Design of Copper Solvent Extraction Circuit - Effect of Dithionate On Copper Solvent Extraction Recovery

PROJECT METALLURGIST
Design of Copper
solvent extraction
circuit
Effect of dithionate on copper solvent
extraction recovery in sulfate media
Kafumbila Kasonta Joseph
2022
Design of Copper solvent extraction circuit: Effect of dithionate on copper solvent
extraction recovery in sulfate media
© 2022 Joseph Kafumbila
jokafumbila@hotmail.com
Joseph Kafumbila Page 1

Contents
1. INTRODUCTION 6
2. CHEMISTRY OF SOLVENT EXTRACTION 8
2.1. CLASSIFICATION OF METAL SOLVENT EXTRACTION 8

2.1.1. Extraction by salvation 8
2.1.2. Extraction by cation exchange 8
2.1.3. Extraction by anion exchange 8
2.1.4. Extraction by chelation 9
2.2. CHEMISTRY OF COPPER SOLVENT EXTRACTION 9
3. CONSTRUCTION OF DISTRIBUTION ISOTHERMS 11
3.1. LABORATORY-SCALE TEST 11

3.2. PREDICTED DISTRIBUTION ISOTHERMS 12
3.2.1. Classification of predicted distribution isotherms 12
3.2.2. Empirical model 12
3.2.3. Semi-empirical model 13
3.2.4. Chemical model 14
4. NEW SEMI-EMPIRICAL MODEL 16
4.1. EQUILIBRIUM CONDITION 16

4.2. VALUE OF 𝛙𝐞𝟏 17
4.2.1. Definition 17
4.2.2. Copper molar concentration in organic phase 17
4.2.3. Free extractant molar concentration in organic phase 17
4.2.4. Cu-Sulfate system 18
4.2.5. Constraint during copper solvent extraction 22
4.3. VALUE OF 𝛙𝐞𝟐 25
4.3.1. Definition 25
4.4. EQUATION OF THERMODYNAMIC EQUILIBRIUM CONDITION 26
4.4.1. Equation of modelling of equilibrium condition 26
4.4.2. Effect of initial free acid concentration 27
4.4.3. Effect of extractant volume percent in organic phase 29
4.4.4. Effect of presence of other elements in solution 30
4.4.5. Effect of high acid concentration (stripping step) 39
4.4.6. Equation of equilibrium condition 40
5. MACCABE -THIELE DIAGRAM 42
5.1. EXTRACTION STEP 42

5.2. STRIPPING STEP 43
6. METALLURGICAL CONSTRAINTS OF COPPER SX 45

6.1. DESCRIPTION OF COPPER SX 45
6.2. DESIGN CRITERIA OF COPPER SX 46
6.2.1. Maximum copper loading 46
6.2.2. Extractant volume percent 47
6.2.3. Copper net transfer 47
6.2.4. Percentage to maximum loading 47
6.2.5. Copper recovery 47
6.2.6. Advance and operating ratios (O/A) 48
6.2.7. Phase continuity 49
6.2.8. Number of stages on extraction step 49
6.2.9. Number of stages on stripping step 51
6.2.10. Stage efficiency 51
6.3. METALLURGICAL CONSTRAINTS OF COPPER SX 52
6.3.1. Constraints between extraction and stripping steps 52
6.3.2. Advance ratio (O/A) 53
6.3.3. Copper concentration in spent electrolyte 54
6.3.4. Acid concentration in spent electrolyte 55
6.3.5. Copper concentration in advance electrolyte 56
6.3.6. Percentage to maximum loading 56
7. MODELING OF COPPER SX CIRCUIT 59
7.1. FLOW DIAGRAM OF CU SX CIRCUIT 59

7.2. MODELING OF COPPER SX-EW CIRCUIT WITHOUT DITHIONATE 60
7.2.1. Base case - copper alone in PLS 60
7.2.2. Base case - Copper and other elements in PLS 65
7.2.3. Base case - Extraction Fe(3) in organic phase 71
7.2.4. Base case – Aqueous phase entrainment in organic phase 78
7.2.5. Base case – loaded organic wash stage 86
7.2.6. Base case – Aqueous coalescing tank 95
7.2.7. Base case – Spraying water on loaded organic phase 103
7.2.8. Base case – 80% maximum load (optimal configuration) 112
7.3. MODELING OF COPPER SX-EW CIRCUIT WITH DITHIONATE 120
7.3.1. Dithionate case - Copper and other elements in PLS 120
7.3.2. Dithionate case – Aqueous phase entrainment in organic phase 127
7.3.3. Dithionate case – Optimal configuration 135
8. REFERENCES 145

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

prediction, testing, detection of a process behavior unrelated to whether the process is
existing in reality or not. Process simulation is there to increase the level of knowledge
for a particular process and chemical engineering in general.
So, when those two concepts are put together, we can look into the chemical
engineering as a discipline defining how the process should be developed and
simulation as the tool helping us to explore the options. Chemical engineering needs to
know how the process should be designed while chemical engineers use the simulation
to explore all the process design options and define the optimal one.

Abstract
The reductive leaching of Cobalt using SO2 gas as reducing agent is a complex
process. The presence of high state of Cobalt, Manganese and Iron ions in the leach
solution catalysis the production of dithionate by using soluble oxygen, oxygen from air
adsorbed on mineral surface and surface oxygen of minerals. The presence of dithionate
in the leach solution decreases the concentration of free sulfate anions to have the
electrical charge neutrality of solution. The purpose of this publication is to study the
effect of the presence of dithionate in the PLS on the copper solvent extraction recovery.
The first step was the establishments of simulation modeling of copper solvent
extraction that can take account the presence of dithionate in solution. The results of
simulation show that the presence of dithionate or other anions (as phosphate) having
negative electrical charge that decreases the concentration of free sulfate in the PLS
decreases the solvent extraction recoveries of Copper and Iron.

1. Introduction
Copper production technology changes drastically in the last 25 years with

introduction of solvent extraction-electrowinning circuit as a copper production
method. The technology of copper solvent extraction produces the most economical
copper from low-grade copper ore. Copper solvent extraction technology consists of two
circuits connected by a common organic phase. In the first step, called extraction step,
metal is extracted from aqueous phase by organic phase. In the second step, called
stripping step, metal is recovered from organic phase. The second aqueous phase is
more pure and concentrated.
At the beginning, copper solvent extraction configuration operating on dilute

aqueous phases were constituted with two stages respectively to extraction and
stripping steps. Design of this 2Ex2S configuration was simple and based on the value of
copper transfer per extractant volume percentage of 0.22 (g/l/1% v/v). This value gives
copper extraction efficiency greater than 98% and copper stripping efficiency of 60%.
Afterwards, understanding that copper extraction efficiency was not the most important
parameter than the cost of copper production plant, one stage of stripping step was
removed and the value of copper transfer was increased to 0.26 (g/l/1%V). Design of
this 2Ex1S configuration was based on the expected value of copper extraction efficiency
of 90%.
MacCabe Thiele method was introduced in design of copper solvent extraction

configuration when copper solvent extraction technology started to be used for high-
grade copper ore. A large number of laboratory tests were required before obtaining the
optimal configuration by using MacCabe Thiele method. It was at this level that a
simulation model of equilibrium line of extraction and stripping steps was introduced.
Several simulation models of copper solvent extraction using chelating reagents

were made. There are three types of simulation models: empirical model, semi-empirical
model and chemical model. Empirical model is an extrapolation equation of the
distribution isotherms. Semi-empirical model is the extrapolation equation of the
distribution ratio of copper between organic and aqueous phases. Chemical empirical is
based on mass-action equilibrium Equations of intermediate chemical reactions.
In the previous paper (KAFUMBILA J., 2022A), a semi-empirical model which is the
extrapolation of thermodynamic property of a global chemical reaction of copper
solvent extraction has been developed. This model takes account of ionic strength of
solution in sulfate media. This model gives one equilibrium condition for extraction step
and stripping step. In this publication, the model is upgrade by introducing the variation
of volume of aqueous phase during extraction or stripping step and the new model is
developed.
Particularly in the DRC and to some extent in Zambia, the oxide ores with
copper and cobalt are leached in atmospheric systems. The dominant mineralization is
malachite/azurite with accessory Chrysocolla and minor other secondary copper
minerals. The cobalt is present as Heterogenite with cobalt in both the Co2+ and Co3+
oxidation state. The cobaltic minerals are about more than 50% of the total cobalt; and
are not direct acid leachable at normal temperatures and pressures. Alternate methods
of enhancing the cobalt leaching are required. Less than 50% of the cobalt is leached
(along with the copper) mainly from the Co2+ minerals. The other cobaltic minerals
need to be reduced to the 2+ state in order for them to leach. This is achieved with
controlled reductive leaching. The reducing agents used to date are sodium meta bi-
sulfite (SMBS: Na2S2O5), gas from a sulfur burning acid plant (SO2 and N2) and pure SO2
gas During the Co3+ leaching, SMBS and SO2 are oxidized in dithionate and sulfate. In
case where SMBS is used as reducing agent, the oxidation product is sodium dithionate.
On the other hand in case where SO2 gas is used as reducing agent, the oxidation product
is cobalt dithionate. This means that the dithionate anion takes the place of sulfate anion
in the solution (J. KAFUMBILA, 2022B).
The goal of this publication is to simulate the effect of the presence of cobalt
dithionate in the PLS on the copper solvent extraction performance. The simply way is to
simulate using the model of the copper solvent extraction developed previously. The
other simulation models do not yet take into account the presence of the other anions in
the solution.

2. Chemistry of solvent extraction
2.1. Classification of metal solvent extraction
Solvent extraction of metallic cation can be classified on process of extraction.

There are four types [AIDI AMEL, 2013]:
 Extraction by salvation
 Extraction by cation exchange
 Extraction by chelation
 Extraction by anion exchange
2.1.1. Extraction by salvation
Solute molecules are associated with the solvent molecules - this is known as
salvation. In extraction by salvation solvent molecules are directly involved in formation
of the ion association complex. In this case the extracted species is solvated with a
certain number of solvent molecules on condition that the extractant must be inert.
2.1.2. Extraction by cation exchange
The extractant is an organic acid (HR) and can exchange hydrogen with cation.
The extraction will proceed with formation of a neutral uncharged species.
2.1.3. Extraction by anion exchange
The cation forms first a complex in aqueous phase having negative charge. The
extractant have an anion which can be exchange with the aqueous cation complex. The
extraction will proceed with formation of a neutral uncharged species.

2.1.4. Extraction by chelation
. The extractant exchanges cation with hydrogen ion as in extraction by cation

exchange. In additional the extractant have chelating ligand. The ligand with two or
more points of attachments to metal atoms are called chelating ligands. The substance
which brings about chelation is called chelating agent and the product is called chelate.
2.2. Chemistry of copper solvent extraction
In case of copper solvent extraction, the extraction is typically achieved by an

oxime-based chelating mechanism. Under low acidic conditions (pH <1), extractant
exchanges hydrogen with copper (extraction). Under high acidic conditions (180 g/L
H2SO4), extractant exchanges copper with hydrogen (strip). Both extraction and
stripping steps are typically designed to achieve equilibrium conditions. The similarities
with binary distillation lead to the use of the McCabe-Thiele method for modeling the
process. The chemical reactions (2.a) and (2.b) give the copper extraction and stripping
reaction with an oxime-based extractant.
CuSO4 + 2HR → CuR2 + H2SO4 (2.a)
CuR2 + H2SO4 → CuSO4 + 2HR (2.b)
Where HR is the extractant and CuR2 is copper-organic complex
The organic phase is a mixture of extractant and diluent. Extractant is an

organic compound which extracts copper from aqueous phase. In industrial practices,
Properties of extractant are: tailored extractive strength, excellent Cu/Fe selectivity, fast
kinetics, good stability, low crud formation and excellent versatility [RITCEY G.M. ET AL,
1984]. There are three kinds of extractant:
 Ketoximes: Ketoximes are moderately strong copper extractant which operate

best when PLS is relatively warm and pH is ~1.8 or above
 Aldoximes: Modified aldoximes have good metallurgical properties even at low
temperatures and low pH
 Mixture of ketoximes and aldoximes: Properties of aldoxime/ketoxime blends
reflect ratio of components
Diluent is an organic liquid in which extractant is dissolved. In general, diluent

must allow solubilisation of extractant. Diluent must have minimum surface tension to

promote dispersion in mixer, low volatility, and high ignition point. Diluent must be
cheaper. Diluent is constituted with various hydrocarbons. Kerosene is often used as a
diluent [RITCEY G.M. ET AL, 1984].
In industrial practices, maximum value of extractant volume percent (v/v) is

between 30 – 33% [RITCEY G.M. ET AL, 1984]. Viscosity of organic phase increases with
increasing extractant volume percent. Above this value, some organic components must
be added to organic phase to improve viscosity.

3. Construction of distribution isotherms
Extraction and strip isotherms are a graphical representation of the equilibrium

copper concentration in the aqueous and organic phases at different organic-to-aqueous
(O/A) ratios. There are two ways of determining the distribution isotherms for a
particular operation: either by performing laboratory-scale tests or by predicted
distribution isotherms based on the extraction and stripping specific conditions.
3.1. Laboratory-scale test
The following procedure for determining the distribution isotherms is followed:
 Select at least 7 organic-to-aqueous (O/A) ratios at which to perform the

test;
 Measure the initial concentration of copper and free acid (PLS for
extraction isotherm or spent electrolyte for stripping isotherm);
 Combine aqueous feed (PLS for extraction and spent electrolyte for
stripping) with previously stripped organic for extraction isotherm or
loaded organic for stripping isotherm at the specified O/A ratio;
 Agitate mixture for a minimum 5 minutes and allow to settle;
 Once settled, sample and measure the concentrations of copper and free
acid in aqueous phase;
 For each O/A point, perform a mass balance to determine the
equilibrium copper concentration in the organic phase or the organic can
also be analyzed to verify the mass balance points

3.2. Predicted distribution isotherms
3.2.1. Classification of predicted distribution isotherms
The theoretical prediction gives copper concentration in organic phase as a

function of copper concentration in aqueous phase. This function is called the model of
distribution isotherm. There are three types of distribution isotherm model: empirical
model, semi-empirical model and chemical model [NOIROT P.A., 1985].
3.2.2. Empirical model
The empirical model gives the equation that best matches the curve of
equilibrium line. Due to the absence of links with the modeled phenomenon, its
extrapolation can be risky and its use is limited to the field covered by the
experimentation.
The empirical model has been developed for dynamic simulation of copper
solvent extraction plant [MORENO C.M. ET AL, 2009]. The equation (3.1) gives the empirical
model of extraction isotherm.
A∗X
Y = X+B (3.1)
Where “Y” is copper concentration in the organic phase, “X” is copper concentration in
the aqueous phase.
Values of “A” and “B” are given by the equations (3.2) and (3.3).
A = a *ML (3.2)
(10−pH )b
B= (d ∗ CuPLS + f* CuRaff ) (3.3)
MLc
Where “ML” is the maximum loading (g/L), “𝐶𝑢𝑃𝐿𝑆 ” is copper concentration in the PLS
(g/L), “𝐶𝑢𝑟𝑎𝑓𝑓 ” is copper concentration in the raffinate and pH of PLS and “a”, “b”, “c”,
“d” and “f” are the constants.
The equation (3.4) gives the empirical model of stripping isotherm.

Y = C*X +D (3.4)
Where “Y” is copper concentration in the organic phase and “X” is copper
concentration in the aqueous phase.
Values of “C” and “D” are given by the equations (3.5) and (3.6).
C = g* ML (3.5)
h∗V%i
D= +m (3.6)
Acj
Where “V%” is the volume percent of extractant in the organic phase and “Ac” is the
acid concentration of spent electrolyte (g/L). “g”, “h”, “i”, “j” and “m” are the constants.
3.2.3. Semi-empirical model
Just like the preceding one, it is based on an equation but which best fits the
curve of distribution ratio of copper. Semi-empirical model uses the overall solvent
extraction reaction. If an aqueous phase containing copper is contacted with an organic
phase, than copper distributes between the aqueous and organic phase according to
equation (3.7).
Cu
DCu = Cuor (3.7)
aq
Where “𝐷𝐶𝑢 ” is the distribution ratio of copper, “𝐶𝑢𝑜𝑟 ” is copper concentration

in organic phase and “𝐶𝑢𝑎𝑞 ” is copper concentration in aqueous phase.
It has been observed that the distribution ratio (D) is a function of free ligand
concentration in the organic phase [LLOYD PHILIP J.D., 2004]. Equation (3.8) gives the
mathematical expression this observation.
Cu
DCu = Cuor = Do ∗ (Lt − mCuor )n (3.8)
aq
Where “𝐷𝑜 ” is the distribution ratio of copper at trace concentrations, readily

determined in the laboratory, “𝐿𝑡 ” is the total ligand concentration in the extractant,
“m” approximates the ratio of ligand molecules to extracted molecules close to
saturation, “n” approximates the ratio of ligand molecules to extracted molecules close
to infinite dilution.
It should be noted that “m” and “n” in equation (3.8) are sometimes equal, but
often differ in value, which underlines that fact that this equation has no theoretical
basis. It is merely a convenient way of representing much experimental data using three
parameters that can readily be determined experimentally.
3.2.4. Chemical model
Chemical model requires the knowledge of all intermediate chemical reactions

of extraction reaction. The first suggestion of intermediate chemical reactions for copper
solvent extraction with oximes based extractant involves the dissolution of extractant in
aqueous phase [DREISINGER D.B., 1988]. Chemical reactions (3.a), (3.b), (3.c), (3.d) and
(3.e) give the intermediate chemical reactions:
HR or ↔ HR aq (step 1) (3.a)
The step 1 involves the dissolution of extractant in the aqueous phase.
+
HR aq ↔ Haq + R−aq (step 2) (3.b)
The step 2 involves the dissociation of extractant in the aqueous phase.
Cu+2 − +
aq + R aq ↔ CuR aq (step 3) (3.c)
The step 3 the first ligand is added to copper in aqueous phase.
CuR+aq + R−aq ↔ CuR 2 aq (step 4) (3.d)
The step 4 the second ligand is added to copper in aqueous phase.
CuR 2 aq ↔ CuR 2 or (step 5) (3.e)
The step 5 the copper complex is absorbed by the organic phase.
The second suggestion of intermediate chemical reactions for copper solvent

extraction with oximes based extractant involves two forms of extractant molecule in
the organic phase [ALGUACIF F.J., 1998]. Chemical reactions (3.f), (3.g) and (3.h) give the
intermediate chemical reactions:
Cu+2 +
aq + 2∗ HR or ↔ CuR 2 or + 2∗ Haq (3.f)
Cu+2 +
aq + (HR)2 or ↔ CuR 2 or + 2∗ Haq (3.g)
(HR)2 or ↔ 2∗ HR or (3.h)

In the case of sulfate solution, the chemical reaction (3.i) must be taken into
account.
HSO− + 2−
4 ↔ H + SO4 (3.i)
The modeling requires the knowledge of the corresponding mass-action

equilibrium equations for the chemical reactions listed above and the mass-balance of
copper, ligand and hydrogen.
The mass-action equilibrium equations and the mass-balance of copper, ligand

and hydrogen for the second suggestion of intermediate chemical reactions are given by
the equations (3.9), (3.10), (3.11), (3.12), (3.13) and (3.14).
All models consider that the chemical activity coefficients of species in aqueous
and organic phases do not change.
[Cu+2 ]aq ∗[HR]2or

[CuR 2 ]or = K1 * (3.9)
[H+ ]2aq
[Cu+2 ]aq ∗[(HR)2 ]or

[CuR 2 ]or = K 2 * (3.10)
[H+ ]2aq
[(HR)2 ]ot = K 3 * [HR]2or (3.11)
[Cu+2 ]taq = [Cu+2 ]aq + A * CuR 2 or (3.12)
[HR]tor = [HR]or + 2* [(HR)2 ]or + 2* [CuR 2 ]or (3.13)
[H +2 ]aq = [H + ]iaq + 2* A* [CuR 2 ]or (3.14)
Where [𝐶𝑢𝑅2 ]𝑜𝑟 is the concentration of copper complex in the organic phase (mol/L),
[𝐻𝑅]𝑜𝑟 is the concentration of the first molecule form of extractant in organic phase
(mol/L), [(𝐻𝑅)2 ]𝑜𝑟 is the concentration of the second molecule form off extractant in
the organic phase (mol/L), [𝐻𝑅]𝑡𝑜𝑟 is the total concentration of ligand in the organic
phase (mol/L), [𝐶𝑢+2 ]𝑎𝑞 is the concentration of copper in aqueous phase, [𝐶𝑢+2 ]𝑡𝑎𝑞 is
the total concentration of copper in aqueous and organic phases, [𝐻 + ]𝑖𝑎𝑞 is the
concentration of hydrogen ion in the feed solution, [𝐻 +2 ]𝑎𝑞 is the concentration of
hydrogen ion in the aqueous phase, and “A” is the ratio of organic phase volume on
aqueous phase volume.

