DESIGN AND OPTIMIZATION

OF COPPER SOLVENT
EXTRACTION
CONFIGURATIONS

Joseph Kafumbila
Design and optimization of copper solvent extraction configurations
© 2017 Joseph Kafumbila
jokafumbila@hotmail.com

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https://www.researchgate.net/publication/321849653_Design_and_optimization_of_copper_so
lvent_extraction_configurations

Joseph kafumbila Page 1
Contents

1. INTRODUCTION..................................................................................................................... 4

2. CHEMISTRY OF SOLVENT EXTRACTION .................................................................................. 6

2.1. CLASSIFICATION OF METAL SOLVENT EXTRACTION .............................................................................. 6
2.2. CHEMISTRY OF COPPER SOLVENT EXTRACTION................................................................................... 7

3. CONSTRUCTION OF DISTRIBUTION ISOTHERMS .................................................................... 8

3.1. LABORATORY-SCALE TEST ............................................................................................................. 8
3.2. PREDICTED DISTRIBUTION ISOTHERMS ............................................................................................. 8

4. NEW SEMI-EMPIRICAL MODEL ............................................................................................ 13

4.1. EXTRACTION STEP ..................................................................................................................... 13
4.2. STRIPPING STEP ........................................................................................................................ 25
4.3. RESOLUTION OF EQUATIONS OF EQUILIBRIUM CONDITION ................................................................. 29
4.4. COMPARISON OF PREDICTED AND EXPERIMENTAL RESULTS ................................................................ 34

5. MACCABE -THIELE DIAGRAM .............................................................................................. 39

5.1. EXTRACTION STEP ..................................................................................................................... 39
5.2. STRIPPING STEP ........................................................................................................................ 40

6. METALLURGICAL CONSTRAINTS OF COPPER SX .................................................................. 42

6.1. DESCRIPTION AND DESIGN CRITERIA OF COPPER SX .......................................................................... 42
6.2. METALLURGICAL CONSTRAINTS OF COPPER SX ................................................................................ 54

7. STATIC MODELLING ............................................................................................................ 64

7.1. CONCEPT ................................................................................................................................ 64
7.2. STATIC MODELLING PROGRAM DESIGN .......................................................................................... 64

8. SX PLANT OPTIMIZATION .................................................................................................... 75

8.1. CONCEPT ................................................................................................................................ 75
8.2. DATA CORRECTION AND MASS BALANCE ........................................................................................ 75
8.3. SOLVENT EXTRACTION PLANT PARAMETERS .................................................................................... 90

REFERENCES ................................................................................................................................... 98

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Foreword

“The Faraday’s law on the electrolysis of metals gives the quantity of material
deposited at the cathode as a function of time and the intensity of the electric
current. Faraday had found that there is a loss of the electric current. Tafel, in
studying the mechanism of metal deposition at the cathode, had found that the
loss of current is due to the electrical resistance of the circuit and to the over-
potential. Tafel had found the relationship between the current intensity and
the over-potential. In industrial practice the Faraday’s law continues to be used
since it is simple.”

This paper is the final report on design and optimization of copper
solvent extraction configurations. It is a upgrade of metallurgical
engineering paper called “static simulation program of copper
solvent extraction configurations using Microsoft Excel solver”
and metallurgical engineering paper called “data correction and
copper mass balance operations before evaluation of copper
extraction plant performance”

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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.

The goal of this paper is to develop a semi-empirical model which is the extrapolation of
thermodynamic property of a global chemical reaction of copper solvent extraction. Equilibrium condition
of global chemical reaction is resulted on the assumption that chemical activity coefficients of species
change very little only in aqueous phase. On the other hand, chemical activity coefficients of species
change in organic phase. The semi-empirical model is developed using lix984N as copper extractant and
corrections between concentrations of copper in organic and aqueous are obtained. The simple procedure
which allows designers to quickly have a static modeling for complex configuration or new product that
have not yet simulation program developed by supplier is developed using the semi-empirical model.

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The paper gives also a procedure for determining the values of extractant volume percent,
maximum loading, percentage to maximum loading, extraction recovery, stripping recovery and stage
efficiencies of operating plant. These parameters give the performance of operating plant.

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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 [1]:

 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

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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 (a) and (b) give the copper extraction and stripping reaction with an oxime-based
extractant.

CuSO4 + 2*HR → CuR2 + H2SO4 (a)

CuR2 + H2SO4 → CuSO4 + 2*HR (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 [2]. There are three kinds of extractant:

 Ketoximes: Ketoximes are moderately strong copper extractants 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 [2].

In industrial practices, maximum value of extractant volume percent (v/v) is between 30 – 33%
[2]. 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.

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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 [3].

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3.2.1.1. 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 [4]. The equation (1) gives the empirical model of extraction isotherm.

A∗X
Y = X+B (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 (2) and (3).

A = a *ML (2)

(10−pH )b
B= (d ∗ CuPLS + f* CuRaff ) (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 (4) gives the empirical model of stripping isotherm.

Y = C*X +D (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 (5) and (6).

C = g* ML (5)

h∗V%i
D= +m (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.

3.2.1.2. 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 (7).

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Cu
DCu = Cuor (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 [5]. Equation (8) gives the mathematical expression this observation.

Cu
DCu = Cuor = Do ∗ (Lt − mCuor )n (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 (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.

3.2.1.3. 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 [6]. Chemical reactions (c), (d),
(e), (f) and (g) give the intermediate chemical reactions:

HR or ↔ HR aq Step 1 (c)

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

+
HR aq ↔ Haq + R−aq Step 2 (d)

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

Cu+2 − +
aq + R aq ↔ CuR aq Step 3 (e)

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

CuR+aq + R−aq ↔ CuR 2 aq Step 4 (f)

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

CuR 2 aq ↔ CuR 2 or Step 5 (g)

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 [7]. Chemical
reactions (h), (i) and (j) give the intermediate chemical reactions:

Cu+2 +
aq + 2∗ HR or ↔ CuR 2 or + 2∗ Haq (h)

Cu+2 +
aq + (HR)2 or ↔ CuR 2 or + 2∗ Haq (i)

(HR)2 or ↔ 2∗ HR or (j)

In the case of sulfate solution, the chemical reaction (k) must be taken into account.

HSO− + 2−
4 ↔ H + SO4 (k)

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 (9), (10), (11), (12),
(13) and (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 * (9)
[H+ ]2aq

[Cu+2 ]aq ∗[(HR)2 ]or
[CuR 2 ]or = K 2 * (10)
[H+ ]2aq

[(HR)2 ]ot = K 3 * [HR]2or (11)

[Cu+2 ]taq = [Cu+2 ]aq + A * CuR 2 or (12)

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[HR]tor = [HR]or + 2* [(HR)2 ]or+ 2* [CuR 2 ]or (13)

[H +2 ]aq = [H + ]iaq + 2* A* [CuR 2 ]or (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, [𝐻 + ]𝑖𝑎𝑞 is the concentration of
hydrogen ion in the initial aqueous phase and “A” is the ratio of organic phase volume on aqueous phase volume.

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4. New semi-empirical model

4.1. Extraction step

4.1.1. 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 (l) [8]. 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 + (l)

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 (l) is given by equation (15)
[9].

μCuR2 + 2μH+ - μCu+2 - 2μHR = 0 (15)

where μ𝜌 is chemical potential of species ‘ρ’

Chemical potential of species ‘ρ’ is given by equation (16).

Cρ (16)
μρ = RTln(βρ x γρ x )
C0ρ

where 𝛽𝜌 is standard-state activity of species ‘ρ’ and is a function of solvent nature and temperature, 𝛾𝜌 is
chemical activity coefficient of specie ‘ρ’, 𝐶𝜌 is molar concentration of species ‘ρ’, 𝐶𝜌0 is reference molar concentration
which by convention is 1 molar concentration, R is the perfect gas constant, and T is the temperature

The substitution of equation (16) for all species in equation (15) gives equation (17) which is the
thermodynamic equilibrium condition.

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[Cueor ] x [Heaq ]2 βCu x βHR 2 γ x γHR 2
[Cueaq ] x [HReor
= 2 x γ Cu = ψe (17)
]2 βCuR2 x βH CuR2 x γH 2

4.1.2. Value of 𝛙𝐞 from molar concentration

4.1.2.1. Definition

The value of thermodynamic equilibrium condition ψe from molar concentrations called ψe1 is
given by equation (18).

[Cue ]x[He ]2
ψe1 =[Cueor]x[HRaqe ]2 (18)
aq or

4.1.2.2. Copper molar concentrations

The values of copper molar concentrations at the steady-state in organic and aqueous phases are
respectively given by equations (19) and (20).

Cue
[Cueor ] = 63.55
or
(19)

Cue
aq
[Cueaq ] = 63.55 (20)

𝑒 𝑒
where 𝐶𝑢𝑎𝑞 and 𝐶𝑢𝑜𝑟 are respectively copper concentrations (g/L) in aqueous and organic phases

Equation (21) gives copper mass balance at the steady-state.

Vaq
Cueor = Cuior + (Cuiaq - Cueaq ) x V (21)
or

𝑖 𝑖
where 𝐶𝑢𝑎𝑞 and 𝐶𝑢𝑜𝑟 are respectively initial copper concentrations (g/L) in aqueous and organic phases. 𝑉𝑎𝑞
and 𝑉𝑜𝑟 are respectively volumes of aqueous and organic phases.

4.1.2.3. Free extractant molar concentration in organic phase

The value of free extractant molar concentration in organic phase is given by equation (22).

V% x 0.91 x 1000 Cue
[HReor ] = or
- 2 x 63.55 (22)
100 x 270

where 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.

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4.1.2.4. Hydrogen ion molar concentration in aqueous phase

The value of hydrogen ion molar concentration in aqueous phase comes from sulfuric acid
dissociation reaction. Sulfuric acid dissociation reaction has followed chemical reactions (m) and (n).

H2 SO4 ↔ HSO−
4 +H
+
K1ac = 104 (m)

HSO− −2
4 ↔ SO4 + H
+
K ac
2 = 1.25 10
−2 (n)

The corresponding mass-action equilibrium expressions for the chemical reactions (m) and (n)
are given by equations (23) and (24).

[HSO− +
4 ]∗[H ]
= K1ac = 104 (23)
[H2 SO4 ]

[SO−2 +
4 ]∗[H ]
= K ac
2 = 1.25 10
−2 (24)
[HSO−
4]

Where [𝐻𝑆𝑂4− ], [𝑆𝑂4−2 ], [𝐻2 𝑆𝑂4], and [𝐻 + ] are molar concentration of corresponding species in the aqueous
phase.

If C1 is free sulfuric acid molar concentration in aqueous phase and C2 is molar concentration of
anion SO−2 4 associated with copper and buffers in aqueous phase at the initial state. Sulfuric acid
dissociation reaction (m) is complete because the value of chemical reaction equilibrium constant K1ac is
big. Following mass balance comes from sulfuric dissociation reaction (m).

H2 SO4 HSO−
4 H+
Initial state C1 0 0
Final state -C1 C1 C1
Mass balance 0 C1 C1

Sulfuric acid dissociation reaction (n) is not complete because the value of chemical reaction
equilibrium constant K ac
2 is not big enough. Following mass balance comes from sulfuric acid dissociation
reaction (n). “ω” is molar concentration of anion HSO− 4 which goes into dissociation.

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HSO−
4 SO−2
4 H+
Initial state C1 C2 C1
Final state -ω ω ω
Mass balance C1-ω C2+ω C1+ω

Thermodynamic equilibrium condition of sulfuric acid dissociation reaction (n) given by equation
(24) is changed in equation (25). Resolution of the mathematical expression (25) gives second-degree
equation. Hydrogen ion molar concentration in aqueous phase is given by equation (26). The value of
molar concentration “ω” is given by equation (27) and the values of constants “E” and “F” are given by
equations (28) and (29).

(C2 +ω)(C1 +ω)
K ac
2 = (25)
(C1 −ω)

e
[Haq ] = C1 + ω (26)

(−E+ √E2 −4 x F)
ω= (27)
2

E = C1 + C2 + K ac
2 (28)

F = C1 x (C2 - K ac
2 ) (29)

From equation (27), the value of molar concentration “ω” becomes zero when the value of molar
concentration C2 is equal to the value of chemical reaction equilibrium constant K ac 2 . When the value of
molar concentration C2 is greater than the value of chemical reaction equilibrium constant K ac2 , the value
of molar concentration “ω” is lower than zero. In this condition, the value of molar concentration “ω” in
equation (26) is zero. When the value of molar concentration C2 is lower than the value of chemical
reaction equilibrium constant k ac
2 , the value of molar concentration “ω” is greater than zero.

