 0.149 0.166 0.166 0.640
C % 0.000 0.000 0.000 1.500
Pulp
mass t/h 60.688 61.599 20.464 5.867
volume m3/h
SG solid t/m3
%solid 15.000 13.289 40.000 20.000
Liquid
mass t/h 51.585 0.912 53.414 24.557 65.692 12.279 4.694
volume m3/h 50.041 0.507 50.537 24.557 62.850 12.219 4.694
SG liquid t/m3 1.031 1.800 1.057 1.000 1.045 1.005 1.000
S2O6 g/l 13.646 13.512 10.648 1.118
Cu g/l 0.000 0.000 0.000 0.000
Co g/l 0.791 6.129 4.830 0.507
Zn g/l 0.000 0.001 0.001 0.000
Ni g/l 0.131 1.702 1.341 0.141
Mn g/l 1.349 1.369 1.079 0.113
Mg g/l 3.644 5.853 4.612 0.484
Al g/l 0.000 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000
Ca g/l 0.756 0.550 0.433 0.045
S g/l 9.434 576.729 15.928 12.552 1.318
P g/l 0.000 0.000 0.000 0.000
Si g/l 0.024 0.024 0.019 0.002
C g/l 0.000 0.000 0.000 0.000
Ac g/l 0.000 1764.000 0.000 0.000 0.000

57 58 59 60 61 62 63
CP2O2 OCP2 CP2TKFc CP2TKOF CP2TKUF CDAc OCD
Solid/gas
mass t/h 0.058 3.410 0.0001 3.410 2.652
volume m3/h 0.0001
SG solid t/m3 2.650
Cu % 0.000 0.000 0.000
Co % 10.988 10.987 0.001
Zn % 0.000 0.000 0.000
Ni % 1.856 1.856 0.000
Mn % 9.438 9.437 7.529
Mg % 0.227 0.227 0.036
Al % 0.103 0.103 0.133
Fe(II) % 0.000 0.000 0.000
Fe(III) % 0.069 0.069 0.089
Ca % 16.219 16.218 21.092
S % 10.713 10.713 15.713
P % 0.000 0.000 0.000
Si % 0.220 0.220 0.000
C % 0.516 0.516 0.000
Pulp
mass t/h 528.998 0.055 22.735 24.056
volume m3/h
SG solid t/m3
%solid 0.645 0.250 15.000 11.023
Liquid
mass t/h 525.588 0.054 506.318 19.325 1.321 21.404
volume m3/h 511.605 0.054 492.849 18.811 0.734 19.069
SG liquid t/m3 1.027 1.000 1.027 1.027 1.800 1.122
S2O6 g/l 13.534 13.533 13.533 13.350
Cu g/l 0.000 0.000 0.000 0.000
Co g/l 0.052 0.052 0.052 19.699
Zn g/l 0.000 0.000 0.000 0.000
Ni g/l 0.006 0.006 0.006 3.326
Mn g/l 0.709 0.709 0.709 7.108
Mg g/l 3.644 3.644 3.644 3.951
Al g/l 0.000 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000
Ca g/l 0.849 0.849 0.849 0.511
S g/l 8.642 8.641 8.641 576.729 28.025
P g/l 0.000 0.000 0.000 0.000
Si g/l 0.024 0.024 0.024 0.023
C g/l 0.000 0.000 0.000 0.831
Ac g/l 0.000 0.000 0.000 1764.000 4.520