4. New semi-empirical model
4.1. Equilibrium condition
Extraction step is guided by thermodynamic disequilibrium between aqueous

and organic phases. Copper mass transfer is stopped when thermodynamic property
reaches equilibrium condition in both phases. Global copper solvent extraction chemical
reaction with Lix984N extractant is followed chemical reaction (2.a) [HOSSEN AMINIAN,
1999]. LIX 984N reagent, a 1:1 volume blend of LIX 860N-I and LIX 84N-I, is a mixture of
5-nonylsalicylaldoxime and 2-hydroxy-5-nonylacetophenone oxime.
Cu2+ + 2HR ↔ CuR 2 + 2H + (2.a)
where 𝐶𝑢2+and 𝐻 + are copper and hydrogen ionic species in aqueous phase, HR is acid
form of Lix984N extractant, and 𝐶𝑢𝑅2 is copper complex form in organic phase
Thermodynamic equilibrium condition of global chemical reaction (2a) is given

by equation (4.1) [BAUER G.L ET AL, 1976].
μ(CuR2) + 2μ(H+ ) - μ(Cu+2 ) - 2μ(HR) = 0 (4.1)
where μ𝜌 is chemical potential of species ‘ρ’
Chemical potential of species ‘ρ’ is given by equation (4.2).
μρ = μ°ρ +RTln( γρ ∗ Cρ ) (4.2)
where 𝜇𝜌° is standard chemical potential of species ‘ρ’, 𝛾𝜌 is chemical activity coefficient
of specie ‘ρ’, 𝐶𝜌 is molar concentration of species ‘ρ’, R is the perfect gas constant, and T
is the temperature
The substitution of equation (4.2) for all species in equation (4.1) gives
equation (4.3) which is the thermodynamic equilibrium condition. Equation (4.4) gives
Gibbs standard free energy of the chemical reaction (2.a).
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2 −Δ𝐺° (γ(HR) )2

= e( )
(H )
RT * = ψe (4.3)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2 γ(CuR2)

ΔG° =μ°(CuR2 ) -μ°(Cu+2 ) -2μ°(HR) (4.4)
Where 𝐶𝜌𝑒 is equilibrium molar concentration of species “ρ”.
4.2. Value of 𝛙𝐞𝟏
4.2.1. Definition
The value of thermodynamic equilibrium condition ψe from left component of

Equation (4.3) called ψe1 is given by equation (4.5).
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
= ψe1 (4.5)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
4.2.2. Copper molar concentration in organic phase
The value of copper molar concentration at the steady-state in organic is given

by equation (4.6).
e Cue(or)
C(CuR 2)
= (4.6)
63.54
𝑒
where 𝐶𝑢𝑜𝑟 is copper concentration (g/L) in organic phase.
4.2.3. Free extractant molar concentration in organic phase
The value of free extractant molar concentration in organic phase is given by

Equation (4.7).
v/V%∗ 0.91∗ 1000

C(HR) = (4.7)
100∗ 270
where v/v% is extractant volume percentage (v/v%) in organic phase. 0.91 is the
density of Lix984N extractant. 270 is the mass molar of Lix984N extractant.
After extraction of Copper, the value of free extractant molar concentration in

organic phase is given by Equation (4.8). The assumption is that the variation of organic
phase volume due to the presence of Copper in organic phase is negligible.

e v/V%∗ 0.91∗ 1000 e
C(HR) = – 2*C(CuR 2)
(4.8)
100∗ 270
4.2.4. Cu-Sulfate system
4.2.4.1. Activity of soluble species
 Ionic strength
The ionic strength (I) of the solution is the first to know because the
electrostatic interactions depend on the concentration of charge. The value of ionic
strength is calculated using Equation (4.9). “Zn ” is the charge of soluble compound “n”
and “Cn ” is the concentration of soluble compound “n”. The ionic strength has
concentration units.
1
I=2 x ∑n Zn2 ∗ Cn (4.9)
 Helgeson Equation
The calculations of individual ion activity coefficient have been approximated by

Equation (4.10) in concentrated as well as dilute electrolyte solutions involved in
geochemical processes at high temperatures and pressures (H.C. HELGESON ET AL, 1981)
and suitable for overall equilibrium diagram calculations. “γp ” is the activity coefficient
of soluble compound “p”, “Zp ” is the electrical charge of compound “p” and “I” is the ionic
strength (mol/kg of water). “A”, “B” and “b” are temperature-dependent parameters.
Table (4.1) gives values of parameters “A”, “B” and “b” at 25°C (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).
Z2p A√I
Log(γp )= - (1+Bä√I) – log(1+0.018015*I)+b*I (4.10)
Table 4.1: values of A, B and b parameter at 25°C
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).

In copper solvent extraction the concentrations of species are less the 2mol/L.
In this case, molarity is equal to molality.
 Activity of water
The activity of water (solvent) (𝑎𝑤 ) is given by Equation (4.11). “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)
W
ln(aw ) = - 1000 *ϕ *∑i mi (4.11)
The calculations of osmotic coefficient have been approximated by Equation

(4.12) (H.C. HELGESON, 1969). The value of “u” is given by Equation (4.13). Table (4.2)
gives values of parameters “a”, “b”, “c” and “d” at 25°C. “A” comes from Debrye-Huckel
equation for activity coefficient and is function of temperature. The value of “A” is
0.5092 at 25°C. “I” is the ionic strength (mol/kg of water).
2.303∗A 1 b∗I 2c∗I2 3d∗I3

ϕ=1- [u -2ln(u) - u] + + + (4.12)
a3 ∗I 2 3 4
u=1+a*√I (4.13)
Table 4.2: values of a, b, c and d parameter at 25°C
a b c d
1.454 0.02236 9.38 x10−3 -5.362x10−4
4.2.4.2. Cu-Sulfate-Water System
 Water
The chemical reaction (4.a) gives the water ionization reaction. Logarithm of the
equilibrium constant of the chemical reaction (4.a) is given in Table (4.3) at 25°C
(MINTEQA2-V.4, 1999).
H2 O = H + + OH − (4.a)
Table 4.3: Log(K) of reaction (4.a) at 25°C
Chemical reactions logK Reference

4.a -13.998 MINTEQA2-V.4, 1999

At pH below 2, the concentration of OH − is negligible in aqueous solution. The
designation of concentration (mol/L) of H + is C(H+) . Equation (4.14) gives the value of
C(H+) from a known value of pH.
10(−pH)
C(H+ ) = (4.14)
γ(H+ )
 Free sulfate
The free soluble compounds are the following: H2 SO4 , HSO4 − and SO4 −2 . The
chemical reactions (4.b) and (4.c) give the equilibrium reaction between SO4 −2 and
other substances. Table (4.4) gives the equilibrium constant of the chemical reaction
(5.b).
SO−2 + −
4 + H =HSO4 (4.b)
SO−2 +
4 + 2H =H2 SO4 (4.c)
Table 4.4: Log(K) of reaction (4.b) and (4.c) at 25°C

4.a 1.99 MINTEQA2-V.4, 1999
4.b -0.053 MINTEQA2-V.4, 1999
The designation of concentration (mol/L) of soluble substances of sulfate is the

following:
Concentration of SO−2
4 is C(SO−2
4 )
,
Concentration of HSO−4 is C(HSO−4 ) ,
Concentration of H2 SO4 is C(H2 SO4) .
The concentrations C(HSO−4 ) and C(H2 SO4) are calculated as function of

concentration of soluble compounds (H + and SO−2
4 ) using Equations (4.15) and (4.16)
coming from the mass actions of the chemical reaction (4.b) and (4.c). The
concentration C(SO−2
4 )
is is unknown value.
(−1)
C(HSO−4 ) =10(1.99) *C(H+) *γ(H+) *C(SO−2
4 )
*γ(SO−2
4 )
*γ(HSO−4 ) (4.15)
C(H2 SO4 ) =10(−0.053) *(C(H+ ) ∗ γ(H+ ) )(2) *C(SO−2

4 )
*γ(SO−2
4 )
(4.16)

The assumption is that the positive charge of H + is neutralized by the negative
charge of HSO− 4 which is the major sulfate soluble compounds in the range of pH from
0.0 to 2.0. In this condition Equation (4.17) gives the concentration of free acid (C(Ac))
(g/L) in aqueous solution.
C(Ac) =(C(H+) +C(H2 SO4) )*98.08 (g/L) (4.17)
 Copper
The major copper soluble compounds in the range of pH from 0.0 to 2.0 are the
following: Cu+2 , and CuSO4 . The chemical reaction (4.d) gives the equilibrium reaction
between the major soluble compounds of copper. Table (4.5) gives the equilibrium
constant of the chemical reaction (4.d).
Cu+2 + SO−2
4 = CuSO4 (4.d)
Table 4.5: Log(K) of reaction (4.d) at 25°C

4.d 2.36 MINTEQA2-V.4, 1999
The designation of concentration of soluble substances of copper soluble

compounds is the following:
Concentration of Cu+2 is C(Cu+2 ) ,

Concentration of CuSO4 is C(CuSO4) .
The concentration C(CuSO4) is calculated as function of concentration of Cu+2 ,

and SO4 −2 using Equation (4.18) coming from the mass action of the chemical reaction
(4.d). The concentration C(Cu+2 ) is unknown value.
C(CuSO4 ) =10(2.36) *C(Cu+2 ) *γ(Cu+2 ) *C(SO−2

4 )
*γ(SO−2
4 )
(4.18)
Equation (4.19) gives the concentration of Copper in aqueous solution (Cu(aq) )

in (g/L).
C(CuT) =(C(Cu+2 ) +C(CuSO4 ))*63.54 (4.19)
 Electrical neutrality of aqueous solution
The electrical neutrality of solution is given by Equation (4.20).
C(HSO−4 ) +2C(SO−2
4 )
=C(H+) +2C(Cu+2 ) (4.20)

 Constraints in the aqueous solution
 The concentration C(H+) is given by Equation (4.14) when pH is the

known value or by Equation (4.17) when free acid concentration is the
known value.
 Equations (4.15), (4.16), (4.18), (4.19) and (4.20) give the values of
C(HSO−4 ) , C(SO−2
4 )
, C(H2 SO4 ), C(Cu+2 ) and C(CuSO4 ) .
4.2.5. Constraint during copper solvent extraction
4.2.5.1. Initial aqueous phase
i
The known values in the initial aqueous phase are the initial volume (V(aq) ) (m3)
i i
and the concentrations of Copper (C(CuT) ) and free acid (C(Ac) ) (g/L). The molar
concentrations of soluble species (H + , SO−2 −
4 , HSO4 , H2 SO4 , Cu
+2
and CuSO4 ) are
unknown.
i −2 i i
The molar concentration of H + (C(H + ) ), SO4 (C
(SO−2 ) ) and Cu
+2
(C(Cu +2 ) ) are the
4
i
molar concentrations from which the molar concentrations of HSO−
4 (C(HSO−
4)
), H2 SO4
i i
(C(H 2 SO4 )
) and CuSO4 (C(CuSO 4)
) according to Equations (4.21), (4.22) and (4.23).
i i
C(iHSO−4 ) )=10(1.99) *C(H + ) *C
i
(SO−2 ) *γ(2) (4.21)
4
i i i (2) i
C(H 2 SO4 )
=10(−0.053) *(C(H + ) ∗ γ(1) ) *C(SO−2 ) *γi(2) (4.22)
4
i i i i
C(CuSO 4)
=10(2.36) *C(Cu+2 ) *C(SO−2 ) *(γ(2) )
2
(4.23)
4
The values of γi(1) and γi(2) are given by Equations (4.24) and (4.25). The value of
ionic strength (Ii ) is given by Equation (4.26).
0.509∗√Ii
Log(γi(1) )= - – log(1+0.018015*Ii )+0.064*Ii (4.24)
(1+1.22∗√Ii )
4∗0.509∗√Ii
Log(γi(2) )= - – log(1+0.018015*Ii )+0.064*Ii (4.25)
(1+1.22∗√Ii )
1 i i i i
Ii =2*(C(H + ) +4*C
(SO−2 ) +C(HSO4 ) +4*C(Cu+2 ) )
− (4.26)
4

i i
Equations (4.27), (4.28) and (4.29) allow calculating the values of C(H +) , C
(SO−2 )4
i
and C(Cu+2 ) . Equation (4.29) gives the electrical charge neutrality of solution.
i i i
C(CuT) =(C(Cu+2 ) +C(CuSO ) )*63.54
4
(4.27)
i i i
C(Ac) =(C(H + ) +C(H SO ) )*98.08
2 4
(4.28)
i i i i
C(H + ) +2*C(Cu+2 ) =2*C
(SO−2 ) +C(HSO4 )
− (4.29)
4
Equation (4.30) gives the specific gravity of aqueous phase (J. KAFUMBILA, 2017A).
Equation (4.31) gives the value of CT .
i
SG(aq) = -6.139 * 10−7 x [CTi ]2 + 9.742 * 10−4 *CTi + 1 (4.30)
𝑖
Where “𝑆𝐺(𝑎𝑞) ” is liquid specific gravity (t/m3) and “𝐶𝑇𝑖 ” is total concentration of
soluble species (g/L)
i i i i i
CTi =1.007*C(H + ) +96.06*(C(CuSO ) +C
4 (SO−2 ) )+97.07*C(HSO4 ) +98.08*C(H2 SO4 ) +
−
4
i
C(CuT) (4.31)
Where 1.007 is molar mass of 𝐻 + , 96.06 is molar mass of 𝑆𝑂4−2 , 97.07 is molar
mass of 𝐻𝑆𝑂4− and 98.08 is molar mass of 𝐻2 𝑆𝑂4.
Equation (4.32) gives the mass of aqueous phase for a known volume. Where
i
V(aq) is initial volume of aqueous phase.
i i i
M(aq) =SG(aq) *V(aq) (t) (4.32)
Equation (4.33) gives total concentration sulfur in solution (g/L). Where 32.065
is molar mass of sulfur.
i i i i i
C(ST) =(C(SO −2 ) +C(HSO− ) +C(H SO ) +C(CuSO ) )*32.065
4 2 4 4
(4.33)
4
4.2.5.2. Equilibrium aqueous phase
The known value in the equilibrium aqueous phase is the concentration of

e
Copper (C(CuT) ) (g/L). The molar concentrations of soluble species (H + , SO−2 −
4 , HSO4 ,
H2 SO4 , Cu+2 and CuSO4 ) are unknown.

e −2 e e
The molar concentration of H + (C(H + ) ), SO4 (C
(SO−2 ) ) and Cu
+2
(C(Cu +2 ) ) are the
4
𝑒
molar concentrations from which the molar concentrations of HSO−
4 (C(HSO−
4)
), H2 SO4
e e
(C(H 2 SO4 )
) and CuSO4 (C(CuSO 4)
) according to Equations (4.34), (4.35) and (4.36).
e e
C(eHSO−4 ) )=10(1.99) *C(H + ) *C
e
(SO−2 ) *γ(2) (4.34)
4
e e e (2) e
C(H 2 SO4 )
=10(−0.053) *(C(H + ) ∗ γ(1) ) *C(SO−2 ) *γe(2) (4.35)
4
e e e e
C(CuSO 4)
=10(2.36) *C(Cu+2 ) *C
(SO−2 ) *(γ(2) )
2
(4.36)
4
The values of γe(1) and γe(2) are given by Equations (4.37) and (4.38). The value of
ionic strength (Ie ) is given by Equation (4.39).
0.509∗√Ie
Log(γe(1) )= - (1+1.22∗√Ie ) – log(1+0.018015*Ie )+0.064*Ie (4.37)
4∗0.509∗√Ie
Log(γ𝑒(2) )= - (1+1.22∗√Ie ) – log(1+0.018015*Ie )+0.064*Ie (4.38)
1 e e e e
Ie =2*(C(H + ) +4*C
(SO−2 ) +C(HSO4 ) +4*C(Cu+2 ) )
− (4.39)
4
Equation (4.40) gives mass of aqueous phase at equilibrium. Where MCu is

extracted mass of Cu from aqueous phase and MH is stripped mass of H from organic
phase. Equation (4.41) gives the value of MH . Where 1.007 is molar mass of H and 63.54
e
is molar mass of Cu. Equation (4.42) gives the value of MCu. Where V(aq) (m3) is the value
of volume of aqueous phase at equilibrium and is unknown value.
e i
M(aq) =M(aq) - MCu + MH (t) (4.40)
1.007
MH =MCu*2*63.54 (t) (4.41)
i i e e
MCu=(V(aq) *C(CuT) - V(aq) *C(CuT) )/1000 (t) (4.42)
e e
Equation (4.43) gives the relation between M(aq) and V(aq) .
e e e
M(aq) =SG(aq) *V(aq) (4.43)

𝑒
SG(aq) = -6.139 * 10−7 x [CTe ]2 + 9.742 * 10−4 *CTe + 1 (4.44)
𝑒
e e e e e
CTe =1.007*C(H + ) +96.06*(C(CuSO ) +C
4 (SO−2 ) )+97.07*C(HSO4 ) +98.08*C(H2 SO4 ) +
−
4
e
C(CuT) (4.45)
e e
Equations (4.46), (4.47) and (4.48) allow calculating the values of C(H +) , C
(SO−2 )4
e
and C(Cu+2 ) . Equation (4.47) gives the electrical charge neutrality of solution. Equation
e
(4.49) gives the value of C(ST) .
e e e
C(CuT) =(C(Cu+2 ) +C(CuSO ) )*63.54
4
(4.46)
e e e e
C(H + ) +2*C(Cu+2 ) =2*C
(SO−2 ) +C(HSO4 )
− (4.47)
4
i i e e
C(ST) *V(aq) =C(ST) *V(aq) (4.48)
𝑒 e e e e
C(ST) =(C(SO −2 ) +C(HSO− ) +C(H SO ) +C(CuSO ) )*32.065
4 2 4 4
(4.49)
4
4.3. Value of 𝛙𝐞𝟐
4.3.1. Definition
The value of thermodynamic equilibrium condition ψe from right component of

Equation (4.3) called ψe2 is given by equation (4.50).
−Δ𝐺° (γ(HR) )2
e( RT
)
* =ψe2 (4.50)
γ(CuR2)
In organic phase, the study done on the extractant Kelex 100, which is chelating
copper solvent extraction reagent, shows that ratio of chemical activity coefficients of
species in organic phase is a function of copper concentration in organic phase [ BAUER
G.L ET AL, 1976]. The assumption is that this thermodynamic property is also true for
chelating copper extractant as Lix984N.