4.1.3. Value of 𝛙𝐞 from chemical activity coefficients

4.1.3.1. Definition

The value of thermodynamic equilibrium condition ψe from chemical activity coefficients of
species called ψe2 is given by equation (30).

βCu x βHR 2 γ x γHR 2
ψe2 = 2 x γ Cu (30)
βCuR2 x βH CuR2 x γH 2

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The value of ψe2 is multiplication of two ratios. First ratio is the ratio of standard – state
activities of species which is a constant and second ratio is the ratio of chemical activity coefficients of
species. The second ratio of chemical activity coefficients also is multiplication of ratios of chemical
activity coefficients in organic and aqueous phases respectively.

4.1.3.2. Ratio of chemical activity coefficients in aqueous phase

Depending on molar concentrations of species in aqueous phase, three cases are possible [1]:

 Aqueous phase very diluted. In this condition, the values of chemical activity coefficients
tend to 1.
 Ionic strength in aqueous phase varies very little. In the condition, the value of ratio of
chemical activity coefficients is a constant.
 Ionic strength in aqueous phase varies. In this condition, the value of ratio of chemical
activity coefficients is a variable.

The assumption is that ionic strength varies very little. So, ratio of chemical activity coefficients is
a constant in aqueous phase.

4.1.3.3. Ratio of chemical activity coefficients in organic phase

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 [9].

The assumption is that this thermodynamic property is also true for chelating copper extractant.

4.1.4. Observations

Conclusion from preceding observations is that the thermodynamic equilibrium condition is
given by equation (31).

[Cueor ]x[Heaq ]2
[Cueaq ]x[HReor ]2
= f([Cueor ]) (31)

4.1.5. Equation of thermodynamic equilibrium condition

4.1.5.1. Pure copper sulfate aqueous phase

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.

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 Extractant: Lix984N.
 Extractant volume percentage in organic: 20%.

Table (1) gives equilibrium line data of lab test 1 from which the values of thermodynamic
equilibrium condition ψe1 of each steady-state position are calculated. Data of steady-state position having
the value of copper concentration in aqueous of 0.79 g/L are derived from condition that the value of
molar concentration C2 is equal to the value of chemical reaction equilibrium constant K ac
2 . Corresponding
copper concentration in organic phase is obtained by extrapolation on equilibrium line. Figure 1 gives the
values of thermodynamic equilibrium condition ψe1 versus the values of copper concentration in organic
phase.

Figure 1: Values of ψe1 versus values of copper concentrations in organic phase of lab test 1

Results show that:

 The values of thermodynamic equilibrium condition ψe1 are not the same for steady-state
positions of equilibrium line.
 The value of thermodynamic equilibrium condition ψe1 is a linear function of the value of
copper concentration in organic phase.
 The values of line slope are not the same in the ranges (0.8 to 5.75 g/L Cu) and (5.75 to
10.8 g/L Cu) where molar concentration “ω” is greater or lower than zero respectively.

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Table 1: Value of ψe1 from equilibrium line data of lab test 1

Lab test 1 Organic Aqueous
Aq Org ψe1
Cu Cu Cu Free Lix984N Cu ω C1 C2 H
g/l g/l moles/l moles/l moles/l moles/l moles/l moles/l moles/l
0.04 0.80 0.013 0.649 0.001 0.010 0.176 0.001 0.187 1.666
0.09 1.58 0.025 0.624 0.001 0.010 0.175 0.001 0.185 1.550
0.35 3.83 0.060 0.554 0.006 0.006 0.171 0.006 0.178 1.125
0.79 5.75 0.090 0.493 0.012 0.000 0.164 0.012 0.164 0.805
1.19 6.76 0.106 0.461 0.019 -0.005 0.158 0.019 0.158 0.668
3.38 9.26 0.146 0.383 0.053 -0.032 0.124 0.053 0.124 0.287
5.92 10.45 0.164 0.345 0.093 -0.048 0.084 0.093 0.084 0.104
6.92 10.80 0.170 0.334 0.109 -0.046 0.068 0.109 0.068 0.065

4.1.5.2. Industrial copper sulfate aqueous phase

Test conditions of lab test 2 done with industrial copper sulfate aqueous phase are the following:

 Elements grade of industrial copper sulfate aqueous phase is given in Table (2).
 Extractant: Lix984N.
 Extractant volume percentage in the organic: 18%.

Table 2: 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 (3) gives equilibrium line data from which the values of thermodynamic equilibrium
condition ψe1 of each steady-state position are calculated. Figure (2) gives the values of thermodynamic
equilibrium condition ψe1 versus the value of copper concentration in organic phase.

Results show that:

 In the industrial aqueous phase containing various sulfate buffers, molar concentration C2
is greater than the value of chemical reaction equilibrium constant K ac 2 . So, molar
concentration “ω” is lower than zero.
 The value of thermodynamic equilibrium condition ψe1 also is a linear function of the
value of copper concentration in organic phase.

Joseph kafumbila Page 19
Table 3: Value of ψe1 from equilibrium line data of lab test 2

Lab test 2 Organic Aqueous
Aq Org ψe1
Cu Cu Cu Free Lix984N Cu ω C1 C2 H
g/l g/l moles/l moles/l moles/l moles/l moles/l moles/l moles/l
0.067 1.721 0.027 0.553 0.0011 -0.107 0.134 0.216 0.134 1.515
0.120 2.555 0.040 0.526 0.0019 -0.106 0.133 0.217 0.133 1.367
0.191 3.359 0.053 0.501 0.0030 -0.106 0.132 0.218 0.132 1.225
0.410 4.819 0.076 0.455 0.0065 -0.104 0.129 0.221 0.129 0.942
1.510 7.438 0.117 0.373 0.0238 -0.094 0.112 0.239 0.112 0.441
4.300 9.290 0.146 0.314 0.0677 -0.060 0.068 0.283 0.068 0.100

Figure 2: Values of ψe1 versus values of copper concentration in organic phase of lab test 2

4.1.5.3. Observations

In order to get closer to industrial conditions, only the range where molar concentrations “ω” are
lower than zero will be taken in static model. In this condition hydrogen ion concentration in aqueous
phase is given now by equation (32). Equation (33) gives sulfuric acid concentrations in aqueous phase at
steady state.

e ACeaq
[Hor ]= (32)
98

e i
Acaq = Acaq + (Cuiaq - Cueaq ) x 1,54 (33)

Joseph kafumbila Page 20
𝑒 𝑖
where 𝐴𝑐𝑎𝑞 is sulfuric acid concentration (g/L) in aqueous phase at the steady-state and 𝐴𝑐𝑎𝑞 is initial
sulfuric acid concentration (g/L) in aqueous phase.

The substitution of equations (19), (20), (22) and (32) in equation (18) gives equation (34) which
gives the value of thermodynamic equilibrium condition ψ1e1 as a function of extractant volume
percentage in organic phase, free acid concentration in aqueous phase and copper concentrations in
organic and aqueous phases.

Cueorg [Ace ]2
ψ1e1 = aq
* [3.3030∗ V%−3.0842∗ = G * Cueorg + H (34)
Cueaq Cue
org ]2

Where “G” and “H” are the constants.

4.1.5.4. Effect of initial free acid concentration

The value of thermodynamic equilibrium condition ψ1e1 obtained from the equation (34) is
plotted versus the values of copper concentration in organic phase in the range where the value of molar
concentration “ω” is lower than zero using pure copper sulfate aqueous phases. Table (4) gives equilibrium
line data of lab test 1, 3, 4 and 5 (value in blue color). Figure (3) gives the value of thermodynamic
equilibrium condition ψ1e1 versus the values of copper concentration in organic phase.

The values of constants “G” and “H” for different concentration of free acid in the feed solution
are given in Table (5)

Table 5: Values of constants “G” and “H”

Free acid concentration (g/L) G H
5 -0.1532 1.7042
10 -0.1406 1.5509
15 -0.1597 1.7313
20 -0.1489 1.6342

Joseph kafumbila Page 21
Table 4: Equilibrium line data of lab tests 1, 3, 4 and 5 of extraction step

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% 20 % V% 20 % V% 20 % V% 20 %
e e e e
Cuaq Cueor Cuaq Cueor Cuaq Cueor Cuaq Cueor
0.04 0.80 0.08 0.80 0.10 0.80 0.15 0.79
0.09 1.58 0.17 1.57 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

Results in Table (5) shows that initial free acid concentration of feed solution does not affect the
values of constants “G” and “H”.

Figure 3: Values of ψe1 versus values of copper concentration in organic phase of
lab tests 1, 3, 4 and 5

Joseph kafumbila Page 22
4.1.5.5. Effect of extractant volume percent in organic phase

The value of thermodynamic equilibrium condition ψ1e1 obtained from the equation (34) is
plotted versus the values of copper concentration in organic phase in the range where the value of molar
concentration “ω” is lower than zero using pure copper sulfate aqueous phases. Table (6) gives equilibrium
line data of lab test 1, 6 and 7 (value in blue color). Figure (4) gives the value of thermodynamic
equilibrium condition ψ1e1 versus the values of copper concentration in organic phase. Results show that:

Results in Table (7) show that:

 Value of constant “G” increases with increasing of value of extractant volume percent.
 Value of constant “H” decreases with increasing of value of extractant volume percent.

Table 6: 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% 15 % V% 18 % V% 20 %
e e e
Cuaq Cueor Cuaq Cueor 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

The values of constants “G” and “H” for different extractant volume percent in organic phase
are given in Table (7)

Table 7: Values of constants “G” and “H”

Extractant volume percent (%) G H
15 -0.252 2.0386
18 -0.1991 1.8381
20 -0.1507 1.6848

Joseph kafumbila Page 23
Figure 4: Values of ψe1 versus values of copper concentration in organic phase of
lab tests 1, 6, and 7

4.1.5.6. Equation of equilibrium condition

The values of constants “G” and “H” are only function of extractant volume percentage.
Equilibrium condition on extraction step is given by equation (35) in the range from 8 to 32% of
extractant volume percent.

Cueorg [Aceaq ]2
Cueaq
* [3.3030∗ V%−3.0842∗ Cue ]2
=(-25.698 * v%(−1.704) ) ∗ Cueor+ 10.663 * v%(−0.608) (35)
org

Table (8) gives the experimental data and data from extraction step equilibrium condition
equation for lab test (1)(pure sulfate solution) and lab test (2) (industrial solution). Results show that:

 For lab test (1), the gap between the values of copper concentration in the organic phase
of experimental and model data is around 5.02% in the range where the value of “ω” is
greater than zero (red color in Table (8)).
 For lab test (1), the gap between the values of copper concentration in the organic phase
of experimental and model data is around 0.30% in the range where the value of “ω” is
less than zero (blue color in Table (8)).

Joseph kafumbila Page 24
 For lab test (2), the gap between the values of copper concentration in the organic phase
of experimental and model data is around 0.27%.

Table 8: Experimental and model data for lab test 1

Lab test 1 Lab test 2
Aqueous phase Organic phase Aqueous phase Organic phase
Experimental Model Experimental Model
Cu (g/L) Cu (g/L) Cu (g/L) Cu (g/L) Cu (g/L) Cu (g/L)
0.04 0.80 0.86 0.067 1.721 1.724
0.09 1.58 1.66 0.120 2.555 2.550
0.35 3.83 3.97 0.191 3.359 3.341
1.19 6.76 6.77 0.410 4.819 4.816
3.38 9.26 9.24 1.510 7.438 7.470
5.92 10.45 10.40 4.300 9.290 9.316
6.93 10.70 10.66

4.2. Stripping step

4.2.1. Equilibrium condition

Stripping 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. Copper stripping chemical reaction with Lix984N extractant is followed chemical reaction (p)
which is the reverse reaction of copper extraction chemical reaction.

CuR 2 + 2H + ↔ Cu2+ + 2HR (p)

Equation (36) gives the thermodynamic equilibrium condition.

[Cueor ] x [Heaq ]2 βCu x βHR 2 γ x γHR 2
[Cueaq ] x [HReor ]2
= 2 x γ Cu = ψs (36)
βCuR2 x βH CuR2 x γH 2

4.2.2. Simulation with extraction step equilibrium condition

Thermodynamic equilibrium condition of extraction and stripping steps are similar. Equilibrium
condition equation of extraction step is used to simulate equilibrium line of 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.
Joseph kafumbila Page 25
 Copper concentration in loaded organic: 15.98 g/l.
 Extractant: Lix984N.
 Extractant volume percentage in organic: 32%.

Table (9) gives equilibrium line data and the values of copper concentration in organic phase
from model of extraction step. Figure (5) gives the graphical representation of results of Table (9).