64 65 66 67 68 69 70
CDFLW CDFLF CDFLCa SPQL SPO2 OSP STTKFS
Solid/gas
mass t/h 2.652 6.348 0.114 17.057 0.0007
volume m3/h 0.0003
SG solid t/m3 2.650
Cu % 0.000 3.367
Co % 0.001 11.263
Zn % 0.000 0.982
Ni % 0.000 0.436
Mn % 7.529 1.780
Mg % 0.036 1.972 0.221
Al % 0.133 0.300 1.514
Fe(II) % 0.000 0.000
Fe(III) % 0.089 0.200 0.624
Ca % 21.092 51.458 17.292
S % 15.713 10.731
P % 0.000 0.153
Si % 0.000 0.640 0.238
C % 0.000 1.500 0.558
Pulp
mass t/h 6.629 31.742 333.56 0.273
volume m3/h
SG solid t/m3
%solid 40.000 20.000 5.11 0.250
Liquid
mass t/h 7.955 25.382 3.978 25.393 316.505 0.272
volume m3/h 7.955 23.052 3.927 25.393 310.955 0.272
SG liquid t/m3 1.000 1.101 1.013 1.000 1.018 1.000
S2O6 g/l 10.822 1.297 12.055
Cu g/l 0.000 0.000 0.000
Co g/l 15.969 1.913 0.035
Zn g/l 0.000 0.000 0.000
Ni g/l 2.696 0.323 0.001
Mn g/l 5.762 0.690 0.090
Mg g/l 3.203 0.384 1.572
Al g/l 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000
Ca g/l 0.415 0.050 1.609
S g/l 22.719 2.722 5.846
P g/l 0.000 0.000 0.000
Si g/l 0.019 0.002 0.024
C g/l 0.674 0.081 0.000
Ac g/l 3.976 0.920 0.000

71 72 73 74 75 76 77
STTKOF STTKUF STFLF STFLCa ENQL ENO2 OEN
Solid/gas
mass t/h 17.058 17.058 8.134 0.000 48.829
volume m3/h
SG solid t/m3
Cu % 3.366 3.366 0.026
Co % 11.262 11.262 0.145
Zn % 0.982 0.982 0.650
Ni % 0.436 0.436 0.011
Mn % 1.780 1.780 1.199
Mg % 0.221 0.221 1.972 0.320
Al % 1.514 1.514 0.300 1.238
Fe(II) % 0.000 0.000 0.000
Fe(III) % 0.624 0.624 0.200 1.450
Ca % 17.291 17.291 51.458 21.765
S % 10.731 10.731 14.544
P % 0.153 0.153 0.445
Si % 0.238 0.238 0.640 0.438
C % 0.558 0.558 1.500 0.399
Pulp
mass t/h 113.718 42.644 40.668 926.041
volume m3/h
SG solid t/m3
%solid 15.000 40.000 20.000 5.273
Liquid
mass t/h 220.117 96.660 71.074 25.586 32.534 877.212
volume m3/h 216.261 94.967 69.828 25.138 32.534 859.424
SG liquid t/m3 1.018 1.018 1.018 1.018 1.000 1.021
S2O6 g/l 12.044 12.044 12.044 12.044 11.802
Cu g/l 0.000 0.000 0.000 0.000 0.000
Co g/l 0.034 0.034 0.034 0.034 0.000
Zn g/l 0.000 0.000 0.000 0.000 0.000
Ni g/l 0.001 0.001 0.001 0.001 0.000
Mn g/l 0.090 0.090 0.090 0.090 0.001
Mg g/l 1.571 1.571 1.571 1.571 2.648
Al g/l 0.000 0.000 0.000 0.000 0.000
Fe(II) g/l 0.000 0.000 0.000 0.000 0.000
Fe(III) g/l 0.000 0.000 0.000 0.000 0.000
Ca g/l 1.607 1.607 1.607 1.607 1.044
S g/l 5.841 5.841 5.841 5.841 6.679
P g/l 0.000 0.000 0.000 0.000 0.022
Si g/l 0.024 0.024 0.024 0.024 0.024
C g/l 0.000 0.000 0.000 0.000 0.000
Ac g/l 0.000 0.000 0.000 0.000 0.000