Conclusion from this assumption is that the thermodynamic equilibrium
condition is given by equation (4.51).
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H ) e
=f(C(CuR 2)
) (4.51)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
4.4. Equation of thermodynamic equilibrium condition
4.4.1. Equation of modelling of equilibrium condition
Test conditions of lab test 1 done with pure copper sulfate aqueous phase are
the following:
 Initial copper concentration in aqueous phase: 8 g/l.

 Initial free acid concentration in aqueous phase: 5 g/l.
 Extractant: Lix984N.
 Extractant volume percentage in organic (v/v%): 20%.
Table (4.6) gives equilibrium line data of lab test 1 from which the values of
thermodynamic equilibrium condition ψe1 of each steady-state position are calculated.
Table 4.6: Value of ψe1 from equilibrium line data of lab test 1
Cu(aq) (g/L) 0.04 0.09 0.35 1.19 3.38 5.92 6.93

Cu(or) (g/L) 0.80 1.58 3.83 6.76 9.26 10.45 10.70
Figure (4.1) gives the values of thermodynamic equilibrium condition ψe1

versus the values of copper concentration in organic phase.
Results show that the value of thermodynamic equilibrium condition ψe1 is a

linear function of the value of copper concentration in organic phase. Equation (4.52)
gives the modelling of thermodynamic equilibrium condition.
ψe1 =a*Cu(or) +b (4.52)

Figure 4.1: Values of ψe1 versus values of copper concentrations in organic
phase of lab test 1
4.4.2. Effect of initial free acid concentration
Table (4.7) gives equilibrium line data of lab test 1, 3, 4 and 5. The initial acid
concentration is increased from 5 to 20g/L. Figure (4.2) gives the value of
thermodynamic equilibrium condition ψe1 versus the values of copper concentration in
organic phase for Data in Table (4.7).
The results on Figure 4.2 show that when the initial acid concentration
increases the thermodynamic equilibrium condition remains a linear function of copper
concentration in the organic phase and the initial free acid concentration of feed solution
does not affect the values of constants “a” and “b”.

Table 4.7: Equilibrium line data of lab tests 1, 3, 4 and 5
Lab test 1 Lab test 3 Lab test 4 Lab test 5

Cuiaq 8 g/l Cuiaq 8 g/l Cuiaq 8 g/l Cuiaq 8 g/l
i 5 g/l i 10 g/l i 15 g/l i 20 g/l
Acaq Acaq Acaq Acaq
V/V% 20 % V/V% 20 % V/V% 20 % V/V% 20 %
Cueaq Cueor Cueaq Cueor Cueaq Cueor Cueaq Cueor
0.04 0.80 0.10 0.80 0.15 0.79
0.09 1.58 0.23 1.56 0.33 1.54
0.35 3.83 0.57 3.74 0.76 3.63 0.98 3.52
1.19 6.76 1.70 6.31 2.00 6.01 2.42 5.59
3.38 9.26 3.80 8.40 4.20 7.80 4.41 7.20
5.92 10.45 6.10 9.55 6.30 9.00 6.35 8.30
6.93 10.70 7.00 10.01 7.10 9.30 7.17 8.74
Figure 4.2: Values of ψe1 versus values of copper concentration in

organic phase of lab tests 1, 3, 4 and 5

4.4.3. Effect of extractant volume percent in organic phase
Table (4.8) gives equilibrium line data of lab test 1, 6 and 7. Figure (4.3) gives
the value of thermodynamic equilibrium condition ψe1 versus the values of copper
concentration in organic phase.
The results of Figure (4.3) show that the slope of equilibrium condition line
decreases when the extractant volume percent increases.
Table 4.8: Equilibrium line data of lab tests 1, 6, and 7 of extraction step
Lab test 6 Lab test 7 Lab test 1

Cuiaq 8.04 g/l Cuiaq 5.5 g/l Cuiaq 8.01 g/l
i 20 g/l i 0.980 g/l i 5.0 g/l
Acaq Acaq Acaq
v/v% 15 % v/v% 18 % v/v% 20 %
e
Cuaq Cueor Cueaq Cueor e
Cuaq Cueor
0.27 0.78 0.08 2.89 0.04 0.80
0.48 1.50 0.13 3.82 0.09 1.58
1.56 3.24 0.31 5.57 0.35 3.83
3.30 4.68 1.63 8.20 1.19 6.76
5.16 5.62 2.70 8.77 3.38 9.26
6.80 6.20 3.71 9.07 5.92 10.45
7.40 6.39 5.51 9.23 6.92 10.80

organic phase of lab tests 1, 6, and 7
4.4.4. Effect of presence of other elements in solution
4.4.4.1. Initial aqueous phase
i
The known values in the initial aqueous phase are the initial volume (V(aq) ) (m3)
i i i i
and the concentrations of Copper (C(CuT) ), Co (C(CoT) ), Al (C(AlT) ), Fe (C(FeT) ), Mg
i i i i i
(C(MgT) ), Mn (C(MnT) ), Zn(C(ZnT) ), Ni (C(NiT) ) and free acid (C(Ac) ) (g/L). The molar
concentrations of soluble species (H + , SO−2 − +2 +2
4 , HSO4 , H2 SO4 , Cu , CuSO4 , Co , CoSO4 ,
Al+3 , AlSO+ − +2 +2
4 , Al(SO4 )2 , AlHSO4 , Fe , FeSO4 , Fe+3, FeSO+ − +2
4 , Fe(SO4 )2 , FeHSO4 ,
FeH(SO4 )2, Mg +2 , MgSO4 , Mn+2, MnSO4, Zn+2, ZnSO4 , Ni+2 , and NiSO4 ) are unknown.
i −2 i i
The molar concentration of H + (C(H + ) ), SO4 (C(SO −2 ) ), Cu
+2
(C(Cu +2 ) ), Co
+2
4
i +3 i +2 i +2 i +2 i +2 i
(C(Co +2 ) ), Al (C(Al +3 ) ), Fe (C(Fe+2 ) ), Mg (C(Mg +2 ) ), Mn (C(Mn +2 ) ), Zn (C(Zn+2 ) )
+2 i
and Ni (C(Ni+2 ) ) are the molar concentrations from which the molar concentrations of
remaining soluble compounds are calculated according to Equations (4.21), (4.22),

(4.23) and from (4.53) to (4.65).

i i
C(iHSO−4 ) )=10(1.99) *C(H + ) *C
i
(SO−2 ) *γ(2) (4.21)
4
i i i (2) i
C(H 2 SO4 )
=10(−0.053) *(C(H + ) ∗ γ(1) ) *C(SO−2 ) *γi(2) (4.22)
4
i i i i
C(CuSO 4)
=10(2.36) *C(Cu+2 ) *C
(SO−2 ) *(γ(2) )
2
(4.23)
4
Co+2 + SO−2
4 = CoSO4 (4.e)
i i i i
C(CoSO 4)
=10(2.30)*C(Co +2 ) *C
(SO−2 ) *(γ(2) )
2
(4.53)
4
Al+3 + SO−2 +
4 = AlSO4 (4.f)
i (3.59) i i i i i (−1)
C(AlSO + ) =10 *C(Al+3 )*C(SO −2 ) *γ(3) *γ(2) *(γ(1) ) (4.53)
4 4
Al+3 +2SO−2 −
4 = Al(SO4 )2 (4.g)
i (4.92) i i (2) i
C(Al(SO − =10
4 )2 )
*C(Al+3 ) *(C(SO −2 ) ) *γ(3) *(γi(2) )(2) *γi(2) *(γi(1) )(−1) (4.54)
4
Al+3 +H + + SO−2 +2
4 = AlHSO4 (4.h)
i (2.45) i i i i i
C(AlHSO+2 ) =10 *C(Al+3 ) *C(H + ) *C
(SO−2 ) *γ(3) *γ(1) (4.55)
4 4
Fe+2 + SO−2
4 = FeSO4 (4.i)
i i i i
C(FeSO 4)
=10(2.39) *C(Fe+2 ) *C(SO−2 ) *(γ(2) )
2
(4.56)
4
Fe+3+e− =Fe+2 (4.j)
(E−E° )∗96485
i
C(Fe i i i
+3 ) =C(Fe+2 ) *(γ(2) *(γ(3) )
(−1)
*10(8.314∗298.15∗2.303) (4.57)
Where E=0.57V and 𝐸 ° =0.77
Fe+3 + SO−2 +
4 = FeSO4 (4.k)
i (4.05) i i i i i (−1)
C(FeSO + ) =10 *C(Fe+3 )*C(SO −2 ) *γ(3) *γ(2) *(γ(1) ) (4.58)
4 4
Fe+3 +2SO−2 −
4 = Fe(SO4 )2 (4.l)
i (5.38) i i (2) i
C(Fe(SO − =10
4 )2 )
*C(Fe+3 ) *(C(SO −2 ) ) *γ(3) *(γi(2) )(2) *γi(2) *(γi(1) )(−1) (4.59)
4

Fe+3 +H + + SO−2 +2
4 = FeHSO4 (4.m)
i (2.48) i i i i i
C(FeHSO +2 =10
) *C(Fe+3 ) *C(H + ) *C
(SO−2 ) *γ(3) *γ(1) (4.60)
4 4
Fe+3 +H + + 2SO−2
4 =FeH(SO4 )2 (4.n)
i i i i i i i
C(FeH(SO 4 )2 )
=10(8.10) *C(Fe+3 ) *C(H+ ) *(C
(2)
(SO−2 ) ) **γ(3) *γ(1) *(γ(2) )
2
(4.61)
4
Mg +2 + SO−2
4 = MgSO4 (4.o)
i i i i
C(MgSO 4)
=10(2.26) *C(Mg +2 ) *C(SO−2 ) *(γ(2) )
2
(4.62)
4
Mn+2 + SO−2
4 = MnSO4 (4.p)
i i i i
C(MnSO 4)
=10(2.25) *C(Mn +2 ) *C(SO−2 ) *(γ(2) )
2
(4.63)
4
Zn+2 + SO−2
4 = ZnSO4 (4.q)
i i i i
C(ZnSO 4)
=10(2.46)*C(Zn +2 ) *C(SO−2 ) *(γ(2) )
2
(4.64)
4
Ni+2 + SO−2
4 = NiSO4 (4.r)
i i i i
C(NiSO 4)
=10(2.46) *C(Ni+2 ) *C(SO−2 ) *(γ(2) )
2
(4.65)
4
The values of γi(1) , γi(2) and γi(3) are given by Equations (4.24), (4.25) and (4.66).
The value of ionic strength (Ii ) is given by Equation (4.67).
0.509∗√Ii
Log(γi(1) )= - – log(1+0.018015*Ii )+0.064*Ii (4.24)
(1+1.22∗√Ii )
4∗0.509∗√Ii
Log(γi(2) )= - – log(1+0.018015*Ii )+0.064*Ii (4.25)
(1+1.22∗√Ii )
9∗0.509∗√Ii
Log(γi(3) )= - – log(1+0.018015*Ii )+0.064*Ii (4.66)
(1+1.22∗√Ii )
1 i i i i i i i i
Ii =2*(C(H + ) +4*C
(SO−2 ) +C(HSO4 ) +4*C(Cu+2 ) +4*C(Co+2 ) +9*C(Al+3 ) +C(AlSO+ ) +C(Al(SO4 )2 ) +
− −
4 4
i i i i i i i
4*C(AlHSO +2 ) +4*C(Fe+2 ) +9*C(Fe+3 ) +C(FeSO+ ) +C(Fe(SO )− ) +4*C(FeHSO+2 ) +4*C(Mg+2 ) +
4 2
4 4 4
i i i
4*C(Mn +2 ) +4*C(Zn+2 ) +4*C(Ni+2 ) ) (4.67)

Equations (4.27), (4.28), (4.29) and from (4.68) to (4.75) allow calculating the
values of concentrations of soluble compounds. Equation (4.75) gives the electrical
charge neutrality of solution.
i i i
C(CuT) =(C(Cu+2 ) +C(CuSO ) )*63.54
4
(4.27)
i i i
C(Ac) =(C(H + ) +C(H SO ) )*98.08
2 4
(4.28)
i i i
C(CoT) =(C(Co +2 ) +C(CoSO ) )*58.93
4
(4.68)
i i i i i
C(AlT) =(C(Al +3 ) +C(AlSO+ ) +C(Al(SO )− ) +C(AlHSO+2 ) )*26.98
4 2
(4.69)
4 4
i i i i i i i i
C(FeT) =(C(Fe+2 ) +C(FeSO ) +C(Fe+3 ) +C(FeSO+ ) +C(Fe(SO )− ) +C(FeHSO+2 ) +C(FeH(SO ) ) )
4 4 2 4 2
4 4
*55.85 (4.70)
i i i
C(MgT) =(C(Mg +2 ) +C(MgSO ) )*24.31
4
(4.71)
i i i
C(MnT) =(C(Mn +2 ) +C(MnSO ) )*54.94
4
(4.72)
i i i
C(ZnT) =(C(Zn+2 ) +C(ZnSO ) )*65.38
4
(4.73)
i i i
C(NiT) =(C(Ni+2 ) +C(NiSO ) )*58.69
4
(4.74)
i i i i i i i i
C(H + ) +2*C(Cu+2 ) +2*C(Co+2 ) +C(Al+3 ) +C(AlSO+ ) +2*C
(AlHSO+2 ) +C(Fe+2 ) +C(Fe+3 ) +
4 4
i i i i i i i
C(FeSO + ) +2*C
(FeHSO+2 ) +2*C(Mg+2 ) +2*C(Mn+2 ) +2*C(Zn+2 ) +2*C(Ni+2 ) =2*C(SO−2 ) +
4 4 4
C(iHSO−4 ) +C(Al(SO
i i
− +C(Fe(SO )− )
4 )2 ) 4 2
(4.75)
i
SG(aq) = -6.139 * 10−7 x [CTi ]2 + 9.742 * 10−4 *CTi + 1 (4.30)
𝑖
i i i i i i
CTi =1.007*(C(H + ) +C
(AlHSO+2 ) +C(FeHSO+2 ) +C(FeH(SO4 )2 ) )+96.06*(C(SO−2 ) +C(CuSO4 )
4 4 4
i i i i i i i
+C(CoSO4)
+C(AlSO + ) +2*C(Al(SO )− ) +C
(AlHSO+2 +C(FeSO 4)
+C(FeSO + ) +2*C(Fe(SO )− ) +
4 4 2 4 ) 4 4 2
i i i i i i
C(FeHSO +2 ) +2*C(FeH(SO ) ) +C(MgSO ) +C(MnSO ) +C(ZnSO ) +C(NiSO ) )+97.07*
4 2 4 4 4 4
4

C(iHSO−4 ) +98.08*C(H
i
2 SO4 )
i
+C(CuT) i
+C(CoT) i
+C(AlT) i
+C(FeT) i
+C(MgT) i
+C(MnT) i
+C(ZnT) +
i
+C(NiT) + (4.76)
Where 1.007 is molar mass of H, 96.06 is molar mass of 𝑆𝑂4−2 , 97.07 is molar
Equation (4.32) gives the mass of aqueous phase for a known volume. Where
i
V(aq) is initial volume of aqueous phase.
i i i
M(aq) =SG(aq) *V(aq) (t) (4.32)
Equation (4.77) gives total concentration sulfur in solution (g/L). Where 32.065
is molar mass of sulfur.
i i i i i i i i
C(ST) =(C(SO −2 ) +C(HSO− ) +C(H SO ) +C(CuSO ) +C(CoSO ) +C(AlSO+ ) +2*C(Al(SO )− ) +
4 2 4 4 4 4 2
4 4
i i i i i i i
C(AlHSO+2 ) +C(FeSO ) +C(FeSO+ ) +2*C(Fe(SO )− ) +C(FeHSO+2 ) +2*C(FeH(SO ) ) +C(MgSO )
4 4 2 4 2 4
4 4 4
i i i
+C(MnSO4)+C(ZnSO4 )+C(NiSO4) )*32.065 (4.77)
4.4.4.2. Equilibrium aqueous phase
The known value in the equilibrium aqueous phase is the concentration of

e
Copper (C(CuT) ) (g/L). The molar concentrations of soluble species (H + , SO−2 −
4 , HSO4 ,
H2 SO4 , Cu+2, CuSO4 , Co+2 , CoSO4 , Al+3 , AlSO4+ , Al(SO4 )− +2 +2 +3
2 , AlHSO4 , Fe , FeSO4 , Fe ,
FeSO+ − +2 +2 +2 +2
4 , Fe(SO4 )2 , FeHSO4 , FeH(SO4 )2 , Mg , MgSO4 , Mn , MnSO4 , Zn , ZnSO4 , Ni ,
+2
and NiSO4 ) are unknown.
e −2 e e
The molar concentration of H + (C(H + ) ), SO4 (C(SO −2 ) ), Cu
+2
(C(Cu+2 ) ) Co
+2
4
e +3 e +2 e +2 e +2 e +2 e
(C(Co +2 ) ), Al (C(Al +3 ) ), Fe (C(Fe+2 ) ), Mg (C(Mg +2 ) ), Mn (C(Mn +2 ) ), Zn (C(Zn+2 ) )
e
and Ni+2 (C(Ni+2 ) )are the molar concentrations from which the molar concentrations of
other soluble compounds are calculated according to Equations (4.34), (4.35), (4.36).
e e
C(eHSO−4 ) )=10(1.99) *C(H + ) *C
e
(SO−2 ) *γ(2) (4.34)
4
e e e (2) e
C(H 2 SO4 )
=10(−0.053) *(C(H + ) ∗ γ(1) ) *C(SO−2 ) *γe(2) (4.35)
4
e e e e
C(CuSO 4)
=10(2.36) *C(Cu+2 ) *C(SO−2 ) *(γ(2) )
2
(4.36)
4
e e e e 2
C(CoSO 4)
=10(2.30)*C(Co +2 ) *C(SO−2 ) *(γ(2) ) (4.78)
4

e (3.59) e i e e e (−1)
C(AlSO + =10
) *C(Al+3 )*C(SO −2 ) *γ(3) *γ(2) *(γ(1) ) (4.79)
4 4
e (4.92) e e (2) e
C(Al(SO − =10
4 )2 )
*C(Al+3 ) *(C(SO −2 ) ) *γ(3) *(γe(2) )(2) *γe(2) *(γe(1) )(−1) (4.80)
4
e (2.45) e e e e e
C(AlHSO+2 =10
) *C(Al+3 ) *C(H + ) *C
(SO−2 ) *γ(3) *γ(1) (4.81)
4 4
e e e e 2
C(FeSO 4)
=10(2.39) *C(Fe+2 ) *C
(SO−2 ) *(γ(2) ) (4.82)
4
(E−E° )∗96485
e
C(Fe e e e (−1)
+3 ) =C(Fe+2 ) *(γ(2) *(γ(3) ) *10(8.314∗298.15∗2.303) (4.83)
Where E=0.57V and 𝐸 ° =0.77
e (4.05) e e e e e (−1)
C(FeSO + ) =10 *C(Fe+3 )*C(SO −2 ) *γ(3) *γ(2) *(γ(1) ) (4.84)
4 4
e (5.38) e e (2) e
C(Fe(SO − =10
4 )2 )
*C(Fe+3 ) *(C(SO −2 ) ) *γ(3) *(γe(2) )(2) *γe(2) *(γe(1) )(−1) (4.85)
4
e (2.48) e e e e e
C(FeHSO +2 ) =10 *C(Fe+3 ) *C(H + ) *C
(SO−2 ) *γ(3) *γ(1) (4.86)
4 4
e e e e
C(FeH(SO 4 )2 )
=10(8.10) *C(Fe+3 ) *C(H+ ) *(C(SO−2 ) )
(2)
**γe(3) *γe(1) *(γe(2) )2 (4.87)
4
e e e e 2
C(MgSO 4)
=10(2.26) *C(Mg +2 ) *C(SO−2 ) *(γ(2) ) (4.88)
4
e e e e
C(MnSO 4)
=10(2.25) *C(Mn +2 ) *C(SO−2 ) *(γ(2) )
2
(4.89)
4
e e e e 2
C(ZnSO 4)
=10(2.46)*C(Zn +2 ) *C(SO−2 ) *(γ(2) ) (4.90)
4
e e e e 2
C(NiSO 4)
=10(2.46) *C(Ni+2 ) *C(SO−2 ) *(γ(2) ) (4.91)
4
The values of γe(1) , γe(2) and γe(3) are given by Equations (4.37), (4.38) and (4.92).
The value of ionic strength (Ie ) is given by Equation (4.93).
0.509∗√Ie
Log(γe(1) )= - – log(1+0.018015*Ie )+0.064*Ie (4.37)
(1+1.22∗√Ie )
4∗0.509∗√Ie
Log(γ𝑒(2) )= - (1+1.22∗√Ie ) – log(1+0.018015*Ie )+0.064*Ie (4.38)
9∗0.509∗√Ie
Log(γ𝑒(3) )= - (1+1.22∗√Ie ) – log(1+0.018015*Ie )+0.064*Ie (4.92)