Results show that there is a gap between the values of copper concentration from experimental
data and data of extraction step model. Results show that the stripping step has a similar model because
experimental and model data have the same profile. The gap between the experimental and model data is
due to the difference of ion strength of the solutions of extraction and stripping steps. The ratios of
chemical activity coefficients in aqueous phase are not the same for PLS solution and spent electrolyte.

Table 9: Copper concentration in organic simulated with extraction step model

Equilibrium line data Model
Aqueous Organic Organic
Cu (g/L) Cu (g/L) Cu (g/L)
37.24 4.45 6.91
39.61 4.74 7.25
41.58 4.90 7.54
47.63 5.71 8.37
49.74 5.84 8.66
53.95 6.42 9.22

Joseph kafumbila Page 26
Figure (5): Graphical representation of results of Table (9)

4.2.3. Equation of equilibrium condition of stripping step

Table (10) gives equilibrium line data and the values of thermodynamic equilibrium condition
ψs1 of lab test 8. Figure (6) gives the value of thermodynamic equilibrium condition ψs1 versus the values
of copper concentration in organic phase.

Results show that:

 The value of thermodynamic equilibrium condition ψs1 is a linear function of the values
of copper concentration in organic phase.
 Accuracy of the value of thermodynamic equilibrium condition ψs1 depends on accuracy
in chemical analysis of copper concentration in aqueous phase.
 The value of molar concentration “ω” is lower than zero.

Joseph kafumbila Page 27
Table 10: Value of ψs1 from equilibrium line data of lab test 8

Lab test 1 Organic Aqueous
Aq Org ψs1
Cu Cu Cu Free Lix984N Cu ω C1 C2 H
g/l g/l moles/l moles/l moles/l moles/l moles/l moles/l moles/l
37.2 4.45 0.070 0.938 0.586 -0.562 1.802 0.586 1.802 0.441
39.6 4.74 0.075 0.929 0.623 -0.598 1.764 0.623 1.764 0.432
41.6 4.90 0.077 0.924 0.634 -0.628 1.733 0.654 1.733 0.415
47.6 5.71 0.090 0.899 0.750 -0.718 1.638 0.750 1.638 0.398
49.7 5.84 0.092 0.895 0.783 -0.748 1.605 0.783 1.605 0.378
53.9 6.42 0.101 0.876 0.849 -0.809 1.539 0.849 1.539 0.367

Figure 6: Values of ψs1 versus the values of copper concentration in organic phase of lab test 8

Results show that value of ψs1 is linear function of the concentration of copper in the organic
phase. Value of ψs1 is affected only by the extractant volume percent in organic phase. Equation (37)
gives the mathematical expression of equilibrium condition of stripping step in the range from 8 to 32% of
extractant volume percent.

Joseph kafumbila Page 28
Cueorg [Ace ]2
Cueaq
aq
* [3.3030∗ V%−3.0842∗ Cue ]2
=(5.11*10(−3) *V%-0.194) ∗ Cueor + 12.81 * v%(−0.901) (37)
org

4.3. Resolution of equations of equilibrium condition

4.3.1. Extraction step

The second semi-empirical model of extraction step using Lix984N as extractant is given by the
equation (35). Equation (33) gives the concentration of free acid at equilibrium.

Cueorg (Aceaq )2
x =(-25.698 * v%(−1.704) ) ∗ Cueor + 10.663 * v%(−0.608) (35)
Cueaq (3.3030 x V%−3.0842 x Cueorg )2

e i
Acaq = Acaq + (Cuiaq - Cueaq ) * 1,54 (33)

𝑖 𝑖
Where “𝐶𝑢𝑎𝑞 ”is the concentration of copper in the PLS (g/L) and “𝐴𝑐𝑎𝑞 ” is the concentration of free acid in
the PLS (g/L).

Equation (38) gives the concentration of free acid as function of pH.

i
Acaq = 98* 10(−pH) (38)

e
The value of “Acaq ” in equation (35) is replaced by the equation (33), it appears equation (39).

Cueorg (Aciaq +(Cuiaq −Cueaq )∗1.54) 2
Cueaq
x (3.3030∗ V%−3.0842∗ Cue )2
=(-25.698 * v%(−1.704) ) ∗ Cueor + 10.663 * v%(−0.608) (39)
org

After arrangement equation (39) becomes equation (40).

Cueorg ((Aciaq +1.54∗Cuiaq )−1.54∗Cueaq )) 2
Cueaq
x (3.3030∗ V%−3.0842∗ Cueorg )2
=(-25.698 * v%(−1.704) ) ∗ Cueor + 10.663 * v%(−0.608) (40)

The new designations are introduced and equation (40) becomes equation (41).

 Y = Cueor
 X = Cueaq

Y (a +b ∗X)2
* ex ex = eex *Y + fex (41)
X (c +d ∗Y)2
ex ex

Joseph kafumbila Page 29
Equations (42), (43), (44), (45), (46) and (47) give the values of “aex ”, “bex ”, “cex ”, “dex ”, “eex ”,
and “fex ”.

i
aex =Acaq + 1.54 * Cuiaq (42)

bex = −1.54 (43)

cex = 3.303*V% (44)

dex = −3.0842 (45)

eex = −25.698 * V%(−1.704) (46)

fex = 10.663 * V%(−0.608) (47)

Equation (41) becomes equation (48) after placing “Y” on one side and “X” on other side.

(aex +bex ∗X)2 (eex ∗Y+fex )∗(cex +dex ∗Y)2
= (48)
X Y

4.3.1.1. Known value of concentration of copper in aqueous

The value of concentration of copper in the aqueous phase at equilibrium is known value. The
unknown value is the concentration of copper in the organic phase at equilibrium.

Equation (49) gives the value of constant “g ex ”.

(aex +bex ∗X)2 (49)
g ex = X

Equation (48) becomes equation (50) after introducing equation (49) where values of constants
“αex ”, “λex ” and “εex ” are given by equations (51), (52) and (53) respectively.

Y 3 + αex *Y 2 +λex *Y +εex =0 (50)

2∗cex ∗dex ∗eex +(dex )2 ∗fex
αex = (51)
(dex )2 ∗eex

2∗cex ∗dex ∗fex + (cex )2 ∗eex − gex
λex = (52)
(dex )2 ∗eex

f ∗(cex )2
εex = (dex (53)
2
ex ) ∗eex

Joseph kafumbila Page 30
Equation (54) gives the value of variable “Y” as a function of variable “t ex ”.

αex
Y = t ex - (54)
3

Equation (50) becomes equation (55) after replacing the variable “Y” by equation (54). Equations
(56) and (57) give the values of constants “pex ” and “q ex ”.

t 3 +pex *t +q ex =0 (55)

(αex )2 (56)
pex = λex - 3

αex ∗λex 2 (57)
q ex = εex - + 27* (αex )3
3

Equation (55) has a form of Cardan formula (three degree equation). The value of “t ex ” is given
by the equation (58).

1 1 1 1
qex 1 4 qex 1 4
t ex = [− 2
− 2 ∗ ((qex )2 + 27 ∗ (pex )3 )(2) ](3) + [− 2
+ 2
∗ ((qex )2 + 27 ∗ (pex )3 )(2) ](3) (58)

4.3.1.2. Known value of concentration of copper in organic

Equation (59) gives the value of constant “hex ”.

(eex ∗Y+fex )∗(cex +dex ∗Y)2 (59)
hex =
Y

Equation (48) becomes equation (60) after introducing equation (59).

(bex )2*X 2 + (2*aex *bex -hex )*X + (aex )2 = 0 (60)

Equation (61) gives the value of concentration of copper in aqueous phase.

1
( )
hex −2∗aex ∗bex −((hex )2 −4∗aex ∗bex ∗hex ) 2 (61)
X= 2∗(bex )2

4.3.2. Stripping step

The second semi-empirical model of stripping step using Lix984N as extractant is given by the
equation (37). Equation (33) gives the concentration of free acid at equilibrium.

Joseph kafumbila Page 31
Cueorg [Aceaq ]2
* =(5.11*10(−3) *V%-0.194) ∗ Cueor + 12.81 * v%(−0.901) (37)
Cueaq [3.3030∗ V%−3.0842∗ Cueorg ]2

e i
Acaq = Acaq + (Cuiaq - Cueaq ) * 1,54 (33)

𝑖 𝑖
Where “𝐶𝑢𝑎𝑞 ”is the concentration of copper in the spent electrolyte (g/L) and “𝐴𝑐𝑎𝑞 ” is the concentration of free
acid in the spent electrolyte (g/L).

e
The value of “Acaq ” in equation (37) is replaced by the equation (33), it appears equation (62).

Cueorg (Aci +(Cui −Cue )∗1.54) 2
Cueaq
aq
x (3.3030∗ aq aq
V%−3.0842∗ Cue )2
=(5.11*10(−3) *V%-0.194) ∗ Cueor + 12.81 * v%(−0.901) (62)
org

After arrangement equation (62) becomes equation (63).

Cueorg ((Aciaq +1.54∗Cuiaq )−1.54∗Cueaq )) 2
Cueaq
x (3.3030∗ V%−3.0842∗ Cueorg )2
=(5.11*10(−3) *V%-0.194) ∗ Cueor+ 12.81 * v%(−0.901) (63)

The new designations are introduced and equation (63) becomes equation (64).

 Y = Cueor
 X = Cueaq

Y (a +b ∗X)2
* st st = est *Y + fst (64)
X (c +d ∗Y)2st st

Equations (65), (66), (67), (68), (69) and (70) give the values of “ast ”, “bst ”, “cst ”, “dst ”, “est ”,
and “fst ”.

i
ast =Acaq + 1.54 * Cuiaq (65)

bst = −1.54 (66)

cst = 3.303*V% (67)

dst = −3.0842 (68)

est = 5.11 ∗ 10(−3) * V%-0.194 (69)

fst = 12.81 * V%(−0.901) (70)

Joseph kafumbila Page 32
Equation (64) becomes equation (71) after placing “Y” on one side and “X” on other side.

(ast +bst ∗X)2 (est ∗Y+fst )∗(cst +dst ∗Y)2
= (71)
X Y

4.3.2.1. Known value of concentration of copper in aqueous

The value of concentration of copper in the aqueous phase at equilibrium is known value. The
unknown value is the concentration of copper in the organic phase at equilibrium.

Equation (72) gives the value of constant “g st ”.

(ast +bst ∗X)2 (72)
g st = X

Equation (71) becomes equation (73) after introducing equation (72) where values of constants
“αst ”, “λst ” and “εst ” are given by equations (74), (75) and (76) respectively.

Y 3 + αex *Y 2 +λex *Y +εex =0 (73)

2∗cst ∗dst ∗est +(dst )2 ∗fst
αst = (74)
(dst )2 ∗est

2∗cst ∗dst ∗fst + (cst )2 ∗est − gst
λst = (75)
(dst )2 ∗est

f ∗(cst )2
εst = (dst (76)
2
st ) ∗est

Equation (77) gives the value of variable “Y” as a function of variable “t st ”.

αst
Y = t st - (77)
3

Equation (73) becomes equation (78) after replacing the variable “Y” by equation (77). Equations
(79) and (80) give the values of constants “pst ” and “q st ”.

t 3 +pst *t +q st =0 (78)

(αst )2 (79)
pst = λst - 3

αst ∗λst 2 (80)
q st = εst - + 27* (αst )3
3

Joseph kafumbila Page 33
Equation (78) has form of Cardan formula (three degree equation). The value of “t st ” is given by
the equation (81).

1 1 1 1
qst 1 4 qst 1 4
t st = [− 2
− 2 ∗ ((qst )2 + 27 ∗ (pst )3 )(2) ](3) + [− 2
+ 2
∗ ((qst )2 + 27 ∗ (pst )3 )(2) ](3) (81)

4.3.2.2. Known value of concentration of copper in organic

Equation (82) gives the value of constant “hst ”.

(est ∗Y+fst )∗(cst +dst ∗Y)2 (82)
hst = Y

Equation (71) becomes equation (83) after introducing equation (82).

(bst )2*X 2 + (2*ast *bst -hst )*X + (ast )2 = 0 (83)

Equation (84) gives the value of concentration of copper in aqueous phase.

1
( )
hst −2∗ast ∗bst −((hst )2 −4∗ast ∗bst ∗hst ) 2 (84)
X= 2∗(bst )2

4.4. Comparison of predicted and experimental results

4.4.1. Extraction step

Table (11) gives example of extraction isotherm from laboratory scale test [10]. PLS contains 2.5
g/L of copper and 1.3 g/L of iron at pH 1.8. The organic phase contains 1.8 g/L of copper and 8.7% of
Lix984N as extractant.