ODS OFALSP OFAQLP

CaCO3 (unreacted) 74.932 0.294 525.215 1.645 167.848 1.559
Ca(OH)2 212.195 0.832 212.195 0.665 502.300 4.666
CaSiO3 294.981 1.157 387.357 1.213 126.941 1.179
MgCO3 0.000 0.000 54.503 0.171 0.000 0.000
Mg(OH)2 (unreacted) 11.922 0.047 11.922 0.037 28.222 0.262
Al2O3 63.186 0.248 117.072 0.367 27.191 0.253
Fe2O3 31.872 0.125 79.022 0.247 13.716 0.127
SiO2 0.000 0.000 129.262 0.405 0.000 0.000
CaSO4.2H2O 22130.872 86.767 25778.754 80.739 8680.533 80.638
AlPO4.2H2O 0.000 0.000 1203.885 3.771 16.300 0.151
Fe(OH)3 0.011 0.000 4.701 0.015 0.000 0.000
FeFe4(SO4)6(OH)2.20H2O 0.004 0.000 0.007 0.000 0.000 0.000
(Al)(2/3)Fe4(SO4)6(OH)2.20H2O 2685.985 10.531 3424.572 10.726 0.000 0.000
Cu(OH)2 0.000 0.000 0.001 0.000 0.000 0.000
CuFe2O4.2H2O 0.000 0.000 0.000 0.000 51.683 0.480
CoAl2O4.2H2O 0.000 0.000 0.000 0.000 1150.142 10.684
Total 25505.961 31928.468 10764.876

OCP1 OMGD OCP2

CaCO3 (unreacted) 0.000 0.000 0.000 0.000 66.741 1.957
Ca(OH)2 15.252 0.168 8.278 0.101 203.057 5.955
CaSiO3 0.000 0.000 0.000 0.000 31.062 0.911
Mg(OH)2 (unreacted) 593.860 6.524 322.324 3.938 11.409 0.335
Al2O3 0.000 0.000 0.000 0.000 6.654 0.195
Fe2O3 0.000 0.000 0.000 0.000 3.356 0.098
SiO2 28.982 0.318 28.982 0.354 0.000 0.000
CaSO4.2H2O 0.000 0.000 59.419 0.726 1743.123 51.116
Co3(PO4)2.8H2O 0.111 0.001 0.111 0.001 0.000 0.000
Fe(OH)3 97.983 1.076 97.983 1.197 0.000 0.000
Co2Cu3(OH)6(SO4)2.5H2O 0.006 0.000 0.814 0.010 0.000 0.000
Cu(OH)2 5.060 0.056 4.717 0.058 0.000 0.000
ZnCo3(OH)6(SO4).3H2O 574.659 6.313 574.057 7.013 0.049 0.001
Zn(OH)2 0.027 0.000 0.056 0.001 0.000 0.000
Co5(OH)6(SO4)2.3H2O 7217.690 79.291 6712.293 82.000 396.755 11.635
Co(OH)2 105.540 1.159 18.195 0.222 82.053 2.406
Ni4(OH)6SO4 54.174 0.595 34.560 0.422 14.812 0.434
Ni(OH)2 151.982 1.670 43.284 0.529 87.290 2.560
Mn(OH)2 2.573 0.028 0.059 0.001 15.972 0.468
CoAl2O4.2H2O 11.118 0.122 11.118 0.136 0.000 0.000
CoCO3 0.000 0.000 0.112 0.001 0.000 0.000
MnCO3 0.218 0.002 0.000 0.000 91.879 2.694
CoOOH 234.514 2.576 260.848 3.187 219.644 6.441
MnOOH 8.432 0.093 8.449 0.103 429.097 12.583
Total 9102.787 8185.681 3410.107