1 e e e e e e e e
Ie =2*(C(H + ) +4*C
(SO−2 ) +C(HSO4 ) +4*C(Cu+2 ) +4*C(Co+2 ) +9*C(Al+3 ) +C(AlSO+ ) +C(Al(SO4 )2 ) +
− −
4 4
e e e e e e e
4*C(AlHSO +2 +4*C(Fe+2 ) +9*C(Fe+3 ) +C(FeSO+ ) +C(Fe(SO )− ) +4*C
(FeHSO+2 +4*C(Mg +2 ) +
4 ) 4 4 2 4 )
e e e
4*C(Mn+2 ) +4*C(Zn+2 )+4*C(Ni+2 ) ) (4.93)
Equation (4.40) gives mass of aqueous phase at equilibrium. Where MCu is

extracted mass of Cu from aqueous phase and MH is stripped mass of H from organic
phase. Equation (4.41) gives the value of MH . Where 1.007 is molar mass of H and 63.54
e
is molar mass of Cu. Equation (4.42) gives the value of MCu. Where V(aq) (m3) is the value
of volume of aqueous phase at equilibrium and is unknown value.
e i
M(aq) =M(aq) - MCu + MH (t) (4.40)
1.007
MH =MCu*2*63.54 (t) (4.41)
i i e e
MCu=(V(aq) *C(CuT) - V(aq) *C(CuT) )/1000 (t) (4.42)
e e
Equation (4.43) gives the relation between M(aq) and V(aq) .
e e e
M(aq) =SG(aq) *V(aq) (4.43)
Equation (4.44) gives the specific gravity of aqueous phase (J. KAFUMBILA, 2017).
𝑒
SG(aq) = -6.139 * 10−7 x [CTe ]2 + 9.742 * 10−4 *CTe + 1 (4.44)
𝑒
e e e e e e
CTe =1.007*(C(H + ) +C
(AlHSO+2 ) +C(FeHSO+2 ) +C(FeH(SO4 )2 ) )+96.06*(C(SO−2 ) +C(CuSO4 )
4 4 4
e e e e e e e
+C(CoSO4)
+C(AlSO + ) +2*C(Al(SO )− ) +C
4 2 (AlHSO+2 ) +C(FeSO4 ) +C(FeSO+ ) +2*C(Fe(SO4 )2 ) +
−
4 4 4
e e e e e e
C(FeHSO +2 ) +2*C(FeH(SO ) ) +C(MgSO ) +C(MnSO ) +C(ZnSO ) +C(NiSO ) )+97.07*
4 2 4 4 4 4
4
C(eHSO−4 ) +98.08*C(H
e
2 SO4 )
e
+C(CuT) e
+C(CoT) e
+C(AlT) e
+C(FeT) e
+C(MgT) e
+C(MnT) e
+C(ZnT) +
e
+C(NiT) + (4.94)
Equations (4.46), (4.48) and (4.95) to (4.103) allow calculating the values of
concentrations of soluble compounds. Equation (4.103) gives the electrical charge
e
neutrality of solution. Equation (4.104) gives the value of C(ST) .

e e e
C(CuT) =(C(Cu+2 ) +C(CuSO ) )*63.54
4
(4.46)
i i e e
C(ST) *V(aq) =C(ST) *V(aq) (4.48)
e e e
C(Ac) =(C(H + ) +C(H SO ) )*98.08
2 4
(4.95)
e e e
C(CoT) =(C(Co +2 ) +C(CoSO ) )*58.93
4
(4.96)
e e e e e
C(AlT) =(C(Al +3 ) +C(AlSO+ ) +C(Al(SO )− ) +C
4 2 (AlHSO+2 ) )*26.98 (4.97)
4 4
e e e e e e e e
C(FeT) =(C(Fe+2 ) +C(FeSO ) +C(Fe+3 ) +C(FeSO+ ) +C(Fe(SO )− ) +C(FeHSO+2 ) +C(FeH(SO ) ) )
4 4 2 4 2
4 4
*55.85 (4.98)
e e e
C(MgT) =(C(Mg +2 ) +C(MgSO ) )*24.31
4
(4.99)
e e e
C(MnT) =(C(Mn +2 ) +C(MnSO ) )*54.94
4
(4.100)
e e e
C(ZnT) =(C(Zn+2 ) +C(ZnSO ) )*65.38
4
(4.101)
e e e
C(NiT) =(C(Ni+2 ) +C(NiSO ) )*58.69
4
(4.102)
e e e e e e e e
C(H + ) +2*C(Cu+2 ) +2*C(Co+2 ) +C(Al+3 ) +C
(AlSO+ ) +2*C(AlHSO+2 ) +C(Fe+2 ) +C(Fe+3 ) +
4 4
e e e e e e e
C(FeSO + ) +2*C
(FeHSO+2 +2*C(Mg +2 ) +2*C(Mn+2 ) +2*C(Zn+2 ) +2*C(Ni+2 ) =2*C(SO−2 ) +
4 4 ) 4
e e i
C(HSO−4 ) +C(Al(SO4)−2 ) +C(Fe(SO4 )−2 ) (4.103)
e e e e e e e e
C(ST) =(C(SO −2 ) +C(HSO− ) +C(H SO ) +C(CuSO ) +C(CoSO ) +C(AlSO+ ) +2*C(Al(SO )− ) +
4 2 4 4 4 4 2
4 4
e e e e e e e
C(AlHSO+2 ) +C(FeSO ) +C(FeSO+ ) +2*C(Fe(SO )− ) +C(FeHSO+2 ) +2*C(FeH(SO ) ) +C(MgSO )
4 4 2 4 2 4
4 4 4
e e e
+C(MnSO4)+C(ZnSO4 )+C(NiSO4) )*32.065 (4.104)
4.4.4.3. Values of thermodynamic equilibrium condition
Test conditions of lab test 2 done with industrial copper sulfate aqueous phase
are the following:
 Element concentrations of industrial copper sulfate aqueous phase are

given in Table (4.9).

 Extractant volume percentage in the organic: 18%.
Table 4.9: Element concentrations of industrial copper sulfate

aqueous phase of lab test 2
Cu Co Al Fe Mg Mn Zn Ni Acid
g/l g/l g/l g/l g/l g/l g/l g/l g/l
5.23 4.40 0.50 0.82 1.40 1.59 0.43 .0.27 5.20
Table (4.12) gives equilibrium line Data of Lab test 2
Cu(aq) (g/L) 0.067 0.120 0.191 0.410 1.510 4.300

Cu(or) (g/L) 1.721 2.555 3.359 4.819 7.438 9.290

versus the value of copper concentration in organic phase. Results show that the slopes
of thermodynamic equilibrium conditions of extractant percent in organic phase of 18%
(pure copper solution) and 18% (pilot plant solution) are close.

organic phase of lab tests 2, and 7

4.4.5. Effect of high acid concentration (stripping step)
Test conditions of lab test 8 of stripping step are the following:
 Initial copper concentration in aqueous phase: 35 g/l

 Initial free acid concentration in aqueous phase: 180 g/l.
 Copper concentration in loaded organic: 15.98 g/l.
 Extractant volume percentage in organic: 32%.
Table (4.13) gives equilibrium line Data of Lab test 8
Cu(aq) (g/L) 37.24 39.61 41.58 47.63 49.74 53.95

Cu(or) (g/L) 4.45 4.74 4.90 5.71 5.84 6.42

versus the value of copper concentration in organic phase.

organic phase of lab test 8

Results show that the value of thermodynamic equilibrium condition ψe1 is a
linear function of the value of copper concentration in organic phase. Equation (4.52)
gives the modeling of thermodynamic equilibrium condition.
4.4.6. Equation of equilibrium condition
The values of constants “a” and “b” are only function of extractant volume
percentage. Equilibrium condition on extraction and stripping steps are given by
equations (4.105) and (4.106) in the range from 8 to 32% of extractant volume percent.
These Equations have been obtained from pure copper aqueous solution.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
Figure (4.6) gives the experimental data of equilibrium line of lab test (1) and
simulated equilibrium line obtained from Equation (4.105).
Figure 4.6: Comparison between experimental Data and simulation

Data on lab test 1

Figure (4.7) gives the experimental data of equilibrium line of lab test (8) and
simulated equilibrium line obtained from Equation (4.106).
Figure 4.7: Comparison between experimental Data and simulation

Data on lab test 8

5. MacCabe -Thiele diagram
5.1. Extraction step
Figure (5.1) gives scheme of stage of rank ‘n’ of extraction step in counter
current configuration. Stage of rank ‘n’ of extraction step receives aqueous phase
n−1 n+1
Eaq from stage of rank ‘n-1’ and organic phase Eor from stage of rank ‘n+1’. Stage of
n n
rank ‘n’ produces aqueous phase Eaq and organic phase Eor .
Figure 5.1: Scheme of stage of rank ‘n’ of extraction step
MacCabe Thiele diagram of stage of rank ‘n’ of extraction step is shown in Figure
(5.2). The Point “E” gives feed coordinates, the Point “B” gives outlet coordinates and the
Point “D” gives outlet equilibrium coordinates. Triangle “A–B–C” gives MacCabe Thiele
diagram of stage of rank ‘n’ of extraction step.
Slope of line “AC” is given by equation (5.1). Slope of line “BE” is given by
equation (5.2).
Y −Y
Slope “AC” = XA−XC (5.1)
A C
Y −Y Y −Y Y −Y
Slope “BE” = XB−X C = XD−XC = XD −XB = - Slope “AC” (5.2)
C A D A D B

Figure 5.2: MacCabe Thiele diagram of stage of rank ‘n’ of extraction step
5.2. Stripping step
Figure (5.3) gives scheme of stage of rank ‘n’ of stripping steps in cascade
n+1
configuration. Stage of rank ‘n’ of stripping step receives aqueous phase Saq from stage
n−1
of rank ‘n+1’ and organic phase Sor from stage of rank ‘n-1’. Stage of rank ‘n’ produces
n n
aqueous phase Saq and organic phase Sor .
Figure 5.3: Scheme of stage of rank ‘n’ of stripping step

MacCabe Thiele diagram of stage of rank ‘n’ of stripping step is shown in Figure
(5.4). The Point “E” gives feed coordinates, the Point “B” gives outlet coordinates and the
Point “D” gives outlet equilibrium coordinates. Triangle “A-B-C” gives MacCabe Thiele
diagram of stage of rank ‘n’ of stripping step.
Slope of line “AC” is given by equation (5.3). Slope of line “EB” is given by
equation (5.4).
Y −Y
Slope “AC” = XA −XB (5.3)
B C
YA −YC YA −YD YB −YD

Slope “EB” = = = = -slope “AC” (5.4)
XC −XB XC −XD XB −XD
Figure 5.4: MacCabe diagram of stage of rank ‘n’ of stripping step

6. Metallurgical constraints of copper SX
6.1. Description of copper SX
Copper solvent extraction technology has been introduced in copper

hydrometallurgy when the solution from leaching of low-grade oxide ore did not have
enough tenor of copper to be processed in direct electrowinning. In this condition
copper solvent extraction unit process has been introduced between leaching and
copper electrowinning unit processes to increase the concentration of copper in copper
electrolyte.
Copper solvent extraction unit process consists of two circuits coupled with
common organic phase. Figure (6.1) gives common Leach/solvent
extraction/electrowinning circuit. On extraction step, copper is extracted from the
copper rich solution called “Pregnant Leach Solution” by copper poor organic phase
called “stripped organic”. Extraction step produces acid rich solution called “Raffinate”
and copper rich organic phase called “Loaded organic”. On stripping step, copper is
recovered from the copper rich organic phase by acid rich electrolyte called “spent
electrolyte” coming from the copper electrowinning unit process. Stripping step
produces copper rich electrolyte called “advance electrolyte” and the copper poor
organic phase. The organic phase of copper solvent extraction technology is a mixture of
extractant and diluent. Extraction and stripping steps are carried out at industrial scale
with mixer–settlers. In mixer, one phase is dispersed into a second phase to provide
interface contact for mass transfer and in a settler mixture of aqueous and organic phase
is decanted to allow phases to coalesce and separate. Consequently, leaching unit
process must be designed to allow the extraction of copper on organic phase and copper
electrowinning unit process must be designed to allow stripping of copper from the
organic phase.

Figure 6.1: Scheme of common leach/solvent extraction/electrowinning circuit
6.2. Design criteria of copper SX
6.2.1. Maximum copper loading
Maximum loading (ML) is concentration of copper in the organic phase at

equilibrium with PLS. Figure (6.2) gives a graphical representation of loaded organic,
maximum loading and predicted absolute maximum loading.
Figure 6.2: Position of loaded organic and maximum loading on

MacCabe-Thiele diagram

6.2.2. Extractant volume percent
Extractant volume percent is the volume percentage of extractant in organic

phase
6.2.3. Copper net transfer
Copper net transfer is the quantity of copper, which is transferred to copper

electrowinning circuit per extractant volume percent. Copper net transfer is given by
equation (6.1). Copper net transfer depends on extractant volume percent, type of
extractant, PLS composition and configurations of extraction and stripping steps.
CuLO −CuSO
NetCu = (6.1)
V%
Where “NetCu” is the copper net transfer ((g/L)/1Vol %), “𝐶𝑢𝐿𝑂 ” is the copper
tenor in loaded organic (g/L), “𝐶𝑢𝑆𝑂 ” is the copper tenor in stripped organic
(g/L), and “V%” is the extractant volume percent (%).
6.2.4. Percentage to maximum loading
Percentage of maximum loading (saturation ratio) is the ratio of copper

concentration in the loaded organic on maximum loading. The value of percentage to
maximum loading is given by equation (6.2).
CuLO
%ML = x100 (6.2)
ML
Where “%ML” is percentage of maximum loading (%), “𝐶𝑢𝐿𝑂 ” is copper tenor in

loaded organic (g/L), and “ML” is maximum loading (g/L).
6.2.5. Copper recovery
Equations (6.3) and (6.4) give respectively copper recovery on extraction and
stripping steps.
CuPLS −CuRaf
RCuex = CuPLS
x 100 (6.3)
CuLO −Cu𝑆𝑂
RCust = x 100 (6.4)
CuSO

Where “𝑅𝐶𝑢𝑒𝑥 ” is extraction recovery (%), “𝑅𝐶𝑢𝑠𝑡 ” is stripping recovery (%),
“𝐶𝑢𝑃𝐿𝑆 ” is copper tenor in PLS (g/L), “𝐶𝑢𝑅𝑎𝑓 ” is copper tenor in raffinate (g/L),
“𝐶𝑢𝐿𝑂 ” is copper tenor in loaded organic (g/L), and “𝐶𝑢𝑆𝑂 ” is copper tenor in
stripped organic (g/L).
6.2.6. Advance and operating ratios (O/A)
Figure (6.3) gives scheme of solvent extraction stage. The scheme shows mixer
and settler of copper solvent extraction installation. Mixer receives a mixture of fresh
and recycle aqueous phases which have volume flowrates, respectively of “a” and “c”
m3/h and a mixture of fresh and recycle organic phases which have volume flowrates,
respectively of “b” and “d” m3/h. Advance ratio (O/A) is ratio of the organic phase
flowrate on aqueous phase flowrate, which are fed to stage. Operating ratio (O/A) is
ratio of the organic phase flowrate on aqueous phase flowrate into the mixer.
Equations (6.5) and (6.6) give respectively values of operating and advance
ratios (O/A) determined with stream flowrates.
(b+d)
O/AOPF = (a+c) (6.5)
b
O/AADF = a (6.6)
Figure 6.3: Scheme of solvent extraction stage

Equations (6.7) and (6.8) give the value of the advance ratio (O/A) as a function
of the concentration of copper in aqueous and organic phases before and after extraction
respectively on extraction and stripping steps.
CuIaq −CuO 1
O/Aex aq
ADA = CuO −CuI = Slope "AC" (6.7)
or or
CuO −CuIaq 1
O/Ast aq
ADA = CuI −CuO = Slope "AC" (6.8)
or or
𝐼 𝑂
Where 𝐶𝑢𝑎𝑞 and 𝐶𝑢𝑎𝑞 are concentrations of copper respectively in inlet and
𝐼 𝑂
outlet aqueous phases on a stage and 𝐶𝑢𝑜𝑟 and 𝐶𝑢𝑜𝑟 are concentrations of
copper respectively in inlet and outlet organic phases on a stage.
6.2.7. Phase continuity
When operating ratio (O/A) is greater than 1.1/1, aqueous phase is dispersed in
the organic phase and mixer works in organic continuity regime. On the other side, when
operating ratio (O/A) is lower than 1/1.1, organic phase is dispersed in the aqueous
phase and mixer works in aqueous continuity regime. Between the two values of the
operating ratio (O/A) there is a transition zone where continuity regime changes
constantly. When mixer works in organic continuity regime organic entrainment in the
aqueous phase is low. On the other hand, when mixer works in aqueous continuity
regime aqueous entrainment in organic phase is low. In the new design of copper
solvent extraction value of operation ratio (O/A) is fixed at 1.25/1 to be far from
transition zone.
6.2.8. Number of stages on extraction step
Figure (6.4) gives the exiting configurations of extraction step of copper solvent
extraction.