The predicted extraction isotherm is obtained by using the procedure explained in chapter
(4.3.1.). Table (12), as it appears on the Excel spreadsheet, gives the predicted extraction isotherm. The
Figure (7) gives graphical representation of laboratory scale test and semi-empirical model results.

Joseph kafumbila Page 34
Table 11: Laboratory scale test - extraction isotherm

O/A Organic phase Aqueous phase
Cu (g/L) Cu (g/L)
10/1 2.04 0.07
5/1 2.28 0.09
2/1 2.96 0.17
3/2 3.26 0.26
1/1 3.70 0.51
1/2 4.19 1.24
1/5 4.35 1.94

A B C D E F G H I J
1
2 Table 12 Semi-empirical model – predicted extraction isotherm
3 V% 8.7 8.7 8.7 8.7 8.7 8.7 8.7 8.7
4 CuPLS (g/L) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
5 AcPLS (g/L) 1.553 1.553 1.553 1.553 1.553 1.553 1.553 1.553
6 Cueaq (g/L) 2.5 1.94 1.24 0.51 0.26 0.17 0.09 0.07
7 Cueor (g/L) 4.414 4.356 4.188 3.662 3.146 2.786 2.223 2.000
8 aex 5.403 5.403 5.403 5.403 5.403 5.403 5.403 5.403
9 bex -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54 -1.54
10 cex 28.736 28.736 28.736 28.736 28.736 28.736 28.736 28.736
11 dex -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842
12 eex -0.644 -0.644 -0.644 -0.644 -0.644 -0.644 -0.644 -0.644
13 fex 2.862 2.862 2.862 2.862 2.862 2.862 2.862 2.862
14 g ex 0.965 3.007 9.842 41.808 96.254 155.48 307.93 400.36
15 αex -28.078 -28.078 -28.078 -28.078 -28.078 -28.078 -28.078 -28.078
16 λex 169.76 170.10 171.21 176.43 185.32 194.98 219.86 234.98
17 εex -385.71 -385.71 -385.71 -385.71 -385.71 -385.71 -385.71 -385.71
18 pex -7.761 -7.428 -6.312 -1.095 7.791 17.458 42.340 57.458
19 q ex 9.788 12.353 20.934 61.068 129.43 203.79 395.19 511.49
20 t ex -3.278 -3.336 -3.505 -4.031 -4.547 -4.907 -5.469 -5.692
21

The excel formula of the excel column “C” are the following:

 aex = C8 = C5+1,54*C4
 bex = C9 = -1.54
 cex = C10 = 3,303*C3
 dex = C11 = -3.0842
 eex = C12= -25.698*C3^-1,704
 fex = C13 = 10.663*C3^-0,608

Joseph kafumbila Page 35
 g ex= C14 = (C8+C9*C6)^2/C6
 αex = C15 = (2*C10*C11*C12+C11^2*C13)/(C11^2*C12)
 λex = C16 = (2*C10*C11*C13+C10^2*C12-C14)/(C11^2*C12)
 εex = C17 = (C13*C10^2)/(C11^2*C12)
 pex = C18 = C16-(C15^2)/3
 q ex= C19 = C17-C15*C16/3+2/27*C15^3
 t ex= C20 = (-C19/2-(1/2)*(C19^2+(4/27)*C18^3)^(1/2))^(1/3)+
(-C19/2+(1/2)*(C19^2+(4/27)*C18^3)^(1/2))^(1/3)
e
 Cuor = C7 = C20-C15/3

One excel formula of excel cell “C” are set up, the excel cells ranged from “C7” to “C20” are
copied and passed to others column.

Figure 7: Laboratory scale test and semi-empirical model extraction isotherms

The gap on the concentration of copper in the organic phase obtained for the low values of
concentration of copper in the aqueous phase is due to the presence of iron in the PLS.

4.4.2. Stripping step

Table (13) gives example of stripping isotherm from laboratory scale test [10]. Spent electrolyte
contains 30.7 g/L of copper and 190 g/L of free acid. The loaded organic phase contains 3.9 g/L of
copper and 8.7% of Lix984N as extractant.

Joseph kafumbila Page 36
Table 13: Laboratory scale test - stripping isotherm

O/A Organic phase Aqueous phase
Cu (g/L) Cu (g/L)
10/1 1.76 51.3
5/1 1.38 43.2
2.5/1 1.21 37.7
1/1 1.07 33.8
1/2 1.01 32.3
1/4 0.98 31.2

The predicted stripping isotherm is obtained by using the procedure explained in chapter (4.3.2.).
Table (14), as it appears on the excel spreadsheet, gives the predicted stripping isotherm. The Figure (8)
gives graphical representation of laboratory scale test and semi-empirical model results.

The excel formula of the excel column “C” are the following:

 ast = C8 = C5+1,54*C4
 b = C9 = -1.54
 cst = C10 = 3,303*C3
 dst = C11 = -3.0842
 est = C12= 5,11*10^-3*C3-0,194
 fst = C13 = 12,81*C3^-0,901
 g st = C14 = (C8+C9*C6)^2/C6
 αst = C15 = (2*C10*C11*C12+C11^2*C13)/(C11^2*C12)
 λst = C16 = (2*C10*C11*C13+C10^2*C12-C14)/(C11^2*C12)
 εst = C17 = (C13*C10^2)/(C11^2*C12)
 pst = C18 = C16-(C15^2)/3
 q st = C19 = C17-C15*C16/3+2/27*C15^3
 t st = C20 = (-C19/2-(1/2)*(C19^2+(4/27)*C18^3)^(1/2))^(1/3)+
(-C19/2+(1/2)*(C19^2+(4/27)*C18^3)^(1/2))^(1/3)
e
 Cuor = C7 = C20-C15/3

One excel formula of excel cell “C” are set up, the excel cells ranged from “C7” to “C20” are
copied and passed to others column.

Joseph kafumbila Page 37
A B C D E F G H I
1
2 Table 14 Semi-empirical model – predicted stripping isotherm
3 V% 8.7 8.7 8.7 8.7 8.7 8.7
4 CuSE (g/L) 30.7 30.7 30.7 30.7 30.7 30.7
5 AcSE (g/L) 190.0 190.0 190.0 190.0 190.0 190.0
6 Cueaq (g/L) 51.3 43.2 37.7 33.8 32.3 31.2
7 Cueor (g/L) 1.76 1.43 1.217 1.072 1.018 0.978
8 ast 236.20 236.20 236.20 236.20 236.20 236.20
9 bst -1.54 -1.54 -1.54 -1.54 -1.54 -1.54
10 cst 28.736 28.736 28.736 28.736 28.736 28.736
11 dst -3.0842 -3.0842 -3.0842 -3.0842 -3.0842 -3.0842
12 est -0.150 -0.150 -0.150 -0.150 -0.150 -0.150
13 fst 1.824 1.824 1.824 1.824 1.824 1.824
14 g st 481.70 666.40 841.77 1003.27 1076.36 1134.65
15 αst -30.832 -30.832 -30.832 -30.832 -30.832 -30.832
16 λst 652.74 782.58 905.86 1019.39 1070.78 1111.76
17 εst -1098.88 -1098.88 -1098.88 -1098.88 -1098.88 -1098.88
18 pst 335.86 465.71 588.99 702.52 753.91 794.88
19 q st 3478.45 4812.90 6079.88 7246.71 7774.82 8195.95
20 t st -8.517 -8.847 -9.060 -9.205 -9.260 -9.299
21

Figure 8: Laboratory scale test and semi-empirical model stripping isotherms

Joseph kafumbila Page 38
5. MacCabe -Thiele diagram

5.1. Extraction step

Figure (9) gives scheme of stage of rank ‘n’ of extraction step in counter current
n−1
configuration. Stage of rank ‘n’ of extraction step receives aqueous phase Eaq from stage of rank
n+1
‘n-1’ and organic phase Eor from stage of rank ‘n+1’. Stage of rank ‘n’ produces aqueous phase
n n
Eaq and organic phase Eor .

Figure 9: Scheme of stage of rank ‘n’ of extraction step

MacCabe Thiele diagram of stage of rank ‘n’ of extraction step is shown in Figure (10).
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 (85). Slope of line “BE” is given by equation
(86).

Y −Y
Slope “AC” = XA −XC (85)
A C

Y −Y Y −Y Y −Y
Slope “BE” = XB−X C = X D−XC = XD −XB = - Slope “AC” (86)
C A D A D B

Joseph kafumbila Page 39
Figure 10: MacCabe Thiele diagram of stage of rank ‘n’ of extraction step

5.2. Stripping step

Figure (11) gives scheme of stage of rank ‘n’ of stripping steps in cascade configuration.
n+1
Stage of rank ‘n’ of stripping step receives aqueous phase Saq from stage of rank ‘n+1’ and
n−1 n
organic phase Sor from stage of rank ‘n-1’. Stage of rank ‘n’ produces aqueous phase Saq and
n
organic phase Sor .

Figure 11: Scheme of stage of rank ‘n’ of stripping step

Joseph kafumbila Page 40
MacCabe Thiele diagram of stage of rank ‘n’ of stripping step is shown in Figure (12).
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 (87). Slope of line “EB” is given by equation
(88).

Y −Y
Slope “AC” = XA −XB (87)
B C

Y −Y Y −Y Y −Y
Slope “EB” = XA−X C = XA−XD = XB −XD = -slope “AC” (88)
C B C D B D

Figure 12: MacCabe diagram of stage of rank ‘n’ of stripping step

Joseph kafumbila Page 41
6. Metallurgical constraints of copper SX

6.1. Description and design criteria of copper SX

6.1.1. 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 (13) 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 13: Scheme of common leach/solvent extraction/electrowinning circuit

Joseph kafumbila Page 42
6.1.2. Design criteria of copper SX

6.1.2.1. Maximum copper loading

Maximum loading (ML) is concentration of copper in the organic phase at equilibrium
with PLS. Maximum loading is determined using either laboratory scale test or simulation
computer model.

 Laboratory scale test

In the laboratory scale test, the maximum loading is determined by the following
procedure:

a. Prepare PLS with concentrations of copper and free acid after data correction
and mass balance operation;
b. Combine prepared PLS and stripped organic with an O/A ratio of 1:1;
c. Agitate for 5 minutes and allow the phases to separate;
d. Repeat steps “b” and “c” until pH does not change, each time with fresh
prepared PLS;
e. The copper tenor in the organic after iterations is the maximum loading.

The absolute maximum loading (AMLL ) is determined following the same procedure
with the synthetic solution (6 g/L Cu at pH 1.8) in place of prepared PLS (Cognis procedure).

 Simulation computer model

Reagent suppliers have developed simulation computer model which can help to
determine the maximum loading.

In case of the new semi-empirical model using Lix984N as extractant, the value of ML
following the procedure explained in chapter (4.3.1.). The equilibrium concentration of copper in
aqueous phase is the concentration of copper in the PLS.

Equation (89) gives the value of ML

αML
ML = t ML - (89)
3

Equation (90) gives the value of “t ML ”

1 1 1 1
qML 1 4 qML 1 4
t ML = [− − ∗ ((qML )2 + ∗ (pML )3 )(2) ](3) + [− + ∗ ((qML )2 + ∗ (pML )3 )(2) ](3) (90)
2 2 27 2 2 27

Joseph kafumbila Page 43
Equations (91) and (92) give the values of constants “pML” and “q ML”.

(αML )2 (91)
pML = λML - 3

αML ∗λML 2 (92)
q ML = εML - + 27* (αML )3
3

“αML ”, “λML ” and “εML ” are given by equations (93), (94) and (95) respectively.

2∗cex ∗dex ∗eex +(dex )2 ∗fex
αML = (93)
(dex )2 ∗eex

2∗cex ∗dex ∗fex + (cex )2 ∗eex − gML
λML = (94)
(dex )2 ∗eex

f ∗(cex )2
εML = (dex (95)
2 ∗e
ex ) ex

Equations (96), (97), (98), (99), (100), (101), and (102) give the values of “aex ”, “bex ”,
“cex ”, “dex ”, “eex ”, “fex ”, and “g ML ”.

aex =AcPLS + 1.54 * CuPLS (96)

bex = −1.54 (97)

cex = 3.303*V% (98)

dex = −3.0842 (99)

eex = −25.698 * V%(−1.704) (100)

fex = 10.663 * V%(−0.608) (101)

(aex +bex ∗CuPLS )2
g ML = (102)
CuPLS

In this paper the predicted absolute maximum loading (AMLP ) is the maximum loading
when the concentration of free acid in the PLS is zero.