OCD OST OEN

CaCO3 (unreacted) 14.668 0.553 361.062 2.117 1022.815 2.095
Ca(OH)2 40.473 1.526 1098.513 6.440 1723.587 3.530
CaSiO3 31.062 1.171 168.041 0.985 633.715 1.298
MgCO3 0.000 0.000 0.000 0.000 54.503 0.112
Mg(OH)2 (unreacted) 2.274 0.086 61.721 0.362 96.842 0.198
Al2O3 6.654 0.251 35.995 0.211 123.726 0.253
Fe2O3 3.356 0.127 18.156 0.106 82.378 0.169
SiO2 0.000 0.000 0.000 0.000 129.262 0.265
CaSO4.2H2O 2237.224 84.370 9246.833 54.211 38025.771 77.876
Co3(PO4)2.8H2O 0.000 0.000 214.662 1.258 0.000 0.000
MnHPO4.3H2O 0.000 0.000 0.000 0.000 1436.754 2.942
Fe(OH)3 0.000 0.000 26.898 0.158 2200.318 4.506
Al4(OH)(11.36).(SO4)(0.32).5H2O 0.000 0.000 0.000 0.000 810.096 1.659
Co2Cu3(OH)6(SO4)2.5H2O 0.000 0.000 7.080 0.042 0.000 0.000
Cu(OH)2 0.000 0.000 803.453 4.710 0.094 0.000
ZnCo3(OH)6(SO4).3H2O 0.000 0.000 1265.943 7.422 0.000 0.000
Zn(OH)2 0.000 0.000 0.171 0.001 0.001 0.000
Co5(OH)6(SO4)2.3H2O 0.000 0.000 255.011 1.495 0.000 0.000
Co(OH)2 0.000 0.000 509.336 2.986 0.000 0.000
Ni(OH)2 0.000 0.000 117.593 0.689 0.024 0.000
Mn(OH)2 0.000 0.000 18.741 0.110 0.834 0.002
Fe(OH)2 0.000 0.000 0.000 0.000 0.000 0.000
CuFe2O4.2H2O 0.000 0.000 212.135 1.244 55.695 0.114
CoAl2O4.2H2O 0.000 0.000 943.835 5.533 255.341 0.523
ZnAl2O4.2H2O 0.000 0.000 0.000 0.000 1065.289 2.182
NiAl2O4.2H2O 0.000 0.000 0.000 0.000 18.957 0.039
MnCO3 0.000 0.000 496.715 2.912 0.000 0.000
FeCO3 0.000 0.000 0.000 0.000 0.000 0.000
CaCO3 (precipitated) 0.000 0.000 535.903 1.098
CoOOH 0.047 0.002 1079.220 6.327 0.047 0.000
MnOOH 0.000 0.000 87.342 0.512 0.000 0.000
R-MnO2 103.830 3.916 0.000 0.000 103.830 0.213
β-MnO2 212.092 7.998 0.000 0.000 212.092 0.434
Total 2651.681 17056.973 48828.595

Inlet
WBB TK1OFS FAPLS FAPQL CPMG ZSXAS/MG/CD/DS SOBL
Cu 6.227 11.691 0.000 0.000 0.000 0.000 82.082
Co 89.401 10.595 0.000 0.000 0.000 0.000 0.004
Zn 89.396 10.600 0.000 0.000 0.000 0.000 0.004
Ni 89.411 10.586 0.000 0.000 0.000 0.000 0.004
Mn 89.400 10.596 0.000 0.000 0.000 0.000 0.004
Mg 29.254 3.467 3.721 10.064 53.492 0.000 0.001
Al 79.756 9.456 4.697 6.088 0.000 0.000 0.003
Ca 4.887 0.869 13.449 80.250 0.545 0.000 0.000
S 65.973 7.814 0.000 0.000 0.000 26.091 0.122
P 89.396 10.600 0.000 0.000 0.000 0.000 0.004
Si 7.247 1.262 43.231 41.180 7.077 0.000 0.002
C 0.003 0.000 65.649 34.348 0.000 0.000 0.000
Fe 82.341 9.759 4.477 3.345 0.000 0.000 0.078
Table (14.27): Distribution of elements in oulet (%)
Outlet
FAPFLCa CO2 ZSXSN MGDFLCa CPOf/STOF/STF LOBL CDDFLCa
Cu 0.028 0.000 0.364 0.100 0.000 99.508 0.000
Co 0.212 0.000 0.569 97.841 0.999 0.166 0.213
Zn 0.154 0.000 80.518 19.302 0.000 0.025 0.000
Ni 0.625 0.000 0.490 89.679 6.338 0.491 2.376
Mn 0.216 0.000 1.187 1.128 63.219 0.169 34.081
Mg 0.921 0.000 0.063 5.813 93.051 0.050 0.102
Al 52.560 0.000 46.338 0.464 0.000 0.058 0.580
Ca 81.592 0.000 0.005 0.238 11.093 0.005 7.066
S 39.309 0.000 8.413 5.421 43.639 0.072 3.145
P 99.991 0.000 0.002 0.006 0.000 0.002 0.000
Si 82.557 0.000 0.009 7.271 10.149 0.009 0.005
C 13.504 86.432 0.000 0.002 0.001 0.000 0.060
Fe 93.385 0.000 2.416 3.795 0.000 0.084 0.319