Figure 6.4: Exiting configurations on extraction step

6.2.9. Number of stages on stripping step
In the industrial practices counter current configuration usually used on

stripping step has either one stage or two stages in series. In the case of two stages in
series, first stage receives loaded organic and second stage receives spent electrolyte.
Figure (6.5) gives a scheme of stripping step having two stages in series. Notice that the
copper recovery increases with increasing the number of stages in series.
Figure 6.5: Scheme of stripping step having two stages in series
6.2.10. Stage efficiency
In industrial installation of copper solvent extraction, copper concentration out

of the mixer in aqueous and organic phases on extraction and stripping steps are not
equilibrium values. This phenomenon is due to [SORDERSTROM M. ET AL, 2010]:
 Residence time into the mixer: stage efficiency increases with increasing of mixer
residence time. In industrial practice residence time is ranged from 2 to 3
minutes.
 Number of mixing stages: stage efficiency increases with increasing number of
mixing stages. In modern copper solvent extraction installation number of mixing
stages is 2.
 Viscosity of solution: stage efficiency decreases with increasing solution viscosity
(presence of impurities as Al and Mg).
 Operating ratio O/A: stage efficiency decreases with increasing of operating ratio
(O/A) (mixing is non-homogenous).
 Energy input and type of impeller: stage efficiency increases with increasing of
intensity of agitation. Notice that intense agitation can produce a mixture of
aqueous and organic phases which needs a long separation phases time.
 Co-extraction of impurities: stage efficiency decreases with increasing of co-
extraction of impurities (iron)

According to Figures (5.2) and (5.4), Equations (6.9) and (6.10) give the stage
efficiencies calculated with the concentrations of copper in organic and in aqueous
respectively on extraction step. Equations (6.11) and (6.12) give the stage efficiencies
calculated with the concentrations of copper in organic and in aqueous respectively on
stripping step.
e YB −YA
Effor = 100 x (6.9)
YD −YA
e XB −XA
Effaq = 100 x (6.10)
XB −XD
s YB −YA
Effor = 100 x (6.11)
YB −YD
s XB −XA
Effaq = 100 x (6.12)
XD −XA
Mixer efficiency is a critical parameter to screen in copper solvent extraction

unit process in order to guarantee high value of copper net transfer. Low values of mixer
efficiency lead to higher reagent usage. With modern extractant and mixing equipment,
mixer efficiencies range from 90 to 100% on extraction step and from 95 to 100% on
stripping step. In industrial practices, average values of mixer efficiencies for the
Lix984N extractant are respectively 95 and 98% on extraction and stripping steps.
6.3. Metallurgical constraints of copper SX
6.3.1. Constraints between extraction and stripping steps
In copper solvent extraction plant having extraction step containing at least two
stages and stripping step containing one or two stages, equilibrium constraints between
extraction and stripping steps are given by Equations (6.13) and (6.14).
LOe = LOs (6.13)
SOe = SOs (6.14)

6.3.2. Advance ratio (O/A)
6.3.2.1. First constraint
The optimum value of advance ratio O/A of the extraction step must give the
smallest size of copper solvent extraction configuration.
6.3.2.2. Second constraint
The organic loss in aqueous phase is low when the mixer works in organic
phase continuity regime. Operating ratio O/A of the last stage on extraction step and the
first stage on stripping step must be 1.25/1 to have organic continuity regime to reduce
loss of organic phase. In this continuity regime organic phase tenor in raffinate is around
50 ppm. Recovery of organic phase in pre-settler raffinate pond and in advance
electrolyte coalescing tank are respectively 30 and 75%.
6.3.2.3. Third constraint
Loss of organic phase increases with increasing of crud formation. Crud is a

solid formed by mixing aqueous phase containing fine suspended solids with organic
phase. Crud is a thin and compact layer of solid around 50% organic by weight in
organic-aqueous interface in settler, which is stabilized emulsion. Solid particles that
give emulsion stability are typically demonstrated as silica, but any fine solid (<2
micron) that passes thickeners can cause crud formation. Clays, iron precipitate,
gypsum, quartz, and micas have all been linked to the crud formation in copper solvent
extraction. Silica is always present in PLS as fine silica particles and dissolved silica.
Dissolved silica precipitates and polymerizes as chains of colloidal silicon, which
absorbs organic. It has been observed that running organic continuous decreased silica
tenor in high acid strip where silica precipitation is most prevalent [LIU JIARSHE ET AL,
2002 and READETT, D.J. ET AL, 1995]. Crud formation linked to iron precipitate is due to high
pH in PLS. Hydrolysis and polymerization reactions of ferric are formed at pH greater
than 2 [READETT, D.J. ET AL, 1995]. Coagulants are used to remove silica gel in PLS and also
Crud treatment such as centrifugation or clay application is commonly used to recover
the organic phase [MUKUTUMA A. ET AL, 2008]. The second possibility is to add a stage
before the first stage on extraction step. This new stage is contained only diluent which
turns around on a stage. Silica gel is dissolved in diluent and is removed from PLS before
copper solvent extraction. Clay treatment is applied on diluent of new stage to remove
silica gel. First test results show that around 50% of silica gel has been removed from
PLS.

6.3.2.4. Fourth constraint
It has been observed that the stage efficiency on extraction step is greater when
the organic phase continuity regime is used [SORDERSTROM M. ET AL, 2010].
6.3.2.5. Actions
Therefore, all mixers on extraction and stripping steps must work in organic
continuity regime with value of the operating ratio (O/A) of 1.25/1. In this condition,
value of the advance ratio O/A that gives the smallest size of copper solvent extraction is
equal to value of operation ratio O/A of 1.25/1 on extraction step. On stripping step,
value of the advance ratio (O/A) is depended on the copper mass transferred to
stripping step and values of copper tenors in advance and spent electrolyte.
6.3.3. Copper concentration in spent electrolyte
6.3.3.1. Constraint
In the copper electrowinning unit process, anodes are lead alloys because are
cheaper. Observations of operations of copper electrolysis show that corrosion of lead
anodes increases with increasing of current density. There are many scientific
explanations of this phenomenon. Simpler way to explain is that [ANDERSEN T. N., 1974]:
 First step lead anodes are in contact with copper electrolyte: free acid attacks
lead and forms PbSO4 in the form of scales on anode surface.
 Second step current is applied to copper electrowinning: water decomposition
takes place on a lead alloy between PbSO4 scales producing oxygen gas and acid.
Oxygen oxidizes PbSO4 into PbO2. Oxygen evolution on anodes removes lead
oxide because it takes place between scales.
 Once lead oxides are removed from anode surface, the second step starts again.
This phenomenon corrodes anodes. Removal of lead oxide by oxygen gas
evolution increases with increasing of current density of copper deposition.
 Presence of cobalt in copper electrolyte decreases the corrosion rate because
cobalt oxides precipitate between lead oxides scales and oxygen evolution takes
place on cobalt oxides.

6.3.3.2. Actions
In industrial practices maximum value of operating current density is 400 A/m2

to have anode lifetimes around 7 years. The value of design current density is 300 A/m2
[J. KAFUMBILA, 2017B]. The minimum value of copper concentration in spent electrolyte
must be 30 g/L to have a compact copper deposit at design current density (general rule
in copper electrowinning for obtaining a compact copper deposit is: ratio of the
operating current density (A/m2) on copper tenor in spent electrolyte (g/L) must be
less than 10) [WINAND R., 1994]. Optimum copper tenor in spent electrolyte is 35 g/L for
operating current density ranged 280 – 320 A/m2.
6.3.4. Acid concentration in spent electrolyte
6.3.4.1. Constraint
The maximum value of free acid concentration in spent electrolyte is also fixed
by lead anode behaviour. Initially, lead anodes used for direct copper electrowinning
unit process were lead 6-10% antimony. High strength antimony rich eutectic phase of
6-10% Sb lead alloys strengthens anode structure. But the introduction of copper
solvent extraction technology has markedly increased corrosion of Pb-Sb anodes. This
accelerated corrosion has been attributed to high acid levels encountered in these
solutions. Antimony rich phase is selectively attacked by the free acid resulting in high
lead release and anode shot life [ANDERSEN T. N., 1974].
Early 1980 rolled Pb-Ca-Sn alloys anodes have been introduced in the copper
electrowinning unit process to improve lead alloys corrosion behaviour due to free acid.
The corrosion rate of Pb-Ca-Sn alloys anodes is lower than that of Pb-Sb. Anode
corrosion due to high level of the free acid tenor in spent electrolyte for Pb-Ca-Sn alloys
takes place in another form. Free acid breaks contact between lead oxides and lead
alloys [ANDERSEN T. N., 1974].
6.3.4.2. Actions
Today, copper electrowinning circuit coupled to copper solvent extraction unit

process uses Pb-Ca-Sn anode and maximum value of the free acid concentration in spent
electrolyte is 190 g/L which gives anode lifetime of 7 years.

6.3.5. Copper concentration in advance electrolyte
6.3.5.1. First constraint
The maximum value of copper concentration in advance electrolyte is limited at

55 g/L to avoid crystallisation of copper in the first stage of stripping step.
6.3.5.2. Second constraint
Copper concentration in advance electrolyte must be high to minimize the

number of scavenger cells in the copper electrowinning unit process.
6.3.5.3. Actions
In industrial practices, copper concentration in advance electrolyte is ranged

from 50 to 55 g/L. Sometimes copper concentration in advance electrolyte is decreased
to 45 g/L to increase stripping efficiency for stripping step having one stage.
6.3.6. Percentage to maximum loading
6.3.6.1. Old constraint - Highest copper extraction efficiency
At the beginning, configuration of copper solvent extraction had 3 or 4 stages on

extraction step and 2 stages on stripping because the organic phase had low maximum
copper loading ( around 0.39 (g/L)/1Vol%). The maximum copper loading of organic
phase had been improved to reach 0.52 (g/L)/1Vol% and the number of stages on
extraction step had been reduced to 2. This copper solvent extraction configuration was
called the conventional configuration. Metallurgical target was to have high copper
extraction efficiency. Copper concentration in PLS from heap leaching of low grade oxide
ores was around 4 g/L at pH 1.8. Advance and operating ratios (O/A) were the same
(1/1) on extraction step.
6.3.6.2. First new constraint - Highest copper net transfer
Observation of operations of copper solvent extraction in the heap leaching

circuit was shown that copper extraction recovery was not the important parameter.
The most important parameter was capital cost of copper solvent extraction circuit in all
capital cost of the production plant. The capital cost of copper solvent extraction circuit
increases with increasing of flowrate of PLS and number of stages of extraction and
stripping steps. The capital cost of copper solvent extraction decreases with increasing
of copper concentration in PLS. The increase of copper concentration in PLS increases
copper net transfer at the same value of copper concentration in stripped organic.
Actions which have been taken to minimize capital cost of copper solvent
extraction circuit in all capital cost of production plant in the heap leaching circuit were
the following:
 Copper solvent extraction configuration has been changed from 2Ex2S to 2Ex1S to
reduce the number of stages because copper concentrations in PLS are low (less
than 5 g/L).
 Value of copper net transfer must be high (good use of organic phase). In industrial
practices value of copper net transfer with Lix984N reagent range from 0.24 to 0.30
(g/L)/1vol% for 2Ex1S configuration.
 Size of copper solvent extraction must be the smallest (values of advance and
operating ratios (O/A) are the same on extraction step).
6.3.6.3. Second new constraint - Iron rejection on organic phase
It has been observed that ferrous and ferric are transferred to copper
electrowinning circuit by physical entrainment. In addition, ferric is transferred by
chemical entrainment [HANS HEIN, 2005]. Solvent extraction reagents, capable to extract
selectively copper, were characterized on the selectivity of Cu extraction against ferric
contaminant. The test shows that the extraction of Ferric begins at pH around 1.5 [L.
GOTFRYD ET AL, 2013] lower than leaching pH of copper oxide ores of 1.8.
In all copper solvent extraction circuit having two stages in series on extraction
step, it has been observed that the concentration of iron in loaded organic out of stage of
rank 1 is lower than the concentration of iron in partially loaded organic out of stage of
rank 2. This effect is called “crowding” [HANS HEIN, 2005]. “Crowding” works well when
loaded organic is saturated with copper. The effect of the free acid concentration in
raffinate or semi raffinate on iron removal on loaded organic phase is lower than that of
saturation of loaded organic with copper [HANS HEIN, 2005].
Iron in the electrolyte of a copper electrowinning unit process causes reduction

of current efficiency. It is estimated that current efficiency increases by 2-3% for every 1
g/L drop in iron in electrolyte [D.R. SHAW ET AL, 2004]. The maximum concentration of
iron in copper electrolyte is 2g/L, which gives a value of current efficiency ranged from
88 to 92% at operating current density of 300 A/m2. At an operating current density of
375 A/m2 used in modern tank-house, iron concentration in electrolyte must be less
than 1 g/L. Usually bleed of spent electrolyte is applied to maintain iron concentration in
copper electrolyte at maximum level. Increasing of flowrate of spent electrolyte bleed

increases the cost of cobalt reagent which is added to the copper EW circuit and the cost
linked to copper recycled. The cost linked to copper recycled can be evaluated in terms
of copper soluble losses and organic loss linked to increasing of extractant volume
percent caused by copper recycled. Loss of cobalt and copper recycled in electrolyte
bleed can be decreased by using FENIX iron control system [D.R. SHAW ET AL, 2004]. The
FENIX iron control system removes iron with resin on spent electrolyte bleed. A big
portion of outlet solution of FENIX is pumped back to copper electrolyte. Only a small
portion is pumped to leaching unit operation, which controls the level of other elements
in copper electrolyte.
The most important parameter is not the ratio of Cu/Fe in loaded organic phase,
but the ratio of Cu/Fe transferred to electrowinning unit process.
6.3.6.4. Actions
In industrial practice ratio Cu/Fe transferred to copper electrowinning unit

process is ranged from 500 to 1000. In consequence copper recycled can reach 8% of
copper cathode. For reducing physical entrainment of iron in loaded organic phase, the
aqueous coalescing tank is placed before organic surge tank. For reducing chemical
entrainment of iron in loaded organic phase, there are two possibilities:
 Loaded organic phase is saturated with copper. The optimum value of %ML, which
gives the ratio Cu/Fe value of around 1000, is greater than 80% [N.B. DU PREEZ ET AL,
2015]. In industrial practice %ML values depends on the PLS copper tenor and the
copper solvent extraction recovery. The copper solvent extraction recovery must be
greater than 90%.
 Washing step is added between extraction step and stripping step. In this condition
capital cost of copper solvent extraction increases. Wash stage uses an aqueous
solution at pH of 2. Advance ratio (O/A) is around 50/1. In industrial practice iron
stripping efficiency is around 50% and copper recycle from wash stage represent
0.5 % of copper transferred [HANS HEIN, 2005].

7. Modeling of Copper SX circuit
7.1. Flow diagram of Cu SX circuit
Copper SX circuit that has been selected to study the effect of dithionate is the
conventional SX circuit (2Ex2S). Figure (7.1) gives the flow diagram of the conventional
Cu SX circuit
Figure 7.1: Flow diagram of the conventional Cu SX circuit
Abbreviations of unit operations:
 Extraction En: Stage of rank “n” in extraction train.

 Stripping Sn: Stage of rank “n” in stripping train.
Abbreviations of lines between unit operations:
 PLS: Pregnant leach solution.

 RafEn: Raffinate of stage of rank “n” in extraction train.
 LOEn: Loaded organic of stage of rank “n” in extraction train.
 SOSn: Stripped organic of stage of rank “n” in stripping train.
 SP: Spent electrolyte.
 AdSn: Advance electrolyte of stage of rank “n” in stripping train.

7.2. Modeling of Copper SX-EW circuit without dithionate
7.2.1. Base case - copper alone in PLS
7.2.1.1. Flow diagram of base case
Figure (7.2) gives the flow diagram of base case of Copper SX-EW circuit
Figure 7.2: Flow diagram of Copper SX-EW base case with 30% of extractant v/v and
only copper in PLS

 CuEW: Copper electrowinning circuit.


 EWW: Water in copper electrowinning circuit.
 EWCC: Copper cathode in copper electrowinning circuit.
 EWO: Oxygen in copper electrowinning circuit.
7.2.1.2. Design criteria
A. Liquid specific gravity
Equation (7.1) gives the approximate value of specific gravity of liquid in as

function of liquid chemical composition (J. KAFUMBILA, 2017A).
SGL = -6.139 * 10−7 x [CT ]2 + 9.742 * 10−4 * CT + 1 (7.1)
Where “ 𝑆𝐺𝐿 ” is liquid specific gravity (t/m3) and “CT ” is the sum of
concentrations of soluble species (g/L)
B. Extraction train
 PLS flow rate: 100 m3/hrs

 PLS composition:
o Copper concentration: 8 g/L.
o Acid concentration: pH 1.7.
 Type of extractant: Lix984N.
 O/A ratio (Loaded organic of stage of rank “2” on extraction train onto
HGPLS): 1.25.
 Number of stage: 2.
 Mixing efficiency for Copper:
o Stage E1: 95%.
o Stage E2: 96%.
 Equilibrium condition of Cu

Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2
(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
 Model is explained in chapter (4.25)
C. Stripping train
 Cu concentration in advance electrolyte: around 50 g/L.
 Spent electrolyte composition:
o Acid concentration: 180 g/L.
 Mixing efficiency:
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
 Model is explained in chapter (4.25)
D. Cu electrowinning
 Percent of acid in concentrated acid: 98%

 Specific gravity of concentrated acid: 1.84.
 Chemical reaction of Copper electrowinning (7.a).
2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)
Where “EWO” is the quantity of oxygen produced in copper electrowinning

and “EWCC” is copper cathode produced in copper electrowinning.
7.2.1.3. Modeling results
A. Estimation of flowrate of spent electrolyte
Equation (7.3) gives the approximate value of spent electrolyte flowrate

CPLS
Cu ∗ERCu 8∗0.96
Vsp =VPLS * =100*50−35=51.2±51m3/hrs. (7.3)
CAd SP
Cu −CCu
𝑃𝐿𝑆
Where “𝑉𝑠𝑝 ” is flowrate of spent electrolyte, “𝑉𝑃𝐿𝑆 ” is flowrate of PLS, “𝐶𝐶𝑢 ” is
Copper concentration in the PLS, “𝐸𝑅𝐶𝑢 ” is approximate extraction recovery,
𝐴𝑑 𝑆𝑃
“𝐶𝐶𝑢 ” is Copper concentration in advance electrolyte and “𝐶𝐶𝑢 ” is Copper
concentration in spent electrolyte.
B. Optimal extractant volume percent
The constraint is to have the highest value of Copper extraction recovery. The
copper solvent extraction is modeled with different value of extractant volume percent.
Figure (7.3) gives the Copper extraction recovery versus extractant volume percent. The
optimal value of extractant volume percent is 30%.
Figure 7.3: Copper extraction recovery versus extractant volume percent (%)
C. Modeling results with extractant volume percent of 30%
Table (7.1) gives metallurgical performances of Copper SX circuit.
Tables (7.2) and (7.3) give the mass balance results of Copper SX circuit base
case with 30% of extractant volume percent. Figure (7.4) gives copper flowrate in
percentage comparatively to the copper in PLS.