In case of the second semi-empirical model using Lix984N as extractant, equation (103)
gives the value of predicted absolute maximum loading.
Joseph kafumbila Page 44
AMLP = 0.415 * V%(1.096) (103)

Where “𝐴𝑀𝐿𝑃 ” is the predicted absolute maximum loading (g/L).

The absolute maximum loading depends only on the value of the extractant volume
percent.

Figure (14) gives a graphical representation of loaded organic, maximum loading and
predicted absolute maximum loading.

Figure 14: Position of loaded organic, maximum loading and predicted
absolute maximum loading on MacCabe-Thiele diagram

6.1.2.2. Extractant volume percent

During extended tests in both laboratory and industry, there are diluent evaporation and
extractant degradation. It is therefore necessary to regularly check the effective concentration of
extractant.

 Laboratory scale test – conventional method

The procedure for determining the effective extractant volume percent is the following:
Joseph kafumbila Page 45
 Determine the absolute maximum loading using the laboratory scale test method
with a fresh organic phase containing 10% of extractant (AML1L ).
 Determine the absolute maximum loading using the laboratory scale test method
with plant stripped organic ((AML2L ).

The extractant volume percent is given by equation (104).

AML2
V% = 10 * AMLL1 (104)
L

 Laboratory scale test – new method

Observing equation (103), the predicted absolute maximum loading is not a linear
function of the extractant volume percent. By using the equation (104) for determining the
extractant volume percent, the gap between the effective extractant volume percent and the value
calculated from equation (104) will increase with increasing the value of extractant volume
percent. The new method consists to determine the absolute maximum loading using laboratory
scale test with fresh organic phase having extractant volume percent ranged from 5 to 35% and
to determining the extrapolation equation of the function V¨%=f(AMLL ).

In the case of Lix984N is used as extractant, equation (105) gives the value of extractant
volume percent ranged from 2.5 to 32%.

V% = 2.238 * AMLL (0.912) (105)

Where “V%” is in percentage and “𝐴𝑀𝐿𝐿 ” is absolute maximum loading obtained in laboratory with
the synthetic PLS (6 g/L of copper at pH 1.8) (g/L).

6.1.2.3. 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
(106). Copper net transfer depends on extractant volume percent, type of extractant, PLS
composition and configurations of extraction and stripping steps.

CuLO −CuSO
NetCu = (106)
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 (%).

Joseph kafumbila Page 46
6.1.2.4. 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 (107).

CuLO
%ML = x100 (107)
ML

Where “%ML” is percentage of maximum loading (%), “𝐶𝑢𝐿𝑂 ” is copper tenor in loaded organic
(g/L), and “ML” is maximum loading (g/L).

6.1.2.5. Copper recovery

Equations (108) and (109) give respectively copper recovery on extraction and stripping
steps.

CuPLS −CuRaf
RCuex = x 100 (108)
CuPLS

CuLO −Cu𝑆𝑂
RCust = x 100 (109)
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).

6.1.2.6. Advance and operating ratios (O/A)

Figure (15) 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” m 3/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 (110) and (111) give respectively values of operating and advance ratios
(O/A) determined with stream flowrates.

(b+d)
O/AOPF = (110)
(a+c)

Joseph kafumbila Page 47
b
O/AADF = a (111)

Figure 15: Scheme of solvent extraction stage

Equations (112) and (113) 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 = = (112)
CuO I
or −Cuor Slope "AC"

CuO I
aq −Cuaq 1
O/Ast
ADA = = Slope "AC" (113)
CuIor −CuO
or

𝐼 𝑂
Where 𝐶𝑢𝑎𝑞 and 𝐶𝑢𝑎𝑞 are concentrations of copper respectively in inlet and outlet aqueous phases on
𝐼 𝑂
a stage and 𝐶𝑢𝑜𝑟 and 𝐶𝑢𝑜𝑟 are concentrations of copper respectively in inlet and outlet organic phases
on a stage.

6.1.2.7. 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

Joseph kafumbila Page 48
new design of copper solvent extraction value of operation ratio (O/A) is fixed at 1.25/1 to be
far from transition zone.

6.1.2.8. Number of stages on extraction step

The copper recovery on extraction step is improved when two stages at least are used.
The stage configuration can be counter current cascade (Figure 16) or parallel cascade (Figure
17). The counter current cascade is called also “series”.

Figure 16: Scheme of counter current cascade on extraction step with two stages

Figure 17: Scheme of parallel cascade configuration on extraction step with two stages

Figures (18), (19) and (20) give MacCabe Thiele diagrams having respectively one stage,
two stages in series and two stages in parallel on extraction step. The aqueous phase contains 7
g/L of copper and 2 g/L of free acid. The extractant volume percent is 20% (v/v) (Lix984N
extractant). Stripped organic contains 2 g/L of copper. For one stage, values of advance and
operating ratios are 1/1.

Joseph kafumbila Page 49
Figure 18: MacCabe Thiele diagram of extraction step with aqueous phase (7 g/L of copper and
2 g/L of free acid), stripped organic phase (2 g/L of copper), extractant volume percent
(20% v/v Lix984N) and advance and operating ratios (O/A) 1/1.

Figure 18: MacCabe Thiele diagrams having two stages in series with aqueous phase (7 g/L of
copper and 2 g/L of free acid), stripped organic phase (2 g/L of copper), extractant
volume percent (20% v/v Lix984N) and advance and operating ratios (O/A) 1/1.

Joseph kafumbila Page 50
Figure 20: MacCabe Thiele diagram having two stages in parallel with aqueous phase (7 g/L of
copper and 2 g/L of free acid), stripped organic phase (2 g/L of copper), extractant
volume percent (20% v/v Lix984N), and advance and operating ratios at each stage
(O/A) 2/1.

For two stages in series, values of advance and operating ratios are 1/1 on each stage.
For two stages in parallel, values of advance and operating ratios are 2/1 on each stage. In all
cases, the total flowrate of aqueous phase and the total flowrate of organic phase are the same.

Results show that:

 The copper concentration in raffinate of one stage is greater than copper concentration
in global raffinate of two stages in series and in parallel.
 The copper concentration in global raffinate of two stages in parallel is greater than
copper concentration in global raffinate of two stages in series.
 The use of two stages in parallel is based on the desire to reduce the capital cost of
copper solvent extraction plant.

Figure (21) gives the exiting configurations of extraction step of copper solvent
extraction.

Joseph kafumbila Page 51
Figure 21: Exiting configurations on extraction step

Joseph kafumbila Page 52
6.1.2.9. 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 (22) 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 22: Scheme of stripping step having two stages in series

6.1.2.10. 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 [11]:

 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 (10) and (12), equations (114) and (115) give the stage efficiencies
calculated with the concentrations of copper in organic and in aqueous respectively on extraction
step. Equations (116) and (117) give the stage efficiencies calculated with the concentrations of
copper in organic and in aqueous respectively on stripping step.

Joseph kafumbila Page 53
e YB −YA
Effor = 100 x (114)
YD −YA

e XB −XA
Effaq = 100 x (115)
XB −XD

s YB −YA
Effor = 100 x (116)
YB −YD

s XB −XA
Effaq = 100 x (117)
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 98 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.

6.2. Metallurgical constraints of copper SX

6.2.1. 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 (118) and (119).

LOe = LOs (118)

SOe = SOs (119)

6.2.2. Advance ratio (O/A)

6.2.2.1. First constraint

The optimum value of advance ratio O/A of the extraction step must give the smallest
size of copper solvent extraction configuration.

Joseph kafumbila Page 54
6.2.2.2. 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%.

6.2.2.3. 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 [12-13]. 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 [13]. 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 [14]. 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.

6.2.2.4. Fourth constraint

It has been observed that the stage efficiency on extraction step is greater when the
organic phase continuity regime is used [11].

6.2.2.5. 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.
Joseph kafumbila Page 55
6.2.3. Copper concentration in spent electrolyte

6.2.3.1. 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 [15]:

 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.

6.2.3.2. 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 [16]. 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) [17]. Optimum copper tenor in spent electrolyte is
35 g/L for operating current density ranged 280 – 320 A/m2.

6.2.4. Acid concentration in spent electrolyte

6.2.4.1. 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

Joseph kafumbila Page 56
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 [15].

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 [15].

6.2.4.2. 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.

6.2.5. Copper concentration in advance electrolyte

6.2.5.1. 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.

6.2.5.2. Second constraint

Copper concentration in advance electrolyte must be high to minimize the number of
scavenger cells in the copper electrowinning unit process.

6.2.5.3. 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.

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6.2.6. Percentage to maximum loading

6.2.6.1. 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.

2Ex2S configuration is simulated with new reagent (Lix984N) using the new semi-
empirical method. The parameters of simulation are the following:

 Average values of stage efficiencies on extraction and stripping steps are
respectively 95% and 98%.
 Values of advance and operating ratios (O/A) are 1/1 on extraction step.
 Value of the percentage to maximum loading has varied from 60 to 95%.
 Concentration of copper and acid in spent electrolyte are 35 and 170 g/L
respectively.
 Concentration of copper in advance electrolyte is 50 g/L.

Figure (23) gives copper extraction recovery, percentage to maximum loading, and
copper net transfer versus stripping recovery.

Results show that:

 Copper extraction recovery increases with decreasing of stripping recovery. The minimum
value of stripping recovery is 60%, from which the increase of copper extraction recovery
is negligible with decreasing stripping recovery. Value of extraction recovery is 98% at
stripping recovery of 60%.
 Copper net transfer increases with increasing of stripping recovery. The value of copper
net transfer is 0.215 (g/L)/1Vol% at stripping recovery of 60%. In old papers, the average
value of copper net transfer was 0.220 (g/L)/1Vol% for old extractants at stripping
recovery of 60%.

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Figure 23: Copper extraction recovery and Net transfer versus stripping recovery.

Because of copper extraction recovery is near about 100% at stripping recovery of 60%,
approximate value of extractant volume percent has been given by equation (120).

CuPLS (120)
V% = 0.220

Where “𝐶𝑢𝑃𝐿𝑆 ” is copper tenor in PLS (g/L), “V%” is extractant volume percent (%), and
“0.220” is copper net transfer ((g/L)/1Vol %).

6.2.6.2. 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.

Joseph kafumbila Page 59
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 [10].
 Size of copper solvent extraction must be the smallest (values of advance and operating
ratios (O/A) are the same on extraction step).

2Ex1S configuration is simulated with Lix984N reagent using the new semi-empirical
method. The parameters of simulation are the following: Copper concentration in PLS from heap
leaching of low grade oxide ores was around 4 g/L at pH 1.8.

 Average values of mixer efficiencies on extraction and stripping steps are
respectively 95% and 98%.
 Values of operating ratios (O/A) are 1.1/1 on extraction and stripping steps.
 Values of advance ratios of extraction step are 1.1/1.
 Value of the %ML has varied from 75 to 95%.
 Concentration of copper and acid in spent electrolyte are 35 and 190 g/L
respectively.
 Concentration of copper in advance electrolyte is 50 g/L.

Table (15) gives values of %ML versus the values of copper net transfer. Results show
that the values of %ML on boundaries of the good use zone of organic phase range from 77.92
to 95%.

Table 15: %ML versus copper net transfer

%ML % 75 77.92 80 85 90 95
Copper net transfer (g/L)/1%(v/v) 0.228 0.24 0.248 0.267 0.286 0.302

6.2.6.3. 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 [18].
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 [19] lower than leaching pH of copper oxide ores of 1.8.

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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” [18]. “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 [18].

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 [20]. 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 [20]. 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. Table (16) gives simulation results
made by Cognis Corporation Isocalc computer program to predict performance of 2Ex2S and
3Ex1S configurations [21]. Simulations have been made using organic phase containing 0.296
molar of 5-nonyl-2-hydrxyacetophenone oxime (ketoxime) and 0.0964 molar of 5-
nonysalicyladoxime (aldoxime). Cu/Fe transferred is (Loaded organic Cu – Stripped organic
Cu)/loaded organic Fe.

Table (16): Comparison between Cu/Fe in LO and Cu/Fe transferred

Configuration Advance Cu Fe Cu Cu/Fe Cu/Fe Cu stripping
ratio (O/A) in LO in LO in SO in LO transferred efficiency
g/L mg/L g/L %
3Ex1S 1 8.89 1.80 2.84 4939 3361 68.05
3Ex1S 1 8.30 1.85 2.16 4486 3319 73.98
2Ex2S 1 7.81 1.95 1.83 4005 3067 76.57
2Ex2S 1 7.46 1.98 1.42 3767 3051 80.97

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Results show that:

 Ratio Cu/Fe in loaded organic phase is bigger than ratio Cu/Fe transferred to copper
electrowinning unit process.
 Cu/Fe transferred decreases with increasing of copper stripping recovery.