Reaction extent (%)

DS Acid 1.498 T/tCo
FALSP limestone 82.500 0.924 T/tCo
FAQLP stechiometria oxygen 0.858 kg/tCo
FAQLP Quick lime 87.558 1.382 T/tCo
CP1 MgO 80.822 0.642 T/tCo
CP2 Quick lime 79.445 0.338 T/tCo
CD Acid 0.381 T/tCo
ST quick lime 1.829 T/tCo
V/V% Cyanex 272 22.544 %

Cyanex 272 consumption 0.813 kg/tCo
Lix984N 0.547 kg/tCo
Diluent consumption 4.539 kg/tCo
pH of raffinate ZnSXE2 1.691


Limestone 0.924 t/tCo 70.00 64.70
Quick lime 5.893 t/tCo 150.00 884.01
Acid 3.244 t/tCo 120.00 389.28
MgO 0.642 t/tCo 700.00 449.71
Cyanex 272 0.813 kg/tCo 41990.00 34.15
Lix984N 0.547 kg/tCo 9240.00 5.06
Diluent 4.539 kg/tCo 1590.00 7.22
Total 3252.71
Cobalt recovery in the cobalt circuit increases from 97.805 to 97.841%.

15. Reference
1. James W Murray et al, The oxidation of cobalt(II) adsorbed on manganese
dioxide, Geochimica et Cosmochimica, 1979.
2. Barack Morgan et al, The effect of pH on the kinetics of spontaneous Fe(II)
oxidation by O2 in aqueous solution – basic principles and a simple heuristic
description, Chemosphere, 2007.
3. Wensheng Zhang et al, Iron(II) oxidation by SO2/O2 in acidic media: Part I.
Kinetics and mechanism, Hydrometallurgy, 2000.
4. Kathleen S. Smith, Metal sorption on mineral surfaces: An overview with
examples relating to mineral deposits, S.E.G., 1999.
5. K. G. Karthikeyan et al, Role of surface precipitation in copper sorption by
hydrous oxides of Iron and Aluminum, JCIS, 1999.
6. Masanori Okazaki et al, Adsorption of heavy metal cations on hydrates oxides and
oxides of Iron and Aluminum with different crystallinites, Soil Sci. Plant Nutr.,
1986.
7. Huseyin Basturkcu et al, Selective Nickel – Iron separation from atmospheric
leach liquor of lateritic Nickel ore using the para-Goethite method, Phsiochem.
Probl. Miner Process, 2017.
8. Sanchez Espana J. et al, Geochemistry of dissolved aluminum at low pH: Extent
and Significance of Al-Fe(+3) coprecipitation below pH 4.0, Geochimica et
Cosmochimica Acta, 2015.
9. R. Nasanen et al, The equilibria of cupric hydroxysalts in mixed aqueous solution
of cupric and alkali salts at 20°C, J.A.C.S., 1949.
10. Monica M. Jimenez Correa at al, Precipitation of Metals from liquor obtained in
Nickel Mining, TMS, 2016.
11. Masambi S., Evaluation of precipitation processes for the removal of Iron from
chloride – based copper and nickel leach solution, Thesis, Stellenbosch
University, 2015.
12. V. L. Vinograd et al, Thermodymics of the solid solution – Aqueous solution
system (Ba, Sr, Ra) SO4 + H2O: I. The effect of Strontium content on Radium
uptake by barite, Applied Geochemistry, 2018.
13. Josep M. Soler, Thermodynamic description of the solubility of C-S-H gels in
hydrated Portland cement, Working report, 2007.
14. Kafumbila J., Design of counter current decantation in Copper metallurgy, 2017a.
(PDF) DESIGN OF COUNTER CURRENT DECANTATION IN COPPER METALLURGY
(researchgate.net)
15. Charles E. Harvie, Nancy Moller and John H. Weare, 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 (1984).