Table 7.1: Metallurgical performance of Copper SX circuit
Description Value
Copper SX circuit
Type of extractant Lix984N
Extractant volume percent 30 %
Cu extraction recovery (solution) 96.70 %
Net transfer 0.206 g/L/V%
Stripping efficiency 59.08 %
Copper electrowinning
Copper production 0.774 t/hrs
Table 7.2: Mass balance of Cu SX Circuit base case with 30% of Extractant
volume percent
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

PLS RafE1 RafE2 LOE1 LOE2 SOS2 SOS1 SP
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass t/hrs 102,252 101,643 101,503 62,969
Volume m /hrs 100,000 99,969 99,963 125,000 125,000 125,000 125,000 51,000
3
SG t/m3 1,023 1,017 1,015 1,235

Cu g/L 8,000 1,713 0,264 10,475 5,445 4,286 5,617 35,000
Acid g/L 2,775 14,525 17,851 180,000
volume percent
9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

AdS2 AdS1 EWCC EWO EWW
Solid
Mass t/hrs 0,774
Gas
Mass t/hrs 0,195
Liquid
Mass t/hrs 63,130 63,718 0,220
Volume m3/hrs 51,060 51,282 0,220
SG t/m3 1,236 1,243 1,000
Cu g/L 38,218 49,893
Acid g/L 171,865 143,364

Figure 7.4: Copper flowrate (%) for base case with 30% of extractant v/v and
only copper in solution
7.2.2. Base case - Copper and other elements in PLS
Figure (7.2) gives the flow diagram of base case with PLS containing Copper and
other elements of Copper SX-EW circuit


only copper in PLS



B. Extraction train

o Iron concentration: Saturation concentration.
o Cobalt concentration: 9.0 g/L.
o Manganese concentration: 4.0 g/L.
o Magnesium concentration: 2.0 g/L.
o Zinc concentration: 1.5 g/L.
o Aluminum concentration: 1.0 g/L
HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
 Model is explained in chapter (4.4.4)
C. Stripping train
 Spent electrolyte flow rate: 51 m3/hrs

o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)

A. Iron concentration in PLS
Iron is precipitated as copiapite during Copper and Cobalt leaching when the
solubility of Iron reaches the saturation concentration. Equation (7.4) gives
precipitation condition of chemical reaction (7.b). The value of Log(K (7.b) ) is given in
Table (7.4) (J. KAFUMBILA, 2022).
Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)
Log(K (7.b) )=-2*pH-log(a(Fe(+2)) )-4*log(a(Fe(+3)) )-6*log(a(SO−2

4 )
)-22*log(aw ) (7.4)

Table 7.4: Equilibrium constant of chemical reactions at 25°C
reaction Log (k) Reference

7.b 33.737 Calculated
B. Modeling results with extractant volume percent of 30% and other

elements in PLS
Table (7.5) gives metallurgical performances of Copper SX circuit. The presence

of other elements in PLS increases Copper extraction recovery. Increasing of free sulfate
anion (SO−24 ) due to the presence of other elements in aqueous phase decreases the
concentration of free hydrogen ion (H + ) and free copper ion (Cu+2 ) according to
chemical reactions (4.b), (4.c) and (4.d) (FRANCISCO REYES ET AL, 2013).
SO−2 + −
4 + H =HSO4 (4.b)
SO−2 +
4 + 2H =H2 SO4 (4.c)
Cu+2 + SO−2
4 = CuSO4 (4.d)
Tables (7.6) and (7.7) give the mass balance results of Copper SX circuit base
case with 30% of extractant volume percent and presence other elements in PLS. Figure
(7.5) gives copper flowrate (%) for base case with 30% of extractant v/v and other
elements in PLS.
Description Value
Copper SX circuit

volume percent and presence of other elements in PLS
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 107,129 107,009 62,969
Volume m3/hrs 100,000 99,921 99,907 125,000 125,000 125,000 125,000 51,000
SG t/m3 1,078 1,072 1,071 1,235
Cu g/L 8,000 1,469 0,228 10,506 5,281 4,288 5,626 35,000
Fe(2) g/l 1,097 1,098 1,098
Fe(3) g/l 0,104 0,104 0,104
Co g/l 9,000 9,007 9,008
Mn g/l 4,000 4,003 4,004
Mg g/l 2,000 2,002 2,002
Zn g/l 1,500 1,501 1,501
Al g/l 1,000 1,001 1,001
Acid g/L 2,910 9,482 11,012 180,000
volume percent and presence of other elements in PLS
9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

Solid
Mass t/hrs 0,777
Gas
Mass t/hrs 0,196
Liquid
Mass r/hrs 63,131 63,721 0,221
Volume m3/hrs 51,060 51,283 0,221
SG t/m3 1,236 1,243 1,000
Cu g/L 38,233 49,964
Fe(2) g/l
Fe(3) g/l
Co g/l
Mn g/l
Mg g/l
Zn g/l
Al g/l
Acid g/L 171,828 143,198

other elements in PLS
7.2.3. Base case - Extraction Fe(3) in organic phase
Figure (7.6) gives the flow diagram of base case with extraction of Fe(3) on
organic phase of Copper SX-EW circuit



extraction of Fe(3) in organic phase

 EWAc: Concentrated acid added to CuEW.
 EWBl: Iron bleed of CuEW.


B. Extraction train

Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)


HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

 Equilibrium Fe(III) concentration: Data of Lix984 (HOSSEIN AMINIAN, 1999)
on extraction train. Equation (7.5) gives equilibrium constant of
chemical reaction (7.c). This equilibrium constant has been obtained by
using the old method. This method can be used together with the new
model of copper solvent extraction because the level of ferric extraction
in organic phase is very low. The value of “K e ” is given in Table (7.8).
Fe+3+3HR=FeR 3 +3H + (7.c)
[FeR ]∗([H+ ])3

K e =[Fe+33]∗([HR])3 (7.5)
Where “[𝐹𝑒𝑅3 ]” is the concentration of ferric in organic phase (mol/L),

“[𝐹𝑒 +3 ]” is total concentration of ferric in aqueous phase (mol/L), [𝐻 + ] is
concentration of hydrogen ion in aqueous phase (mol/L) and [𝐻𝑅] is the
concentration free extractant in organic phase (mol/L).
Table (7.8): Equilibrium constants of reaction (7.c) at 25°C
Chemical reaction logK Reference

7.c -3.431 Hossein Aminian, 1999
 Mixing efficiency for Fe(III) (assuming the same as for Copper):

o Stage E1: 95%.
o Stage E2: 96%.
C. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

 Fe(3) concentration in organic phase: 1ppp (HANS HEIN, 2005)

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)

 Concentration of Fe in spent electrolyte:

o Fe(2):1.00 g/L.
o Fe(3): 1.00 g/L
 Flowrate of concentrated acid: sulfur mass balance on CuEW
Table (7.9) gives metallurgical performances of Copper SX circuit. Tables (7.10)

and (7.11) give the mass balance results of Copper SX circuit base case with 30% of
extractant volume percent and extraction of Fe(3) in organic phase. Figures (7.7) and
(7.8) give copper and iron flowrates (%) for base case with 30% of extractant v/v and
extraction of Fe(3) in organic phase.
Results show that the concentration of Iron in LOE1 is lower than the iron
concentration in LOE2. 2.93% of Copper is recycled to leach from CuEW because of Iron
extraction in organic phase.

Description Value
Copper SX circuit
Cu/Fe in LOE1 894.63
Table 7.10: Mass balance of Cu SX Circuit base case with 30% of Extractant v/v
and extraction of Fe(3) in organic phase
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 107,129 107,009 63,224
Volume m3/hrs 100,000 99,921 99,908 125,000 125,000 125,000 125,000 51,000
SG t/m3 1,078 1,072 1,071 1,240
Cu g/L 8,000 1,463 0,227 10,487 5,256 4,268 5,608 35,000
Fe(2) g/l 1,097 1,098 1,098 1,000
Fe(3) g/l 0,104 0,106 0,091 0,0117 0,0133 0,0010 0,0010 1,000
Co g/l 9,000 9,007 9,008
Mn g/l 4,000 4,003 4,004
Mg g/l 2,000 2,002 2,002
Zn g/l 1,500 1,501 1,501
Al g/l 1,000 1,001 1,001
Acid g/L 2,910 9,486 11,045 180,000

and extraction of Fe(3) in organic phase
9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

AdS2 AdS1 EWCC EWO EWW EWAc EWBl
Solid
Mass t/hrs 0,754
Gas
Mass t/hrs 0,190
Liquid
Mass r/hrs 63,386 63,977 0,838 0,184 0,831
Volume m3/hrs 51,062 51,346 0,838 0,102 0,670
SG t/m3 1,241 1,246 1,000 1,800 1,240
Cu g/L 38,238 49,904 35,000
Fe(2) g/l 0,999 0,993 1,000
Fe(3) g/l 0,999 1,019 1,000
Co g/l
Mn g/l
Mg g/l
Zn g/l
Al g/l
Acid g/L 171,831 143,062 1763,912 180,000

Figure 7.8: Iron flowrate (%) for base case with 30% of extractant v/v and
7.2.4. Base case – Aqueous phase entrainment in organic phase
Figure (7.9) gives the flow diagram of base case with aqueous phase
entrainment in organic phase of Copper SX-EW circuit



aqueous entrainment in organic phase
 LOEnA: Aqueous entrainment in loaded organic of stage of rank “n” in

extraction train.
 SOSnA: Aqueous entrainment in stripped organic of stage of rank “n” in
stripping train.


B. Extraction train

Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)


HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.

Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Fe+3+3HR=FeR 3 +3H + (7.c)
[FeR ]∗([H+ ])3

K e =[Fe+33]∗([HR])3 (7.5)



o Stage E1: 95%.
o Stage E2: 96%.
 Aqueous entrainment in organic for settle flux about 5-6 m3/m2/hr (G.
MILLER ET AL, 2002):
o Stage E1: 1000ppm.
C. Stripping train

o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

o Stage S1: 300ppm.
o Stage S2: 300ppm.

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)


o Fe(2):1.00 g/L.
o Fe(3): 1.00 g/L

Table (7.12) gives metallurgical performances of Copper SX circuit. Tables

(7.13), (7.14) and (7.15) give the mass balance results of Copper SX circuit base case
with 30% of extractant volume percent and aqueous phase entrainment in organic
phase. Figures (7.10) and (7.11) give copper and iron flowrates (%) for base case with
30% of extractant v/v and aqueous phase entrainment in organic phase.
Results show that sulfate coming with SOS2A in E2 increases the Copper
recovery and Iron coming with LOE1A in S1 increases the flowrate of EWBl.
Description Value
Copper SX circuit
Fe/Mn in spent electrolyte 3.168

and aqueous entrainment in organic phase
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

PLS RafE1 RafE2 LOE1 LOE1A LOE2 LOE2A SOS2
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 107,127 106,920 0,125 0,125
Volume m3/hrs 100,000 99,921 99,820 125,000 0,117 125,000 0,117 125,000
SG t/m3 1,078 1,072 1,071 1,072 1,071
Cu g/L 8,000 1,438 0,223 10,423 1,438 5,256 0,223 4,193
Fe(2) g/l 1,097 1,098 1,098 1,098 1,098
Fe(3) g/l 0,104 0,106 0,091 0,0117 0,106 0,0133 0,091 0,0010
Co g/l 9,000 9,007 9,006 9,007 9,006
Mn g/l 4,000 4,003 4,003 4,003 4,003
Mg g/l 2,000 2,002 2,001 2,002 2,001
Zn g/l 1,500 1,501 1,501 1,501 1,501
Al g/l 1,000 1,001 1,001 1,001 1,001
Acid g/L 2,910 9,515 11,104 9,515 11,104
9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

SOS2A SOS1 SOS1A SP AdS2 AdS1 EWCC EWO
Solid
Mass t/hrs 0,753
Gas
Mass t/hrs 0,190
Liquid
Mass r/hrs 0,038 0,038 63,603 63,764 64,444
Volume m3/hrs 0,030 125,000 0,030 51,000 51,063 51,381
SG t/m3 1,249 1,254 1,247 1,249 1,254
Cu g/L 38,236 5,530 49,878 35,000 38,236 49,878
Fe(2) g/l 0,999 0,994 1,000 0,999 0,994
Fe(3) g/l 0,999 0,0010 1,018 1,000 0,999 1,018
Co g/l 1,419 1,430 1,420 1,419 1,430
Mn g/l 0,631 0,635 0,631 0,631 0,635
Mg g/l 0,315 0,318 0,316 0,315 0,318
Zn g/l 0,236 0,238 0,237 0,236 0,238
Al g/l 0,158 0,159 0,158 0,158 0,159
Acid g/L 171,907 143,177 180,000 171,907 143,177

17,000 18,000 19,000 20,000 21,000 22,000 23,000 24,000

EWW EWAc EWBl
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,783 0,203 0,885
Volume m3/hrs 0,783 0,113 0,709
SG t/m3 1,000 1,800 1,247
Cu g/L 35,000
Fe(2) g/l 1,000
Fe(3) g/l 1,000
Co g/l 1,420
Mn g/l 0,631
Mg g/l 0,316
Zn g/l 0,237
Al g/l 0,158
Acid g/L 1763,912 180,000

7.2.5. Base case – loaded organic wash stage
7.2.5.1. Purpose
The reasons for adding loaded organic wash stage are:
 To remove around 50% of Fe(3) in organic phase.

 To remove aqueous phase entrainment in organic to increase the ratio
Fe/Mn in spent electrolyte
Figure (7.12) gives the flow diagram of base case with loaded organic wash
stage of Copper SX-EW circuit

loaded organic wash stage

 LOW: Loaded organic wash stage

extraction train.
 LOWW: water of loaded organic wash stage.
 LOWAc: Concentrated acid of loaded organic wash stage.
 LOWS: Wash solution of loaded organic wash stage.
 LOWF: Feed of loaded organic wash stage.
 LOWR: Raffinate of loaded organic wash stage.
 LOWRO: Raffinate out of loaded organic wash stage.
 LOWRR: Recycled raffinate inside of loaded organic wash stage.
stripping train.

B. Extraction train

Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)



HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Fe+3+3HR=FeR 3 +3H + (7.c)
[FeR ]∗([H+ ])3

K e =[Fe+33]∗([HR])3 (7.5)



o Stage E1: 95%.
o Stage E2: 96%.
C. Loaded organic wash stage
 O/A advance ratio (Loaded organic of stage of rank “1” on loaded organic
wash solution): 50.
 O/A operating Ratio: 1.25
 Acid concentration in loaded organic wash solution: 50g/L.
 Mixing efficiency: 95%.
MILLER ET AL, 2002): 1000ppm.
D. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

o Stage S1: 300ppm.

o Stage S2: 300ppm.
E. Cu electrowinning

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)


o Fe(2):1.00 g/L.
o Fe(3): 1.00 g/L

(7.16), (7.17), (7.18) and (7.19) give the mass balance results of Copper SX circuit base
case with 30% of extractant volume percent and loaded organic wash stage. Figures
(7.13) and (7.14) give copper and iron flowrates (%) for base case with 30% of
extractant v/v and aqueous phase entrainment in organic phase.
Results show that there is a decrease of copper extraction because of acid

coming with LOWRO to E1 and an accumulation of Copper in the wash stage circuit.

Description Value
Copper SX circuit
Cu Stripping efficiency – Wash stage 2.53 %
Fe Stripping efficiency – Wash stage 41.08 %
Cu/Fe in LOW 1684.99
and loaded organic wash stage
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 109,649 109,417 0,125 0,125
Volume m3/hrs 100,000 102,284 102,181 125,000 0,117 125,000 0,117 125,000
SG t/m3 1,078 1,072 1,071 1,072 1,071
Cu g/L 8,000 1,721 0,273 10,797 1,721 5,459 0,273 4,265
Fe(2) g/l 1,097 1,077 1,077 1,077 1,077
Fe(3) g/l 0,104 0,111 0,099 0,0106 0,111 0,0118 0,099 0,0010
Co g/l 9,000 8,809 8,808 8,809 8,808
Mn g/l 4,000 3,915 3,915 3,915 3,915
Mg g/l 2,000 1,958 1,957 1,958 1,957
Zn g/l 1,500 1,468 1,468 1,468 1,468
Al g/l 1,000 0,979 0,979 0,979 0,979
Acid g/L 2,910 9,828 11,733 9,828 11,733

9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

SOS2A LOWW LOWAc LOWS LOWRR LOWF LOWR LOWRO
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,038 2,043 0,049 2,500 104,457 107,082 106,990 2,533
Volume m3/hrs 0,030 2,043 0,027 2,361 97,522 100,000 99,887 2,365
SG t/m3 1,242 1,000 1,800 1,059 1,071 1,071 1,071 1,071
Cu g/L 38,268 4,880 18,415 18,076 18,415 18,415
Fe(2) g/l 0,999 0,139 0,183 0,183 0,183 0,183
Fe(3) g/l 0,999 0,139 0,357 0,352 0,357 0,357
Co g/l 0,140 0,020 0,433 0,433 0,433 0,433
Mn g/l 0,062 0,009 0,192 0,192 0,192 0,192
Mg g/l 0,031 0,004 0,096 0,096 0,096 0,096
Zn g/l 0,023 0,003 0,072 0,072 0,072 0,072
Al g/l 0,016 0,002 0,048 0,048 0,048 0,048
Acid g/L 171,763 1763,912 50,000 18,749 19,331 18,749 18,749
17,000 18,000 19,000 20,000 21,000 22,000 23,000 24,000

LOW LOWA SOS1 SOS1A SP AdS2 AdS1 EWCC
Solid
Mass t/hrs 0,772
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,125 0,038 63,262 63,426 64,107
Volume m3/hrs 125,000 0,117 125,000 0,030 51,000 51,062 51,374
SG t/m3 1,071 1,248 1,240 1,242 1,248
Cu g/L 10,524 18,415 5,614 49,994 35,000 38,268 49,994
Fe(2) g/l 0,183 0,993 1,000 0,999 0,993
Fe(3) g/l 0,0062 0,357 0,0010 1,006 1,000 0,999 1,006
Co g/l 0,433 0,140 0,141 0,140 0,140
Mn g/l 0,192 0,062 0,062 0,062 0,062
Mg g/l 0,096 0,031 0,031 0,031 0,031
Zn g/l 0,072 0,023 0,023 0,023 0,023
Al g/l 0,048 0,016 0,016 0,016 0,016
Acid g/L 18,749 142,772 180,000 171,763 142,772

25,000 26,000 27,000 28,000 29,000 30,000 31,000 32,000

EWO EWAc EWW EWBl
Solid
Mass t/hrs
Gas
Mass t/hrs 0,195
Liquid
Mass r/hrs 0,092 0,438 0,408
Volume m3/hrs 0,051 0,438 0,329
SG t/m3 1,800 1,000 1,240
Cu g/L 35,000
Fe(2) g/l 1,000
Fe(3) g/l 1,000
Co g/l 0,141
Mn g/l 0,062
Mg g/l 0,031
Zn g/l 0,023
Al g/l 0,016
Acid g/L 1763,912 180,000

7.2.6. Base case – Aqueous coalescing tank
7.2.6.1. Purpose
The reason for adding aqueous coalescing tank is to remove aqueous phase
entrainment in organic to increase the ratio Fe/Mn in spent electrolyte
Figure (7.15) gives the flow diagram of base case with aqueous coalescing tank
of Copper SX-EW circuit

 ACT: Aqueous coalescing tank

aqueous coalescing tank

extraction train.
 LOACT: loaded organic from aqueous coalescing tank.
 LOACTA: Aqueous entrainment of loaded organic from aqueous
coalescing tank.
 ACTS: Solution from aqueous coalescing tank.
stripping train.