6.2.6.4. 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% [22]. 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 [18].

6.2.7. Effect of impurities

6.2.7.1. Nitrate

 Constraint

Nitrate is sometimes present in copper ore in small amounts. Nitrate concentration in
PLS can build up to significant levels, which accelerate nitration of organic phase. Nitrate reacts
with aldoxime extractants and forms Nitro aldoxime which binds too strongly to copper for
industrial strip solutions to remove. This problem is aggravated by high solution potential in PLS
or electrolyte.

 Actions

In any plant with potential for nitrate ions to enter the PLS it is important to choose an
appropriate organic extractant [23].

Joseph kafumbila Page 62
6.2.7.2. Chloride

 Constraint

A certain chloride concentration is desirable in electrolyte as it increases solution
conductivity. But, excess chloride can cause problems if chloride concentration is high enough to
cause chlorine gas evolution. Chlorine gas accelerates corrosion of equipment. Chlorine gas
evolution is aggravated by the presence of high valence manganese ions which increase solution
potential.

 Actions

Wash stage is applied for avoiding excessive chloride tenor in the electrolyte.

6.2.7.3. Manganese

 Constraint

Manganese (II) is always present in PLS. Problems start when it is transferred to
electrolyte via aqueous entrainment. Once in electrolyte manganese (II) is oxidized to higher
valence manganese (III), manganese (IV) and manganese (VII), decreasing current efficiency.
MnO2 formed on anodes detaches in its fall PbO2 thus accelerating anode corrosion. Manganese
also causes nodular growth of copper on the cathodes, reducing final copper quality [24].
Presence of high valence manganese ions in electrolyte increases solution redox potential. The
increase of solution redox potential causes degradation of organic phase. Products of organic
degradation reactions have surface active, which makes them stabilize emulsions and slow down
phase separation in settlers [25].

 Actions

Wash stage is applied for avoiding excessive Mn tenor in the electrolyte. Electrolyte
must contain au minimum 1 g/L of iron giving solution potential less than 600 mV (Ag/AgCl).

Joseph kafumbila Page 63
7. Static modelling

7.1. Concept

Mass balance defines an engineering problem where parameters between unit operations
are partly known. The purpose of mass balance is to mathematically examine the known
parameters to solve for the unknown parameters. Two main types of mass balances are
commonly made: design mass balance and operating plant mass balance. The design mass
balance is typically faced during plant design when the test work results and a flowsheet diagram
are the only known parameters. Design mass balance purpose is to find values for the unknown
parameters. A static modelling is developed for copper solvent extraction plant design using
Lix984N as extractant. The most important feature of this program is that the percentage to
maximum loading (saturation ratio) which is the important parameter for iron rejection
determines the value of the extractant volume percent.

Static modelling of copper solvent extraction configuration is made on excel
spreadsheet and Excel solver program is used for optimization. Excel solver is the Microsoft add-
in program used for what-if analysis. Excel solver program allows finding the optimum value for
a formula in cell called the objective cell.

7.2. Static modelling program design

7.2.1. General

In this paper for good understanding, static modelling program will be made step by
step for a conventional configuration containing two stages in counter current on extraction step
and two stages in counter current on stripping step as an example.

. Table (17) gives data of chosen example for explanation of modelling program
conception. Unlike classical static modelling where the value of extractant volume percent in the
organic phase is a datum, in this static modelling the value of extractant volume percent is found
from the value of percentage to maximum loading.

First step of static modelling is creation of modelling program Table on Excel
spreadsheet. Modelling program Table has three small Tables which are Table of extraction step,

Joseph kafumbila Page 64
Table of stripping step, and Table of set objective. In modelling program Table, data have red
color, solver constraints have blue color and solver constraints have green color. Table (18), as it
appears on excel spreadsheet, gives the static modelling for 2EX2S configuration.

Table17: Data of chosen example of copper solvent extraction configuration

Description Symbol Unity Value
Extraction step
PLS Flow PLS Flow m3/h 400
Copper concentration in PLS CuPLS g/l 7
Acid concentration in PLS AcPLS g/l 1.96
ex
Ratio O/A O/AADF 1.1
Percentage to maximum loading %ML % 80
Number of extraction stage 2
Stage of rank 1 stage efficiency effe1 % 95
Stage of rank 2 stage efficiency 2 % 95
effe
Stripping step
Copper concentration in spent electrolyte CuSP g/l 35
Acid concentration in spent electrolyte AcSP g/l 190
Copper concentration in advance electrolyte CuAD g/l 50
Number of stripping stage 2
Stage of rank 1 stage efficiency effs1 % 98
Stage of rank 2 stage efficiency effs2 % 98

The procedure for modelling design on Excel spreadsheet is the following:

 Extraction step

 Data

- In the excel cell “C6” (PLS flowrate), type number “400” in red color.
- In the excel cell “C7” (PLS copper concentration), type number “7” in red color.
- In the excel cell “C8” (PLS acid concentration), type number “1.96” in red color.
- In the excel cell “C9” (%ML), type number “80” in red color.
- In the excel cell “C10” (advance ratio O/A), type number “1.25” in red color.
- In the excel cell “C11” (stage efficiency – stage 1), type number “95” in red color.
- In the excel cell “C12” (stage efficiency – stage 2), type number “95” in red color.

 Solver variable of data

- In the excel cell “F6” (PLS flowrate), type number “400” in blue color.
- In the excel cell “F7” (PLS copper concentration), type number “7” in blue color.
- In the excel cell “F8” (PLS acid concentration), type number “1.96” in blue color.
- In the excel cell “F9” (%ML), type number “80” in blue color.

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- In the excel cell “F10” (advance ratio O/A), type number “1.25” in blue color.
- In the excel cell “F11” (stage efficiency – stage 1), type number “95” in blue color.
- In the excel cell “F12” (stage efficiency – stage 2), type number “95” in blue color.

 Solver constraints of data

- In the excel cell “I6” (PLS flowrate), type “=F6-C6” in green color.
- In the excel cell “I7” (PLS copper concentration), type “=F7-C7” in green color.
- In the excel cell “I8” (PLS acid concentration), type “=F8-C8” in green color.
- In the excel cell “I9” (%ML), type “=F9-C9” in green color.
- In the excel cell “I10” (advance ratio O/A), type “=F10-C10” in green color.
- In the excel cell “I11” (stage efficiency – stage 1), type “=F11-C11” in green color.
- In the excel cell “I12” (stage efficiency – stage 2), type “=F6-C6” in green color.

 Extractant volume percent solver variable

The starting value of extractant volume percent is random number between 1 and 32%.
The starting value of extractant volume percent is used in all equations of extraction step as
extraction volume percent data. For this case, chosen starting value is 25%.

- In the excel cell “C15” (extractant volume percent), type number “25” in blue color.

 Constants

- In the excel cell “C18” (aex ), type “=F8+F7*1,54”.
- In the excel cell “C19” (bex ), type number “=-1.540”.
- In the excel cell “E18” (cex ), type “=3,303*C15”.
- In the excel cell “E19” (dex ), type number “-3,0842”.
- In the excel cell “G18” (eex ), type “=-25,698*C15^-1,704”.
- In the excel cell “G19” (fex ), type “=10,663*C15^-0,608”.

 General

- In the excel cell “C22” (organic flowrate), type “=F6*F10”.
- In the excel cell “C23”(predicted absolute maximum loading), type “=0,415*C15^1,096”.
- In the excel cell “C25” (g ML ), type “=(C18+C19*F7)^2/F7”.
- In the excel cell “C26” (αex ),
type “=(2*E18*E19*G18+E19^2*G19)/(E19^2*G18)”.
- In the excel cell “E25” (λex ),
type “=(2*E18*E19*G19+E18^2*G18-C25)/(E19^2*G18)”.
- In the excel cell “E26” (εex ), type “=G19*E18^2/(E19^2*G18)”.
- In the excel cell “G25” (pex ), type “=E25-C26^2/3”.
- In the excel cell “G26” (q ex ), type “=E26-C26*E25/3+2/27*C26^3”.

Joseph kafumbila Page 66
- In the excel cell “I25” (t ex ),
type “=(-G26/2-1/2*(G26^2+4/27*G25^3)^(1/2))^(1/3)+
(-G26/2+1/2*(G26^2+4/27*G25^3)^(1/2))^(1/3)”.
- In the excel cell “C24” (maximum loading), type “=I25-C26/3”.

 Extraction stage 1

MacCabe-Thiele diagram of extraction step (Figure 10):

- In the excel cell “C30” (XA1 ), type “=F7”.
- In the excel cell “D30” (YA1), type “=C24*F9/100”.
- In the excel cell “D31” (YB1 ), type “=D30”.

The value of “YD1 ” is a solver variable. Starting value is random number between ML
and “ YA1”. The stating value is “11”.

- In the excel cell “D33” (YD1 ), type number “11” in blue color.
- In the excel cell “F33” (hex ), type “=(G18*D33+G19)*(E18+E19*D33)^2/D33”.
- In the excel cell “C33” (XD1 ),
type “=(F33-2*C18*C19-(F33^2-4*C18*C19*F33)^(1/2))/(2*C19^2)”.
- In the excel cell “C31” (XB1 ), type “=C33+F10*(D33-D31)” equations (86) and (112).
- In the excel cell “C32” (XC1 ), type “=C31”.
- In the excel cell “D32” (YC1), type “=D33+(C33-C30)/F10” equations (86) and (112).
- In the excel cell “H33” (organic stage efficiency), type “=(D31-D32)/(D33-D32)*100”
- In the excel cell “I33” (solver constraint), type “=H33-F11” in green color.

 Extraction stage 2

MacCabe-Thiele diagram of extraction step (Figure 10):

Coordinates of points “C1 ” and “A2 ” are equals.

- In the excel cell “C37” (XA2 ), type “=C32”.
- In the excel cell “D37” (YA2), type “=D32”.
- In the excel cell “D38” (YB2 ), type “=D37”.

The value of “YD2 ” is a solver variable. Starting value is random number between “YD1 ”
and “ YA2”. The stating value is “7”.

- In the excel cell “D40” (YD2 ), type number “7” in blue color.
- In the excel cell “F40” (hex ), type “=(G18*D40+G19)*(E18+E19*D40)^2/D40”.
- In the excel cell “C40” (XD2 ),
type “=(F40-2*C18*C19-(F40^2-4*C18*C19*F40)^(1/2))/(2*C19^2)”.

Joseph kafumbila Page 67
- In the excel cell “C38” (XB2 ), type “=C40+F10*(D40-D38)” equations (86) and (112).
- In the excel cell “C39” (XC2 ), type “=C38”.
- In the excel cell “D39” (YC2), type “=D40+(C40-C37)/F10” equations (86) and (112).
- In the excel cell “H40” (organic stage efficiency), type “=(D38-D39)/(D40-D39)*100”
- In the excel cell “I40” (solver constraint), type “=H40-F12” in green color.

 Performance

- In the excel cell “C43” (raffinate acid concentration), type “=F8+(C30-C39)*1,54”.
- In the excel cell “C44” (copper recovery), type “=(C30-C39)/C30*100”.

 Stripping step

 Data

- In the excel cell “C50” (spent electrolyte copper concentration), type number “35” in red
color.
- In the excel cell “C51” (spent electrolyte acid concentration), type number “190” in red
color.
- In the excel cell “C52” (advance electrolyte copper concentration), type number “50” in red
color.
- In the excel cell “C53” (stage efficiency – stage 1), type number “98” in red color.
- In the excel cell “C54” (stage efficiency – stage 2), type number “98” in red color.

 Solver variable of data

- In the excel cell “F50” (spent electrolyte copper concentration), type number “35” in blue
color.
- In the excel cell “F51” (spent electrolyte acid concentration), type number “190” in blue
color.
- In the excel cell “F52” (advance electrolyte copper concentration), type number “50” in blue
color.
- In the excel cell “F53” (stage efficiency – stage 1), type number “98” in blue color.
- In the excel cell “F54” (stage efficiency – stage 2), type number “98” in blue color.

 Solver constraints of data

- In the excel cell “I50” (spent electrolyte copper concentration), type “=F50-C50” in green
color.
- In the excel cell “I51” (spent electrolyte acid concentration), type “=F51-C51” in green
color.
- In the excel cell “I52” (advance electrolyte copper concentration), type “=F52-C52” in
green color.
- In the excel cell “I53” (stage efficiency – stage 1), type “=F53-C53” in green color.
- In the excel cell “I54” (stage efficiency – stage 2), type “=F54-C54” in green color.