16. H.C. Helgeson, Thermodynamics of hydrothermal systems at elevated
temperatures and pressures, Ameraican Journal of Science 267, 1969.
17. H.C. Helgeson et al, 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,
1981.
18. Bjorn Beverskog, et al, Pourbaix diagrams for the system copper – chlorine at 5 –
100°C, SKI Rapport 98:19, 1998.
19. J. Chivot, Thermodynamique des produits de corrosion, Andra,2004.
20. Yoshiyuki Matsushima et al, Potentiometric studies on sulfato complex of
Aluminum (III) in aqueous solution at elevated temperatures, Chem. Soc. Jpm.,
1988.
21. Jaime Treco Gallardo, 2007, Modeling chalcopyrite leaching, Thesis, University of
British Columbia.
22. La Iglesia A., Estimating the thermodynamic properties of phosphate minerals at
high and low temperature from the sum of constituent units, Estudios Geologicos,
2009.
23. Takacs I. et al, Chemical phosphorus removal to extremely low levels: experience
of two plants in the Washington, DC area, Water Science and technology, 2009.
24. Boyler F. W. jr. et al, Diffraction patterns and solubility products of several
divalent manganese phosphate compounds, Soil Science Society of America
Journal, 1985.
25. Peterson S. R., An overview of the geochemical code MINTEQ, 1987.
26. Wenhao Sun et al, Non-equilibrium crystallization pathways of manganese oxides
in aqueous solution, Nature communications, 2019.
27. Tian Qing-hua et al, The thermodynamic porperties of CoOOH, The Chinese
Journal of Nonferrous metals, 2015.
28. Rubin Alan J. et al, Studies on the hydrolysis and precipitation of Aluminum, The
Ohio State University, 1973.
29. Siclet G. et al, Bull. Soc. Chim. France, 1966.
30. Feitmecht W. Helv. Chem. Acta. 1935.
31. Glibert J. et al, Le dézingage des solutions cobaltifères en circuit
d’electroextraction, Metallutgie, 1969.
32. Kafumbila J., Prediction of dithionate and iron saturation concentrations in
solution during reductive leaching of cobalt using sulfur dioxide gas as reducing
agent, 2022a
(PDF) Prediction of dithionate and iron saturation concentrations in solution
during reductive leaching of cobalt using sulfur dioxide gas as reducing agent
(researchgate.net)
33. D. Rai et al, 1991, An Aqueous thermodynamic model for Ca(+2)-SO3(-2) ion
interactions and the solubility product of crystalline CaSO3.1/2H2O, Journal of
solution chemistry.

34. G. Azimi et al, 2007, Chemical modelling of calcium sulfate phase equilibria in
multi-component electrolyte solutions, Fluid phase equilibria.
35. J. Kafumbila, 2020a, Utilization efficiency of sulfur dioxide during reductive
leaching of Copper – Cobalt ores - (PDF) Utilization efficiency of sulfur dioxide
during reductive leaching of Copper -Cobalt ores (researchgate.net)
36. Peter Warneck, 2018, The oxidation of sulfur (IV) by reactions with iron (III): A
critical review and data, Physical chemical-Chemical physics.
37. Bing Qu et al, 2018, Oxidation kinetics of dithionate compound in the leaching
process of manganese dioxide with manganese dithionate, Reaction kinetics,
mechanisms and catalysis.
38. Hanne Crossland et al, 1961, Estimation of dithionate, Acta Chemica Scandinavica
39. Corey A Cohn et al, 2006, Pyrite – induced hydroxyl radical formation and its
effect on nucleic acids, Geochemical transactions.
40. Qian Peng et al, 2020, High – efficiency catalysis of peroxymonosulfate by MgO
for degradation of organic pollutants, Minerals.
41. Ermakov A. N. et al, 1997, Sulfite oxidation: The state-of-the-art of the problem,
Kinetics and Catalysis.
42. H. A. Evans et al, Modeling cobalt extraction with Cyanex 272, Proceeding of ISEC,
2008.
43. Bershak Andrey, Purification of Nickel sulfate solution via solvent extraction
method, Thesis, LUT University, 2019.
44. Kafumbila J., Comparison between conventional and split circuits: Iron behaviors,
Reagent consumptions and Equipment sizes, 2022c.
(PDF) Comparison between conventional and split circuits: Iron behaviors,
Reagent consumptions and Equipment sizes (researchgate.net)
45. Kafumbila J., Design of agitated leach circuit: reductive leaching of Copper and
Cobalt ores, 2021.
(PDF) Design of agitated leach circuit (researchgate.net)
46. Kafumbila J., Design of Copper solvent extraction circuit: Effect of dithionate on
copper solvent extraction recovery in sulfate media, 2022b.
(PDF) Design of Copper solvent extraction circuit Effect of dithionate on copper
solvent extraction recovery in sulfate media (researchgate.net)