B. Extraction train

Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)


HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Fe+3+3HR=FeR 3 +3H + (7.c)
[FeR ]∗([H+ ])3

K e =[Fe+33]∗([HR])3 (7.5)



o Stage E1: 95%.
o Stage E2: 96%.
C. Aqueous coalescing tank
 Aqueous entrainment in organic for settle flux about 25m3/m2/hr:

400ppm.

D. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

o Stage S1: 300ppm.
o Stage S2: 300ppm.
E. Cu electrowinning

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)


o Fe(2):1.00 g/L.
o Fe(3): 1.00 g/L


(7.21), (7.22) and (7.23) give the mass balance results of Copper SX circuit base case
with 30% of extractant volume percent and aqueous coalescing tank. Figures (7.16) and
(7.17) give copper and iron flowrates (%) for base case with 30% of extractant v/v and
aqueous coalescing tank.
Results show that the ratio Fe/Mn increases to 7.463.
Description Value
Copper SX circuit

and aqueous coalescing tank
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

PLS RafE1 RafE2 LOE1 LOE1A LOE2 LOE2A LOACT
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 107,203 106,996 0,125 0,125
Volume m3/hrs 100,000 99,991 99,890 125,000 0,117 125,000 0,117 125,000
SG t/m3 1,078 1,072 1,071 1,072 1,071
Cu g/L 8,000 1,453 0,227 10,464 1,453 5,226 0,227 10,464
Fe(2) g/l 1,097 1,098 1,098 1,098 1,098
Fe(3) g/l 0,104 0,106 0,091 0,0117 0,106 0,0132 0,091 0,0117
Co g/l 9,000 9,007 9,006 9,007 9,006
Mn g/l 4,000 4,003 4,003 4,003 4,003
Mg g/l 2,000 2,002 2,001 2,002 2,001
Zn g/l 1,500 1,501 1,501 1,501 1,501
Al g/l 1,000 1,001 1,001 1,001 1,001
Acid g/L 2,910 9,497 11,099 9,497 11,099
9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

LOACTA ACTS SOS2 SOS2A SOS1 SOS1A SP AdS2
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,050 0,075 0,038 0,038 63,386 63,548
Volume m3/hrs 0,047 0,070 125,000 0,030 125,000 0,030 51,000 51,062
SG t/m3 1,072 1,072 1,245 1,250 1,243 1,245
Cu g/L 1,453 1,453 4,236 38,239 5,574 49,941 35,000 38,239
Fe(2) g/l 1,098 1,098 0,999 0,994 1,000 0,999
Fe(3) g/l 0,106 0,106 0,0010 0,999 0,0010 1,020 1,000 0,999
Co g/l 9,007 9,007 0,602 0,607 0,603 0,602
Mn g/l 4,003 4,003 0,268 0,270 0,268 0,268
Mg g/l 2,002 2,002 0,134 0,135 0,134 0,134
Zn g/l 1,501 1,501 0,100 0,101 0,100 0,100
Al g/l 1,001 1,001 0,067 0,067 0,067 0,067
Acid g/L 9,497 9,497 171,858 143,171 180,000 171,858

17,000 18,000 19,000 20,000 21,000 22,000 23,000 24,000

AdS1 EWCC EWO EWW EWAc EWBl
Solid
Mass t/hrs 0,754
Gas
Mass t/hrs 0,190
Liquid
Mass r/hrs 64,152 0,815 0,191 0,829
Volume m3/hrs 51,308 0,815 0,106 0,667
SG t/m3 1,250 1,000 1,800 1,243
Cu g/L 49,941 35,000
Fe(2) g/l 0,994 1,000
Fe(3) g/l 1,020 1,000
Co g/l 0,607 0,603
Mn g/l 0,270 0,268
Mg g/l 0,135 0,134
Zn g/l 0,101 0,100
Al g/l 0,067 0,067
Acid g/L 143,171 1763,912 180,000

7.2.7. Base case – Spraying water on loaded organic phase
7.2.7.1. Purpose
The reason for adding aqueous coalescing tank is to remove aqueous phase
entrainment in organic to increase the ratio Fe/Mn in spent electrolyte
Figure (7.18) gives the flow diagram of base case with spraying water on loaded
organic of Copper SX-EW circuit

 ACT: Aqueous coalescing tank.
 DL: Discharge launder of E1

spraying water on loaded organic

extraction train.
 DLW: Spraying water on loaded organic in E1 discharge launder.
 LODL: Loaded organic from E1 discharge launder.
 LODLA: Aqueous entrainment of loaded organic from E1 discharge
launder.
coalescing tank.
stripping train.

B. Extraction train

Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)


HGPLS): 1.25.

o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Fe+3+3HR=FeR 3 +3H + (7.c)
[FeR ]∗([H+ ])3

K e =[Fe+33]∗([HR])3 (7.5)



o Stage E1: 95%.
o Stage E2: 96%.

C. Spraying water in E1 discharge launder
 Wash water in loaded organic: 500ppm
D. Aqueous coalescing tank

400ppm.
E. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

o Stage S1: 300ppm.
o Stage S2: 300ppm.
F. Cu electrowinning

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)

EWO=0.252EWCC (7.2)


o Fe(2):1.00 g/L.
o Fe(3): 1.00 g/L

case with 30% of extractant volume percent and aqueous coalescing tank. Figures (7.19)
and (7.20) give copper and iron flowrates (%) for base case with 30% of extractant v/v
and aqueous coalescing tank.
Results show that the ratio Fe/Mn increases to 11.052.
Description Value
Copper SX circuit

and spraying water on loaded organic
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

PLS RafE1 RafE2 LOE1 LOE1A LOE2 LOE2A DLW
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 107,266 107,058 0,125 0,125 0,063
Volume m3/hrs 100,000 100,052 99,952 125,000 0,117 125,000 0,117 0,063
SG t/m3 1,078 1,072 1,071 1,072 1,071 1,000
Cu g/L 8,000 1,456 0,228 10,474 1,456 5,239 0,228
Fe(2) g/l 1,097 1,098 1,098 1,098 1,098
Fe(3) g/l 0,104 0,106 0,091 0,0117 0,106 0,0132 0,091
Co g/l 9,000 9,003 9,002 9,003 9,002
Mn g/l 4,000 4,001 4,001 4,001 4,001
Mg g/l 2,000 2,001 2,000 2,001 2,000
Zn g/l 1,500 1,501 1,500 1,501 1,500
Al g/l 1,000 1,000 1,000 1,000 1,000
Acid g/L 2,910 9,490 11,094 9,490 11,094
9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

LODL LODLA LOACT LOACTA ACTS SOS2 SOS2A SOS1
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,188 0,050 0,138 0,038
Volume m3/hrs 125,000 0,179 125,000 0,048 0,131 125,000 0,030 125,000
SG t/m3 1,048 1,048 1,048 1,244
Cu g/L 10,474 0,949 10,474 0,949 0,949 4,247 38,242 5,586
Fe(2) g/l 0,715 0,715 0,715 0,999
Fe(3) g/l 0,0117 0,069 0,0117 0,069 0,069 0,0010 0,999 0,0010
Co g/l 5,868 5,868 5,868 0,407
Mn g/l 2,608 2,608 2,608 0,181
Mg g/l 1,304 1,304 1,304 0,090
Zn g/l 0,978 0,978 0,978 0,068
Al g/l 0,652 0,652 0,652 0,045
Acid g/L 7,055 7,055 7,055 171,842

17,000 18,000 19,000 20,000 21,000 22,000 23,000 24,000

SOS1A SP AdS2 AdS1 EWCC EWO EWW EWAc
Solid
Mass t/hrs 0,754
Gas
Mass t/hrs 0,190
Liquid
Mass r/hrs 0,038 63,334 63,496 64,100 0,806 0,189
Volume m3/hrs 0,030 51,000 51,062 51,307 0,806 0,105
SG t/m3 1,249 1,242 1,244 1,249 1,000 1,800
Cu g/L 49,940 35,000 38,242 49,940
Fe(2) g/l 0,994 1,000 0,999 0,994
Fe(3) g/l 1,020 1,000 0,999 1,020
Co g/l 0,410 0,407 0,407 0,410
Mn g/l 0,182 0,181 0,181 0,182
Mg g/l 0,091 0,090 0,090 0,091
Zn g/l 0,068 0,068 0,068 0,068
Al g/l 0,046 0,045 0,045 0,046
Acid g/L 143,126 180,000 171,842 143,126 1763,912
25,000 26,000 27,000 28,000 29,000 30,000 31,000 32,000

EWBl
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,817
Volume m3/hrs 0,658
SG t/m3 1,242
Cu g/L 35,000
Fe(2) g/l 1,000
Fe(3) g/l 1,000
Co g/l 0,407
Mn g/l 0,181
Mg g/l 0,090
Zn g/l 0,068
Al g/l 0,045
Acid g/L 180,000


7.2.8. Base case – 80% maximum load (optimal configuration)
7.2.8.1. Purpose
The reason to have 80% maximum load is to reduce the flowrate of EWBl.
Figure (7.21) gives the flow diagram of base case with 80% maximum load of
Copper SX-EW circuit
Figure 7.21: Flow diagram of Copper SX-EW base case 80% maximum load



extraction train.
launder.
coalescing tank.
stripping train.

B. Extraction train


Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)


HGPLS): 1.25.
 Ratio LO/ML: 80%.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Fe+3+3HR=FeR 3 +3H + (7.c)

[FeR ]∗([H+ ])3
K e =[Fe+33]∗([HR])3 (7.5)



o Stage E1: 95%.
o Stage E2: 96%.

400ppm.
E. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.

Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

o Stage S1: 300ppm.
o Stage S2: 300ppm.

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)


o Fe(2):1.00 g/L.
o Fe(3): 1.00 g/L

with 80% maximum load. Figures (7.22) and (7.23) give copper and iron flowrates (%)
for base case with 80% of maximum load.
Results show that comparatively to Copper solvent extraction with 30% and
loaded organic wash stage, extractant percent in organic phase decreases from 30% to
25.98%. But the copper in the raffinate increases from 3.49% to 4.27%.

Description Value
Copper SX circuit
Extractant volume percent 25.98 %
Ratio LO/ML 80 %
Table 7.30: Mass balance of Cu SX Circuit base case with 80% maximum load
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 107,909 107,643 0,125 0,125 0,188
Volume m3/hrs 100,000 100,543 100,434 125,000 0,116 125,000 0,117 0,188
SG t/m3 1,078 1,073 1,072 1,073 1,072 1,000
Cu g/L 8,000 2,159 0,340 9,899 2,159 5,132 0,340
Fe(2) g/l 1,097 1,096 1,096 1,096 1,096
Fe(3) g/l 0,104 0,108 0,100 0,0073 0,108 0,0076 0,100
Co g/l 9,000 8,962 8,961 8,962 8,961
Mn g/l 4,000 3,983 3,983 3,983 3,983
Mg g/l 2,000 1,991 1,991 1,991 1,991
Zn g/l 1,500 1,494 1,494 1,494 1,494
Al g/l 1,000 0,996 0,996 0,996 0,996
Acid g/L 2,910 9,274 11,589 9,274 11,589

9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,313 0,050 0,263 0,038
Volume m3/hrs 125,000 0,304 125,000 0,049 0,255 125,000 0,030 125,000
SG t/m3 1,029 1,029 1,029 1,243
Cu g/L 9,899 0,828 9,899 0,828 0,828 3,659 37,989 4,893
Fe(2) g/l 0,420 0,420 0,420 0,999
Fe(3) g/l 0,0073 0,041 0,0073 0,041 0,041 0,0010 0,999 0,0010
Co g/l 3,438 3,438 3,438 0,415
Mn g/l 1,528 1,528 1,528 0,185
Mg g/l 0,764 0,764 0,764 0,092
Zn g/l 0,573 0,573 0,573 0,069
Al g/l 0,382 0,382 0,382 0,046
Acid g/L 4,726 4,726 4,726 172,474
17,000 18,000 19,000 20,000 21,000 22,000 23,000 24,000

SOS1A SP AdS2 AdS1 EWCC EWO EWW EWAc
Solid
Mass t/hrs 0,766
Gas
Mass t/hrs 0,193
Liquid
Mass r/hrs 0,038 63,336 63,485 64,104 0,543 0,110
Volume m3/hrs 0,030 51,000 51,057 51,309 0,543 0,061
SG t/m3 1,249 1,242 1,243 1,249 1,000 1,800
Cu g/L 49,969 35,000 37,989 49,969
Fe(2) g/l 0,994 1,000 0,999 0,994
Fe(3) g/l 1,009 1,000 0,999 1,009
Co g/l 0,416 0,416 0,415 0,416
Mn g/l 0,185 0,185 0,185 0,185
Mg g/l 0,092 0,092 0,092 0,092
Zn g/l 0,069 0,069 0,069 0,069
Al g/l 0,046 0,046 0,046 0,046
Acid g/L 143,090 180,000 172,474 143,090 1763,912

25,000 26,000 27,000 28,000 29,000 30,000 31,000 32,000

EWBl
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,462
Volume m3/hrs 0,372
SG t/m3 1,242
Cu g/L 35,000
Fe(2) g/l 1,000
Fe(3) g/l 1,000
Co g/l 0,416
Mn g/l 0,185
Mg g/l 0,092
Zn g/l 0,069
Al g/l 0,046
Acid g/L 180,000
Figure 7.22: Copper flowrate (%) for base case with 80% maximum load

Figure 7.23: Iron flowrate (%) for base case with 80% maximum load
7.3. Modeling of Copper SX-EW circuit with dithionate
7.3.1. Dithionate case - Copper and other elements in PLS
7.3.1.1. Flow diagram of dithionate case
Figure (7.2) gives the flow diagram of dithionate case with PLS containing
Copper and other elements of Copper SX-EW circuit


only copper in PLS



B. Extraction train

o S2 O−26 concentration: calculated using Equation (7.6) (J.
KAFUMBILA, 2022).
C(S2 O−2
6 )
=19.308+2.471*(CCo +CMn +CFe(2) )-49.112Eh (7.6)
Where “𝐶(𝑆2 𝑂6−2 ) ”, “𝐶𝐶𝑜 ”, “𝐶𝑀𝑛 ” and “𝐶𝐹𝑒(2) ” are the concentrations of 𝑆2 𝑂6−2, Co,
Mn and Fe(2) in solution (g/L) and “Eh” is redox potential of solution (V).
Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)


HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
 In the model is explained in chapter (4.4.4), Equation of negative

electrical charge includes the charge of dithionate and Ionic strength
Equation includes molar of dithionate.
C. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2
 In the model is explained in chapter (4.4.4), Equation of negative

electrical charge includes the charge of dithionate and Ionic strength
Equation includes molar of dithionate.

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)

Table (7.34) gives metallurgical performances of Copper SX circuit. In PLS, the

concentrations of Fe(2) and Fe(3) change from 1.097g/L and 0.104g/L respectively to
1.611g/L and 0.082g/L in presence of dithionate and in equilibrium with copiapite.
Fe(3) concentration decreases in PLS with the presence of dithionate because soluble
compounds of Fe(3) are almost the complex compounds of Fe(3) with sulfate (FeSO+ 4,
− +2
Fe(SO4 )2 , FeHSO4 , FeH(SO4 )2).
The presence of dithionate decreases Copper extraction recovery comparatively

to base case 30% extractant v/v and all elements in PLS. The presence of dithionate
decreases the concentration of free sulfate (SO−2
4 ) to the neutrality on electrical charge
of solution. Decreasing of free sulfate anion (SO−2
4 ) due to the presence of dithionate in
aqueous phase increases the concentration of free hydrogen ion (H + ) and free copper
ion (Cu+2) according to chemical reactions (4.b), (4.c) and (4.d).
SO−2 + −
4 + H =HSO4 (4.b)
SO−2 +
4 + 2H =H2 SO4 (4.c)
Cu+2 + SO−2
4 = CuSO4 (4.d)
Tables (7.35) and (7.36) give the mass balance results of Copper SX circuit
dithionate case with 30% of extractant volume percent. Figure (7.24) gives copper
flowrate (%) for dithionate case with 30% of extractant v/v.

Description Value
Copper SX circuit
Table 7.35: Mass balance of Cu SX Circuit –dithionate case with 30% extractant
v/v
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 107,762 108,070 107,932 62,969
Volume m3/hrs 100,000 99,917 99,898 125,000 125,000 125,000 125,000 51,000
SG t/m3 1,078 1,082 1,080 1,235
Cu g/L 8,000 1,742 0,320 10,427 5,420 4,283 5,605 35,000
Fe(2) g/l 1,611 1,612 1,612
Fe(3) g/l 0,082 0,083 0,083
Co g/l 9,000 9,008 9,009
Mn g/l 4,000 4,003 4,004
Mg g/l 2,000 2,002 2,002
Zn g/l 1,500 1,501 1,502
Al g/l 1,000 1,001 1,001
S2O6(-2) g/l 27,489 27,512 27,517
Acid g/L 2,873 11,360 13,700 180,00

v/v
8,000 9,000 10,000 11,000 12,000 13,000 14,000 15,000

Solid
Mass t/hrs 0,768
Gas
Mass t/hrs 0,194
Liquid
Mass r/hrs 63,129 63,712 0,218
Volume m3/hrs 51,059 51,280 0,218
SG t/m3 1,236 1,242 1,000
Cu g/L 38,195 49,786
Fe(2) g/l
Fe(3) g/l
Co g/l
Mn g/l
Mg g/l
Zn g/l
Al g/l
S2O6(-2) g/l
Acid g/L 171,924 143,618
Figure 7.24: Copper flowrate (%) for dithionate case with 30% extractant v/v

7.3.2. Dithionate case – Aqueous phase entrainment in organic
phase
Figure (7.25) gives the flow diagram of base case with aqueous phase
entrainment in organic phase of Copper SX-EW circuit



extraction train.
stripping train.
 EWS: Elementary sulfur.

B. Extraction train

KAFUMBILA, 2022).

C(S2 O−2
6 )
=19.308+2.471*(CCo +CMn +CFe(2) )-49.112Eh (7.6)
Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)


HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2


Fe+3+3HR=FeR 3 +3H + (7.c)
[FeR ]∗([H+ ])3

K e =[Fe+33]∗([HR])3 (7.5)



o Stage E1: 95%.
o Stage E2: 96%.
C. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2


o Stage S1: 300ppm.
o Stage S2: 300ppm.