Joseph kafumbila Page 68
 Constants

- In the excel cell “C57” (ast ), type “=F51+F50*1,54”.
- In the excel cell “C58” (bst ), type number “=-1.540”.
- In the excel cell “E57” (cst ), type “=3,303*C15”.
- In the excel cell “E58” (dst ), type number “-3,0842”.
- In the excel cell “G57” (est ), type “=5,11*10^-3*C15-0,194”.
- In the excel cell “G58” (fst ), type “=12,81*C15^-0,901”.

 General

- In the excel cell “C61” (advance ratio O/A), type “=(F52-F50)/(D30-D39)”.
- In the excel cell “C62”(spent electrolyte flowrate), type “=C22/C61”.

 Stripping stage 1

MacCabe-Thiele diagram of extraction step (Figure 12):

- In the excel cell “C66” (XA1 ), type “=F52”.
- In the excel cell “D66” (YA1), type “=D30”.
- In the excel cell “C67” (XB1 ), type “=C66”.

The value of “YD1 ” is a solver variable. Starting value is random number less than “
YA1”. The stating value is “ML * 0.5 = 5.63”.

- In the excel cell “D69” (YD1 ), type number “5.63” in blue color.
- In the excel cell “F69” (hst ), type “=(G57*D69+G58)*(E57+E58*D69)^2/D69”.
- In the excel cell “C69” (XD1 ),
type “=(F69-2*C57*C58-(F69^2-4*C57*C58*F69)^(1/2))/(2*C58^2)”.

The starting value of “YD1 ” is changed manually until the value of “XD1 ” is between
“XA1 ” and “XA1 +1”. The new value of the starting value of “YD1 ” is “4.00”.

- In the excel cell “D67” (YB1 ), type “=D69-(C67-C69)/C61” equations (88) and (113).
- In the excel cell “D68” (YC1), type “=D67”.
- In the excel cell “C68” (XC1 ), type “=C67-C61*(D66-D67)” equations (87) and (113).
- In the excel cell “H69” (organic stage efficiency), type “=(D66-D67)/(D66-D69)*100”
- In the excel cell “I69” (solver constraint), type “=H69-F53” in green color.

 Stripping stage 2

MacCabe-Thiele diagram of extraction step (Figure 12):

Coordinates of points “C1 ” and “A2 ” are equals.
Joseph kafumbila Page 69
- In the excel cell “C73” (XA2 ), type “=C68”.
- In the excel cell “D73” (YA2), type “=D68”.
- In the excel cell “C74” (XB2 ), type “=C73”.

The value of “YD2 ” is a solver variable. Starting value is random number less than “
YD1 ”. The stating value is “YD1 * 0.5 = 2.0”.

- In the excel cell “D76” (YD2 ), type number “2.0” in blue color.
- In the excel cell “F76” (hst ), type “=(G57*D76+G58)*(E57+E58*D76)^2/D76”.
- In the excel cell “C76” (XD2 ),
type “=(F76-2*C57*C58-(F76^2-4*C57*C58*F76)^(1/2))/(2*C58^2)”.

The starting value of “YD2 ” is changed manually until the value of “XD2 ” is between
“XA2 ” and “XA2 +1”. The new value of the starting value of “YD1 ” is “2.3”.

- In the excel cell “D74” (YB2 ), type “=D76-(C74-C76)/C61” equations (88) and (113).
- In the excel cell “D75” (YC2), type “=D74”.
- In the excel cell “C75” (XC2 ), type “=C74-C61*(D73-D74)” equations (87) and (113).
- In the excel cell “H76” (organic stage efficiency), type “=(D73-D74)/(D73-D76)*100”
- In the excel cell “I76” (solver constraint), type “=H76-F54” in green color.

 Performance

- In the excel cell “C79” (copper recovery), type “=(D66-D75)/D66*100”.
- In the excel cell “C80” (copper net transfer), type “=(D66-D75)/C15”.

 Set objective

Equation (119)

- In the excel cell “I84” (set objective), type “=D75-D39”.in green color.

 Excel solver program

Excel solver program execution is as follows:

1) On the ‘Data’, in the ‘Analysis group’ click solver (if the solver command is not
available, you must activate the solver add-in).
2) In the ‘Set objective’ box, enter the cell reference ‘I84’ of simulation program constraint.
3) Click ‘Value of’ and then type the number ‘0’ in the box.

Joseph kafumbila Page 70
4) In the ‘By Changing Variable Cells’ box, enter reference for each solver variable (in
blue color in Table 18 – F6, F7, F8, F9, F10, F11, F12, C15, D33, D40, F50, F51, F52,
F53, F54, D69, and D76). Separate references with commas (English version).
5) In the ‘Subject to the constraints’ box, enter solver constraints by doing the following:
5.1. In the ‘Solver Parameters’ dialog box, click ‘Add’.
5.2. In the ‘Cell Reference’ box, enter cell reference “I6”.
5.3. Click the ‘relationship’ ‘=’,
5.4. In the ‘Constraint’ box, type the number ‘0’.
5.5. Click ‘Add’ for the second solver constraint.
5.6. In the ‘Cell Reference’ box, enter cell reference “I7”.
5.7. Click the ‘relationship’ ‘=’,
5.8. In the ‘Constraint’ box, type the number ‘0’.
5.9. Click ‘Add’ for the second solver constraint.
5.10. In the ‘Cell Reference’ box, enter cell reference “I8”.
5.11. Click the ‘relationship’ ‘=’,
5.12. In the ‘Constraint’ box, type the number ‘0’.
5.13. Click ‘Add’ for the second solver constraint.
5.14. In the ‘Cell Reference’ box, enter cell reference “I9”.
5.15. Click the ‘relationship’ ‘=’,
5.16. In the ‘Constraint’ box, type the number ‘0’.
5.17. Click ‘Add’ for the second solver constraint.
5.18. In the ‘Cell Reference’ box, enter cell reference “I10”.
5.19. Click the ‘relationship’ ‘=’,
5.20. In the ‘Constraint’ box, type the number ‘0’.
5.21. Click ‘Add’ for the second solver constraint.
5.22. In the ‘Cell Reference’ box, enter cell reference “I11”.
5.23. Click the ‘relationship’ ‘=’,
5.24. In the ‘Constraint’ box, type the number ‘0’.
5.25. Click ‘Add’ for the second solver constraint.
5.26. In the ‘Cell Reference’ box, enter cell reference “I12”.
5.27. Click the ‘relationship’ ‘=’,
5.28. In the ‘Constraint’ box, type the number ‘0’.
5.29. Click ‘Add’ for the second solver constraint.
5.30. In the ‘Cell Reference’ box, enter cell reference “I33”.
5.31. Click the ‘relationship’ ‘=’,
5.32. In the ‘Constraint’ box, type the number ‘0’.
5.33. Click ‘Add’ for the second solver constraint.
5.34. In the ‘Cell Reference’ box, enter cell reference “I40”.
5.35. Click the ‘relationship’ ‘=’,
5.36. In the ‘Constraint’ box, type the number ‘0’.
5.37. Click ‘Add’ for the second solver constraint.
5.38. In the ‘Cell Reference’ box, enter cell reference “I50”.
5.39. Click the ‘relationship’ ‘=’,
5.40. In the ‘Constraint’ box, type the number ‘0’.
5.41. Click ‘Add’ for the second solver constraint.
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5.42. In the ‘Cell Reference’ box, enter cell reference “I51”.
5.43. Click the ‘relationship’ ‘=’,
5.44. In the ‘Constraint’ box, type the number ‘0’.
5.45. Click ‘Add’ for the second solver constraint.
5.46. In the ‘Cell Reference’ box, enter cell reference “I52”.
5.47. Click the ‘relationship’ ‘=’,
5.48. In the ‘Constraint’ box, type the number ‘0’.
5.49. Click ‘Add’ for the second solver constraint.
5.50. In the ‘Cell Reference’ box, enter cell reference “I53”.
5.51. Click the ‘relationship’ ‘=’,
5.52. In the ‘Constraint’ box, type the number ‘0’.
5.53. Click ‘Add’ for the second solver constraint.
5.54. In the ‘Cell Reference’ box, enter cell reference “I54”.
5.55. Click the ‘relationship’ ‘=’,
5.56. In the ‘Constraint’ box, type the number ‘0’.
5.57. Click ‘Add’ for the second solver constraint.
5.58. In the ‘Cell Reference’ box, enter cell reference “I69”.
5.59. Click the ‘relationship’ ‘=’,
5.60. In the ‘Constraint’ box, type the number ‘0’.
5.61. Click ‘Add’ for the second solver constraint.
5.62. In the ‘Cell Reference’ box, enter cell reference “I76”.
5.63. Click the ‘relationship’ ‘=’,
5.64. In the ‘Constraint’ box, type the number ‘0’.
5.65. Click ‘Add’ for the second solver constraint.
5.66. Click ‘OK’ to return to ‘Solver Parameters’ dialog box.
6) Click ‘Solve’. To keep the solution values on the worksheet, in the ‘Solver Results’
dialog box, click ‘Keep solver solution’.

It appears Table 18 as it appears on Excel Microsoft spreadsheet. Simulation program of
copper solvent extraction configuration (2Ex2S) is made. Data (having red color) will be changed
only for others simulations.

Joseph kafumbila Page 72
A B C D E F G H I
1
2 Table 18 Modelling Table of 2Ex2S - part 1
3
4 Extraction step
5 Data Data solver variables Solver constraints
6 PLS flow 400 m3/h PLS flow 400 m3/h Data-solver 0.000
7 CuPLS 7.0 g/L CuPLS 7.0 g/L Data-solver 0.000
8 AcPLS 1.96 g/L AcPLS 1.96 g/L Data-solver 0.000
9 %ML 80 % %ML 80 % Data-solver 0.000
10 O/Aex
ADF 1.25 ex
O/AADF 1.25 Data-solver 0.000
11 Eff1 95 % Eff1 95 % Data-solver 0.000
12 Eff2 95 % Eff2 95 % Data-solver 0.000
13
14 Extractant volume percent solver variable
15 V% 17.10 %
16
17 Constants
18 aex 12.740 cex 56.479 eex -0.204
19 bex -1.540 dex -3.0842 fex 1.898
20
21 General
22 Organic flow 500.0 m3/h
23 AMLP 9.320 g/L
24 ML 9.286 g/L
25 gML 0.549 λML 676.91 pML -26.683 t ML -6.029
26 αML -45.943 εML -3124.82 q ML 58.238
27
28 Stage1
29 Cuaq Cuor
30 A1 7.000 7.429
31 B1 2.197 7.429
32 C1 2.197 3.586
33 D1 1.944 7.631 hex 48.87 Effor 95.00 0.000
34
35 Stage2
36 Cuaq Cuor
37 A2 2.197 3.586
38 B2 0.337 3.586
39 C2 0.337 2.098
40 D2 0.239 3.664 hex 641.37 Effor 95.00 0.000
41
42 Performance
43 AcRaff 12.222 g/L
44 RCuex 95.19 %

Joseph kafumbila Page 73
A B C D E F G H I
45
46 Table 18 Modelling Table of 2Ex2S - part 2
47
48 Stripping step
49 Data Data solver variables Solver constraints
50 CuSP 35 g/L CuSP 35 g/L Data-solver
51 AcSP 190 g/L AcSP 190 g/L Data-solver 0.000
52 CuAD 50 g/L CuAD 50 g/L Data-solver 0.000
53 Eff1 98 % Eff1 98 % Data-solver 0.000
54 Eff2 98 % Eff2 98 % Data-solver 0.000
55
56 Constants
57 ast 243.90 cst 56.479 est -0.107
58 bst -1.540 dst -3.0842 fst 0.992
59
60 General
61 O/Ast
ADF 2.814
62 SP flow 177.69 m3/h
63
64 Stage 1
65 Cuaq Cuor
66 A1 50.000 7.429
67 B1 50.000 2.935
68 C1 37.356 2.935
69 D1 50.258 2.844 hst 551.62 Effor 98.00 0.000
70
71 Stage 2
72 Cuaq Cuor
73 A2 37.356 2.935
74 B2 37.356 2.098
75 C2 35.000 2.098
76 D2 37.404 2.081 hst 927.89 Effor 98.00 0.000
77
78 Performance
79 RCust 71.76 %
80 NetCu 0.312 (g/L)/1V%
81
82 Set objective
83 Set objective
ex st 0.000
YC2 -YC2

Joseph kafumbila Page 74
8. SX plant optimization

8.1. Concept

Operating plant mass balance is tried to have a large amount of data from operating plant.
Operating plant mass balance purpose is to produce a picture of the state of an operating plant. Static
simulation program has been developed to give a picture of copper solvent extraction plant using Lix984N
as extractant [26]. The main problem of this program is to consider that the measurements of stream
flowrates and concentration of copper in the streams are correct. In reality, operating plant mass balance
requires data correction and copper mass balance between extraction and stripping steps. This step
requires always human reasoning. In most cases the advance ratio O/A calculated with the stream
flowrates is generally different from that calculated with the concentrations of copper in the streams.