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PROJECT METALLURGIST

Modeling and design of

Kafumbila Kasonta Joseph

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

In the publication, realistic simulation program based on thermodynamic

The realistic simulation program is applied to example of cobalt hydroxyl-

Joseph Kafumbila Page 6

2.2. Simplest cobalt circuit

The first precipitation pH is ranged from 4.5 to 4.8. Limestone is used as

At pH high than 4.8, the remaining Al, after amorphous Al phosphate

At pH ranged from 4.5 to 4.8, Cobalt concentration in feed solution must be

Joseph Kafumbila Page 7

Co precipitation is done at pH ranged 8.2 to 8.4 using MgO as precipitation agent

Al precipitates as amorphous cobalt, Copper and Zinc aluminates

Joseph Kafumbila Page 8

2.3. Ferrous oxidation step

2.3.1. Oxygen from Air as oxidation agent

Depending of Ferrous quantity in solution, oxidation time is ranged from 3 and

The first precipitation pH is ranged from 4.5 to 4.8. Limestone is used as

Joseph Kafumbila Page 9

2.3.2. Mixture Air/𝐒𝐎𝟐 as oxidation agent

Joseph Kafumbila Page 10

The first precipitation pH is ranged from 4.5 to 4.8. Limestone is used as

2.3.3. CoOOH and MnOOH as oxidation agent

Joseph Kafumbila Page 11

Underflow of the second cobalt precipitation is recycled to Fe(II) oxidation

The first precipitation pH is ranged from 4.5 to 4.8. Limestone is used as

2.4. Two and three stages of Fe and Al removal step

Joseph Kafumbila Page 12

2.4.2. Two precipitation stage and recycling of UF of second

Figure 2.5: Two precipitation stages of Fe and Al precipitation with recycling of UF of

There is dissolution of amorphous Cu, Co and Zn aluminates (CoAl2 O4 . 2H2 O,

Joseph Kafumbila Page 13

In the case there is an excess of phosphate comparatively to Al concentration,

The second precipitation stage is done at pH ranged from 4.9 to 5.0. Al

2.4.3. Two precipitation stage and recycling of UF of second

Joseph Kafumbila Page 14

When there is not enough ferric to maintain Al concentration at less than

Joseph Kafumbila Page 15

The second precipitation stage is done at pH ranged from 5.0 to 5.2. Al

In the case of recycling of second stage precipitation thickener UF to CCD1 the

Joseph Kafumbila Page 16

There is dissolution of amorphous Cu, Co and Zn aluminates (CoAl2 O4 . 2H2 O,

Joseph Kafumbila Page 17

Figure 2.10: Copper conventional circuit with organic bleed

A bleed of stripped organic is sent to Copper solvent extraction step in cobalt

The second precipitation stage is done at pH ranged from 5.0 to 5.2. Al

Joseph Kafumbila Page 18

2.4.5. Tree stages of Fe and Al removal circuit with copper

There is dissolution of amorphous Cu, Co and Zn aluminates (CoAl2 O4 . 2H2 O,

Joseph Kafumbila Page 19

The third precipitation stage is done at pH 5.2. Al precipitates as amorphous Cu,

2.4.6. Two stages of Fe and Al removal circuit with Cyanex

ΔGc = (υc μC + υd μD )-(- υe FE + υa μA + υb μB ) (3.2)

μA =μ°A +2.303RT.log(γA *XA ) (3.5)

μ(Aα Bβ ) =XA μA +XB μB (3.7)