2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)

 Dithionate decomposition
o Half of dithionate is oxidized to sulfate by oxygen on anode
according to the chemical (7.d). Equation (7.7) gives mass of
oxygen gas used to oxidize dithionate to sulfate.
(−2) (−2)
S2 O6 +O2 +2H2 O=4SO4 +4H + (7.d)
M(O2 ) =0.050*M(S (−2) (7.7)

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

according to the chemical reaction (7.e). Equation (7.8) gives
mass of oxygen gas produced to reduce dithionate to elementary
sulfur.
(−2)
S2 O6 +8H + =10O2 +8S ° +4H2 O (7.e)
M(O2 ) =0.500*M(S (−2) (7.8)

2 O6 )

o Fe (2):1.00 g/L.
o Fe(3): 1.00 g/L


(7.38), (7.39) and (7.40) give the mass balance results of Copper SX circuit dithionate
case with 30% of extractant volume percent and aqueous phase entrainment in organic
phase. Figures (7.26) and (7.27) give copper and iron flowrates (%) for dithionate case
with 30% of extractant v/v and aqueous phase entrainment in organic phase.
The low level of Fe(3) in PLS and the presence of high concentration of
hydrogen ions increase the ratio Cu/Fe in LO from 890.21 to 1908.95 comparatively to
the flow diagram without dithionate.
The copper solvent extraction recovery decreases from 97.22% to 96.20%

comparatively to the flow diagram without dithionate. In this condition, the only
remaining operation is to reduce the ratio Fe/Mn in Cu electrowinning circuit.
Description Value
Copper SX circuit

v/v with aqueous entrainment
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 108,683 108,071 107,849 0,125 0,125
Volume m3/hrs 100,000 99,916 99,812 125,000 0,116 125,000 0,116 125,000
SG t/m3 1,087 1,082 1,081 1,081 1,081
Cu g/L 8,000 1,681 0,305 10,281 1,681 5,225 0,305 4,116
Fe(2) g/l 1,632 1,633 1,633 1,633 1,633
Fe(3) g/l 0,084 0,084 0,078 0,0054 0,084 0,0059 0,078 0,0010
Co g/l 9,000 9,008 9,007 9,008 9,007
Mn g/l 4,000 4,003 4,003 4,003 4,003
Mg g/l 2,000 2,002 2,002 2,002 2,002
Zn g/l 1,500 1,501 1,501 1,501 1,501
Al g/l 1,000 1,001 1,001 1,001 1,001
S2O6(-2) g/l 27,541 27,565 27,561 27,565 27,561
Acid g/L 2,873 11,457 13,812 11,457 13,812
9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

SOS2A SOS1 SOS1A SP AdS2 AdS1 EWCC EWO
Solid
Mass t/hrs 0,758
Gas
Mass t/hrs 0,192
Liquid
Mass r/hrs 0,038 0,038 63,954 64,113 64,788
Volume m3/hrs 0,030 125,000 0,030 51,000 51,063 51,385
SG t/m3 1,256 1,261 1,254 1,256 1,261
Cu g/L 38,178 5,430 49,715 35,000 38,178 49,715
Fe(2) g/l 0,999 0,996 1,000 0,999 0,996
Fe(3) g/l 0,999 0,0010 1,003 1,000 0,999 1,003
Co g/l 2,785 2,787 2,789 2,785 2,787
Mn g/l 1,238 1,238 1,239 1,238 1,238
Mg g/l 0,619 0,619 0,620 0,619 0,619
Zn g/l 0,464 0,464 0,465 0,464 0,464
Al g/l 0,309 0,310 0,310 0,309 0,310
S2O6(-2) g/l 0,000 0,062 0,000 0,000 0,062
Acid g/L 172,090 143,922 180,000 172,090 143,922

17,000 18,000 19,000 20,000 21,000 22,000 23,000 24,000

EWS EWW EWAc EWBl
Solid
Mass t/hrs 6,381E-04
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,448 0,099 0,431
Volume m3/hrs 0,448 0,055 0,344
SG t/m3 1,000 1,800 1,254
Cu g/L 35,000
Fe(2) g/l 1,000
Fe(3) g/l 1,000
Co g/l 2,789
Mn g/l 1,239
Mg g/l 0,620
Zn g/l 0,465
Al g/l 0,310
S2O6(-2) g/l 0,000
Acid g/L 1763,912 180,000
Figure 7.26: Copper flowrate (%) for dithionate case with 30% extractant v/v
and aqueous phase entrainment in organic phase

Figure 7.27: Iron flowrate (%) for dithionate case with 30% extractant v/v and
aqueous phase entrainment in organic phase
7.3.3. Dithionate case – Optimal configuration
7.3.3.1. Purpose
The most important constraint is to have the highest copper solvent extraction
recovery because the presence of dithionate in PLS removes the Iron constraint.
Figure (7.28) gives the flow diagram of dithionate case – optimal configuration
of Copper SX-EW circuit


Figure 7.28: Flow diagram of Copper SX-EW dithionate case – optimal configuration

extraction train.
launder.
coalescing tank.
stripping train.
 EWS: Elementary sulfur.

B. Extraction train

KAFUMBILA, 2022).
C(S2 O−2
6 )
=19.308+2.471*(CCo +CMn +CFe(2) )-49.112Eh (7.6)
Fe+2+4Fe+3 +6SO−2
4 + 22H2 O = Fe5 (SO4 )6 (OH)2 . 20H2 O + 2H
+
(7.b)

4 )
)-22*log(aw ) (7.4)



HGPLS): 1.25.
o Stage E1: 95%.
o Stage E2: 96%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-109.99 * v/v%(−1.699) ) ∗ Cue(or)+ 46.386 * v/v%(−0.618) (4.105)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

Fe+3+3HR=FeR 3 +3H + (7.c)
[FeR ]∗([H+ ])3

K e =[Fe+33]∗([HR])3 (7.5)



o Stage E1: 95%.
o Stage E2: 96%.

400ppm.
E. Stripping train
o Stage S1: 98%.
o Stage S2: 95%.
Ce(CuR2 ) ∗ (Ce + ∗γ(H+ ) )2

(H )
=(-80.719 * v/v%(−1.508) ) ∗ Cue(or)+ 87.123* v/v%(−0.826) (4.106)
Ce(Cu+2 ) ∗γ(Cu+2 ) ∗ (Ce(HR) )2

o Stage S1: 300ppm.
o Stage S2: 300ppm.


2CuSO4 +2H2 O=2Cu° +O2 +2H2 SO4 (7.a)
EWO=0.252EWCC (7.2)

 Dithionate decomposition
o Half of dithionate is oxidized to sulfate by oxygen on anode
according to the chemical (7.d). Equation (7.7) gives mass of
oxygen gas used to oxidize dithionate to sulfate.
(−2) (−2)
S2 O6 +O2 +2H2 O=4SO4 +4H + (7.d)
M(O2 ) =0.050*M(S (−2) (7.7)

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

according to the chemical reaction (7.e). Equation (7.8) gives
mass of oxygen gas produced to reduce dithionate to elementary
sulfur.
(−2)
S2 O6 +8H + =10O2 +8S ° +4H2 O (7.e)
M(O2 ) =0.500*M(S (−2) (7.8)

2 O6 )

o Fe(2):1.00 g/L.
o Fe(3): 1.00 g/L


(7.42), (7.43), (7.44) and (7.45) give the mass balance results of Copper SX circuit
dithionate case – optimal configuration. Figures (7.29) and (7.30) give copper and iron
flowrates (%) for dithionate case – optimal configuration.
Description Value
Copper SX circuit
Table 7.41: Mass balance of Cu SX Circuit –dithionate case optimal configuration
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 108,683 108,758 108,526 0,125 0,125 0,313
Volume m /hrs 100,000 100,523 100,418 125,000 0,116 125,000 0,116 0,313
3
SG t/m3 1,087 1,082 1,081 1,082 1,081 1,000

Cu g/L 8,000 1,829 0,347 10,439 1,829 5,443 0,347
Fe(2) g/l 1,632 1,627 1,627 1,627 1,627
Fe(3) g/l 0,084 0,086 0,081 0,0051 0,086 0,0054 0,081
Co g/l 9,000 8,963 8,963 8,963 8,963
Mn g/l 4,000 3,984 3,983 3,984 3,983
Mg g/l 2,000 1,992 1,992 1,992 1,992
Zn g/l 1,500 1,494 1,494 1,494 1,494
Al g/l 1,000 0,996 0,996 0,996 0,996
S2O6(-2) g/l 27,541 27,426 27,423 27,426 27,423
Acid g/L 2,873 11,698 14,236 11,698 14,236

9,000 10,000 11,000 12,000 13,000 14,000 15,000 16,000

Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,438 0,050 0,388 0,038
Volume m3/hrs 125,000 0,428 125,000 0,049 0,379 125,000 0,030 125,000
SG t/m3 1,023 1,023 1,023 1,244
Cu g/L 10,439 0,494 10,439 0,494 0,494 4,242 38,223 5,573
Fe(2) g/l 0,440 0,440 0,440 0,999
Fe(3) g/l 0,0051 0,023 0,0051 0,023 0,023 0,0010 0,999 0,0010
Co g/l 2,422 2,422 2,422 0,445
Mn g/l 1,077 1,077 1,077 0,198
Mg g/l 0,538 0,538 0,538 0,099
Zn g/l 0,404 0,404 0,404 0,074
Al g/l 0,269 0,269 0,269 0,049
S2O6(-2) g/l 7,412 7,412 7,412 0,000
Acid g/L 3,907 3,907 3,907 171,889
17,000 18,000 19,000 20,000 21,000 22,000 23,000 24,000

SOS1A SP AdS2 AdS1 EWCC EWO EWS EWW
Solid
Mass t/hrs 0,765 7,254E-05
Gas
Mass t/hrs 0,193
Liquid
Mass r/hrs 0,038 63,344 63,505 64,106 0,416
Volume m3/hrs 0,030 51,000 51,061 51,307 0,416
SG t/m3 1,249 1,242 1,244 1,249 1,000
Cu g/L 49,865 35,000 38,223 49,865
Fe(2) g/l 0,994 1,000 0,999 0,994
Fe(3) g/l 1,003 1,000 0,999 1,003
Co g/l 0,445 0,446 0,445 0,445
Mn g/l 0,198 0,198 0,198 0,198
Mg g/l 0,099 0,099 0,099 0,099
Zn g/l 0,074 0,074 0,074 0,074
Al g/l 0,049 0,050 0,049 0,049
S2O6(-2) g/l 0,007 0,000 0,000 0,007
Acid g/L 143,360 180,000 171,889 143,360

25,000 26,000 27,000 28,000 29,000 30,000 31,000 32,000

EWAc EWBl
Solid
Mass t/hrs
Gas
Mass t/hrs
Liquid
Mass r/hrs 0,072 0,293
Volume m3/hrs 0,040 0,236
SG t/m3 1,800 1,242
Cu g/L 35,000
Fe(2) g/l 1,000
Fe(3) g/l 1,000
Co g/l 0,446
Mn g/l 0,198
Mg g/l 0,099
Zn g/l 0,074
Al g/l 0,050
S2O6(-2) g/l 0,000
Acid g/L 1763,912 180,000
Figure 7.29: Copper flowrate (%) for dithionate case optimal configuration

Figure 7.30: Iron flowrate (%) for dithionate case optimal configuration

8. References
J. Kafumbila, 2022A, Prediction method for equilibrium values in Copper solvent

extraction in sulfate system: Effect of ionic strength, 2022.
(PDF) Prediction method for equilibrium values in Copper solvent extraction in
sulfate system: Effect of ionic strength (researchgate.net)
J. Kafumbila, 2022B, Prediction of dithionate and Iron saturation concentrations

in solution during reductive leaching of Cobalt using sulfur dioxide gas as
reducing agent.
(PDF) Prediction of dithionate and iron saturation concentrations in solution during
reductive leaching of cobalt using sulfur dioxide gas as reducing agent (researchgate.net)
AIDI AMEL, Etude thermodynamique de l’extraction des métaux de transition par

Salicylidèneaniline, Thèse, Université Mohamed Khider, 2013.
Ritcey G.M., Ashbrook A.W., Solvent extraction: principles and application of

process metallurgy, Part I, Elsevier, 1984.
Pierre-Antoine Noirot, Logiciels d’étude et de prévision des extractions par

solvants : application à la valorisation des solutions de chlorure de Nickel, Thèse,
Université des sciences et techniques de Lille, 1985.
C.M. Moreno, J.R. Pérez-correa, A. Otero, Dynamic modelling of copper solvent

extraction mixer-settler units, Minerals Engineering, 2009.
Philip J.D. LLOYD, solvent extraction principles and practice-Second Edition,

Taylor & Francis Group, 2004.
D.B. Dreisinger, Solvent extraction kinetic of divalent metals with organophorus

acids using the rotating diffusion cell technique, ISEC’88 volume II, USSR, 1988.
F.J. Alguacif, Modelling copper solvent extraction from acidic sulphate solution
using MOC 45, Rev. Metal. Madrid, 1998.
Hossen Aminian, Modélisation et simulation des opérations d’extraction par

solvant et d’électrolyse du Cuivre, thèse, université de Laval, Canada, 1999.

Gerald L. Bauer and Thomas W. Chapman, Measurement and correlation of
solvent extraction equilibria. The extraction of Copper by kelex 100, Metallurgical
transaction B, 1976.
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, Vol. 281,
December, 1981, PP 1249-1516.
Bjorn Beverskog et al, Pourbaix diagrams for the system copper – chlorine at 5 –
100°C, SKI Rapport 98:19, April 1998.
Charles E. Harvi et al, 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,
Geochemical et Cosmochimica Acta (1984) Vol. 48 pp 723-751.
H.C. Helgeson, Thermodynamics of hydrothermal systems at elevated temperatures

and pressures, American Journal of Science 267, 1969, 729-804.
J. Kafumbila, 2017A, Design of counter current decantation in copper

hydrometallurgy - (PDF) DESIGN OF COUNTER CURRENT DECANTATION IN
COPPER METALLURGY (researchgate.net)
Jaime Treco Gallardo, 2007, Modeling chalcopyrite leaching, Thesis, University

of British Columbia.
Sorderstrom M. et al, Stage efficiency in Copper solvent extraction Plants,

technical paper, 2010.
Liu Jiarshe, Lan Zhuo Yue, Qiu Guarr Zhou, Wang Diarr Zuo, Mechanism of crud
formation in copper solvent extraction, journal CSUT, Vol 9, 2002.
Readett, D.J. and Miller, G.M., The impact of silica on solvent extraction:
Ginlambone copper company case study, Copper, Santiago, Chile, November
1995.
Mukutuma A., Schwarz N., and Feather A., Operation of a Flottweg Tricanter
Centrifuge for crud treatment at Bwana Mkubwa solvent extraction plant, ISEC
2008.

Andersen T.N. Adamson D.L. and Richards K.J., The corrosion of lead anodes in
copper electrowinning, Metallurgical transactions, Volume 5, 1974.
Kafumbila J., Design of copper electrowinning circuit using conventional cells,

2017B.
(PDF) DESIGN OF COPPER ELECTROWINNING CIRCUIT USING CONVENTIONAL
CELLS (researchgate.net)
Winand R., Electrocristallisation. Théorie et application, Journal de physique IV,

1994.
Hans Hein, Importance of a wash stage in copper solvent extraction,

Hydrocopper, 2005.
L. Gotfryd and G. Pieter, Contaminants of post-leaching copper solutions and

their behaviour during extraction with industrial extractants,
Physicochem.Probl.Miner.Process, 49(1), 2013.
D.R. Shaw and D.B. Dreisinger, The commercialization of the FENIX iron control
system for purifying copper electrowinning electrolytes, the journal of the
minerals, metals and materials society, July 2004.
N.B. du Preez et al, Evaluation of copper solvent extraction circuit data and
performance, SAIMM – Base Metals Conference, Livingstone – Zambia, July
2015.
J. Kafumbila, Prediction of dithionate and iron saturation concentrations in

solution during reductive leaching of cobalt using sulfur dioxide gas as reducing
agent, 2022.
(PDF) Prediction of dithionate and iron saturation concentrations in solution
during reductive leaching of cobalt using sulfur dioxide gas as reducing agent
(researchgate.net)
Francisco Reyes et al, Metallurgical performance of small and medium size

copper SX plants: Relevance of the SX reagent formulation, Hydroprocess, 2013.
Miller G., Metallurgical plant design and operating strategies: Selection of

entrainment control processes in copper solvent extraction plants,
Environmental Science, 2002.

Design of Copper Solvent Extraction Circuit - Effect of Dithionate On Copper Solvent Extraction Recovery

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Design of Copper Solvent Extraction Circuit - Effect of Dithionate On Copper Solvent Extraction Recovery

Uploaded by

Copyright:

Available Formats

PROJECT METALLURGIST

Kafumbila Kasonta Joseph

Joseph Kafumbila Page 1

2. CHEMISTRY OF SOLVENT EXTRACTION 8

2.1. CLASSIFICATION OF METAL SOLVENT EXTRACTION 8

3. CONSTRUCTION OF DISTRIBUTION ISOTHERMS 11

3.1. LABORATORY-SCALE TEST 11

4. NEW SEMI-EMPIRICAL MODEL 16

4.1. EQUILIBRIUM CONDITION 16

5. MACCABE -THIELE DIAGRAM 42

5.1. EXTRACTION STEP 42

Joseph Kafumbila Page 2

7. MODELING OF COPPER SX CIRCUIT 59

7.1. FLOW DIAGRAM OF CU SX CIRCUIT 59

Joseph Kafumbila Page 3

Process simulation as discipline uses mathematical models as basis for analysis

Joseph Kafumbila Page 4

Joseph Kafumbila Page 5

Copper production technology changes drastically in the last 25 years with

At the beginning, copper solvent extraction configuration operating on dilute

MacCabe Thiele method was introduced in design of copper solvent extraction

Several simulation models of copper solvent extraction using chelating reagents

Joseph Kafumbila Page 7

2.1. Classification of metal solvent extraction

Solvent extraction of metallic cation can be classified on process of extraction.

2.1.1. Extraction by salvation

2.1.2. Extraction by cation exchange

2.1.3. Extraction by anion exchange

Joseph Kafumbila Page 8

. The extractant exchanges cation with hydrogen ion as in extraction by cation

2.2. Chemistry of copper solvent extraction

In case of copper solvent extraction, the extraction is typically achieved by an

CuSO4 + 2HR → CuR2 + H2SO4 (2.a)

CuR2 + H2SO4 → CuSO4 + 2HR (2.b)

Where HR is the extractant and CuR2 is copper-organic complex

The organic phase is a mixture of extractant and diluent. Extractant is an

 Ketoximes: Ketoximes are moderately strong copper extractant which operate

Diluent is an organic liquid in which extractant is dissolved. In general, diluent

Joseph Kafumbila Page 9

In industrial practices, maximum value of extractant volume percent (v/v) is

Joseph Kafumbila Page 10

Extraction and strip isotherms are a graphical representation of the equilibrium

3.1. Laboratory-scale test

The following procedure for determining the distribution isotherms is followed:

 Select at least 7 organic-to-aqueous (O/A) ratios at which to perform the

Joseph Kafumbila Page 11

3.2.1. Classification of predicted distribution isotherms

The theoretical prediction gives copper concentration in organic phase as a

3.2.2. Empirical model

The equation (3.4) gives the empirical model of stripping isotherm.

Joseph Kafumbila Page 12

3.2.3. Semi-empirical model

Where “𝐷𝐶𝑢 ” is the distribution ratio of copper, “𝐶𝑢𝑜𝑟 ” is copper concentration

Where “𝐷𝑜 ” is the distribution ratio of copper at trace concentrations, readily

3.2.4. Chemical model

Chemical model requires the knowledge of all intermediate chemical reactions

The step 1 involves the dissolution of extractant in the aqueous phase.

The step 2 involves the dissociation of extractant in the aqueous phase.

The step 3 the first ligand is added to copper in aqueous phase.

CuR+aq + R−aq ↔ CuR 2 aq (step 4) (3.d)

The step 4 the second ligand is added to copper in aqueous phase.

CuR 2 aq ↔ CuR 2 or (step 5) (3.e)

The step 5 the copper complex is absorbed by the organic phase.

C(H2 SO4 ) =10(−0.053) (C(H+ ) ∗ γ(H+ ) )(2) C(SO−2

C(CuSO4 ) =10(2.36) C(Cu+2 ) γ(Cu+2 ) *C(SO−2