The objective of this chapter is to give a simple method for data correction operation. This
method is applied to all copper extraction reagents. After this data correction operation, the main
parameters of SX plant optimization can be determined: advance ratio O/A, maximum loading, extractant
volume percent, copper recovery, copper net transfer, percentage to maximum loading and stage
efficiencies. These parameters are calculated regularly and give the performances of copper solvent
extraction plant.

8.2. Data correction and mass balance

8.2.1. Data correction

8.2.1.1. Problem description

Figure (24) gives a MacCabe-Thiele diagram on extraction step having two stages in counter
current configuration. Points “A”, “B” and “C” must be on the straight line. Otherwise the data of Points
“A”, “B” and “C” must be changed to be on the straight line. Equation (121) gives the mathematical
expression of straight line passing through points “A”, “B” and “C”.

Joseph kafumbila Page 75
Figure 24: MacCabe-Thiele diagram on extraction step having two stages

Cuor = φ * Cuaq + π (121)

Where “φ” and “π” are constants.

There are two possibilities for copper solvent extraction configuration:

 The value of “φ” (slope) is known and equation (122) gives the value of the slope. The
unknown value is “π”.
 The values of “φ” and “π” are unknown.

1
φ = O/A (122)
ADF

Where “𝑂/𝐴𝐴𝐷𝐹 ” is the advance ratio O/A (ratio organic flowrate on PLS flowrate)

8.2.1.2. Known slope value

In this case, the regression line has a value of “φ” which is the average value of “φA ”, “φB ” and
“φC ” of straight passing through points “A”, “B” and “C”. The new position can take any position on the
straight line. The approximation to get the new data of points is that: the new position of point is the
interception of the straight line with the line perpendicular to the straight line “AC” and passing through
the old position of point.

Figure (25) gives an example of regression line. The value of the slope of straight line is known.
Joseph kafumbila Page 76
Figure 25: Regression line with known value of the slope

8.2.1.3. Unknown value of the slope

In this case there are three types of regression line:

 The concentrations of copper in the aqueous phase are accurate. In this case the
concentrations of copper in the organic phase are changed by finding the least squares
regression line (Cuor = f(Cuaq ).
 The concentrations of copper in the organic phase are accurate. In this case the
concentrations of copper in aqueous phase are changed by finding the least squares
regression line (Cuaq = f(Cuor ).
 The concentrations of copper in the organic and the aqueous phases are not accurate. In
this condition, the change in concentrations of copper in organic and aqueous can take
several directions. The approximation is that this change takes the orthogonal direction
on the orthogonal regression line.

Figure (26) gives an example of the three possibilities of changes of X and Y coordinates. On
Figure (26) there are three points “A”, “B” and “C” having the coordinates X and Y. The three points
must be on the same straight line.

Joseph kafumbila Page 77
Figure 26: Regression lines with unknown value of slope

There are three possibilities:

 Points in red color changes the position to points in green color when the least squares
regression line Y=f(X) is used.
 Points in red color changes the position to points in violet color when the least squares
regression line X=f(Y) is used.
 Points in red color changes the position to points in blue color when the orthogonal
regression line is used.

8.2.1.4. Application to SX plant

 Plant data

Figure (27) gives an example of copper solvent extraction plant having triple series configuration
on extraction step and series configuration on stripping step [22].

Table (29) gives the coordinates of “A1”, “C1”, “C2” and “C3” on the extraction step and the
coordinates of points “A1”, “C1” and “C2” on the stripping step.

Figures (28) and (29) present respectively the coordinates in form of graphic on extraction and
stripping step. The points are not on the straight line on extraction and stripping steps.

Joseph kafumbila Page 78
Figure 27: Data of copper solvent extraction plant

Figure 29: Point coordinates on extraction step

Joseph kafumbila Page 79
Figure 29: Point coordinates on stripping step

Table 29: coordinates of points of Figure 27

Extraction Strip
Cuaq (g/L) Cuor (g/L) Cuaq (g/L) Cuor (g/L)
A1 39.00 12.30 55.60 12.30
C1 29.00 10.00 43.80 6.00
C2 15.70 7.80 42.00 5.30
C3 10.00 5.30

 Known values of slope

 Extraction step

Table (30), as it appears on the Microsoft Excel spreadsheet, gives data correction of extraction
step. The explanation of the procedure for obtaining the new coordinates is the following:

- On Table (30) the maximum number of data that can be corrected is five (four stages in counter
current configuration).
- The excel cells ranged from “B5” to “B9” give the designation of points
- In excel cells ranged from “C5” to “C9”, type the concentrations of copper in aqueous (g/L) (if there
is not value to type in the cell at the end of the range, the excel cell must be empty).
- In excel cells ranged from “D5” to “D9”, type the corresponding concentration of copper in the
organic (g/L). (If there is not value to type in the cell at the end of the range, the excel cell must be
empty).

Joseph kafumbila Page 80
A B C D E F G H
1
2 Table 30 New coordinates of points extraction step
3 Old coordinates New coordinates
4 Cuaq Cuor 𝜆𝑛 Cuaq Cuor
5 A1 39.00 12.30 1.664 37.58 12.69
6 C1 29.00 10.00 2.091 28.36 10.18
7 C2 15.70 7.80 3.518 17.68 7.26
8 C3 10.00 5.30 2.491 10.39 5.28
9 C4 0.00 0.00 0.00
10 Σ𝜆𝑛
11 9.764
12 O/AAF 3.667
13 n 4
14 φ 0.273
15 π 2.441

- In the excel cells ranged from “E5” to “E9”, type:
o E5= if(C5=0,0,D5-D$13*C5)
o E6= if(C6=0,0,D6-D$13*C6)
o E7= if(C7=0,0,D7-D$13*C7)
o E8= if(C8=0,0,D8-D$13*C8)
o E9= if(C9=0,0,D5-D$13*C9)

- In the excel cells ranged from “F5” to “F9”, type:
o F5=if(C5=0,0,(D5+D$13*C5-D$14)/(2*D$13))
o F6= if(C6=0,0,(D6+D$13*C6-D$14)/(2*D$13))
o F7= if(C7=0,0,(D7+D$13*C7-D$14)/(2*D$13))
o F8= if(C8=0,0,(D8+D$13*C8-D$14)/(2*D$13))
o F9= if(C9=0,0,(D9+D$13*C9-D$14)/(2*D$13))

- In the excel cells ranged from “G5” to “G9”, type:
o F5= if(C5=0,0,(D$14+D5+D$13*C5)/2)
o F6= if(C6=0,0,(D$14+D6+D$13*C6)/2)
o F7= if(C7=0,0,(D$14+D7+D$13*C7)/2)
o F8= if(C8=0,0,(D$14+D8+D$13*C8)/2)
o F9= if(C9=0,0,(D$14+D9+D$13*C9)/2)

- In the excel cell “E11”, type “=SUM(E5:E9)”.
- In the excel cell “D12”, type number “3.667” the advance ratio on extraction step.
- In the excel cell “D13”, type “=COUNT(C5:C9)”.
- In the excel cell “D14”, type “=1/D12”.
- In the excel cell “D15”, type “=E11/D13”.

Figure (30) present the new coordinates of points on extraction step on a graph.

Joseph kafumbila Page 81
Figure 30: Point new coordinates on extraction step of Table (3)

 Stripping step

Table (31) gives the new coordinates on stripping step using the procedure explained in chapter
(extraction step).

A B C D E F G H
1
2 Table 31 New coordinates of points stripping step
3 Old coordinates New coordinates
4 Cuaq Cuor 𝜆𝑛 Cuaq Cuor
5 A1 55.60 12.30 -23.091 54.85 12.78
6 C1 43.80 6.00 -21.880 44.00 5.87
7 C2 42.00 5.30 -21.435 42.55 4.95
8 C3 0.00 0.00 0.00
9 C4 0.00 0.00 0.00
10 Σ𝜆𝑛
11 -66.604
12 O/AADF 1.571
13 n 3
14 φ 0.637
15 π -22.153

Figure (31) present the new coordinates of points on stripping step on a graph.

Joseph kafumbila Page 82
Figure 31: Point new coordinates on stripping step of Table (3)

 Unknown values of slope

 Extraction step

Table (32), as it appears on the Microsoft Excel spreadsheet, gives new coordinates of points on
extraction step. The explanation of the procedure for obtaining the orthogonal regression line is the
following:

- On Table (32) the maximum number of data that can be corrected is five (four stages in counter
current configuration).
- The excel cells ranged from “B6” to “B10” give the designation of points.

Small Table (A)

- In excel cells ranged from “C6” to “C10”, type the concentrations of copper in aqueous (g/L) (if
there is not value to type in the cell at the end of the range, the excel cell must be empty).
- In excel cells ranged from “D6” to “D10”, type the corresponding concentration of copper in the
organic (g/L). (if there is not value to type in the cell at the end of the range, the excel cell must be
empty)
- In the excel cells ranged from “E6” to “E10”, type:
o E6=IF(C6=0,0,C6*D6)
o E7=IF(C7=0,0,C7*D7)
o E8=IF(C8=0,0,C8*D8)
o E9=IF(C9=0,0,C9*D9)
o E10=IF(C10=0,0,C10*D10)

Joseph kafumbila Page 83
A B C D E F G H I J
1
2 Table 32 Orthogonal regression coordinates on extraction step
3
4 Table A 𝐂𝐮𝐨𝐫 =f(𝐂𝐮𝐚𝐪 ) Table B 𝐂𝐮𝐚𝐪 =f(𝐂𝐮𝐨𝐫 )
2
5 Cuaq Cuor Cuaq*Cuor [Cuaq ] Cuor Cuaq Cuaq *Cuor [Cuor ]2
6 A1 39 12.3 479.70 1521.00 12.30 39.00 479.70 151.29
7 C1 29 10 290.00 841.00 10.00 29.00 290.00 100.00
8 C2 15.7 7.8 122.46 246.49 7.80 15.70 122.46 60.84
9 C3 10.3 5.3 54.59 106.09 5.30 10.30 54.59 28.09
10 C4
11
12 ΣCuaq ΣCuor ΣCuaq*Cuor Σ[Cuaq ]2 ΣCuor ΣCuaq ΣCuaq *Cuor Σ[Cuor ]2
13 94.00 35.40 946.75 2714.58 35.40 94.00 946.75 340.22
14
15 n 4 n 4
16 Max 39.00 Max 12.30
17
18 Y=f(x) coefficients X=f(Y) coefficients
19 φ1 0.227 φ2 4.265
20 π1 3.512 π2 -14.243
21
22 Table C Orthogonal coefficients
23 φ3 0.231
24 π3 3.426
25
26 Table D New coordinates
27 Y=f(x) X=f(Y) Orthogonal
c
28 Cuaq Cucor Cuaq Cuor Cucaq Cucor
29 A1 39.00 12.37 38.21 12.30 38.723 12.364
30 C1 29.00 10.10 28.40 10.00 28.741 10.060
31 C2 15.70 7.08 19.02 7.80 17.326 7.425
32 C3 10.30 5.85 8.36 5.30 9.210 5.552
33 C4
34
35 O/AADA 4.332

- In the excel cells ranged from “F6” to “F10”, type:
o F6= C6^2
o F7= C7^2
o F8= C8^2
o F9= C9^2
o F10= C10^2

- In the excel cell “C13”, type “=SUM(C6:C10)”.
- In the excel cell “D13”, type “=SUM(D6:D10)”.
Joseph kafumbila Page 84
- In the excel cell “E13”, type “=SUM(E6:E10)”.
- In the excel cell “F13”, type “=SUM(F6:F10)”.

- In the excel cell “D15”, type “=COUNT(C6:C10)”.
- In the excel cell “D16”, type “=MAX(C6:C10)”.

- In the excel cell “D19” (φ1), type “=(D15*E13-C13*D13)/(D15*F13-C13^2)”.
- In the excel cell “D20” (π1), type “=(D13*F13-C13*E13)/(D15*F13-C13^2)”.

Equation (123) gives the mathematical expression of Cuor = f(Cuaq ) regression line.

Cuor = φ1 * Cuaq + π1 (123)

Small Table (B)

- In the excel cells ranged from “G6” to “G10”, type:
o G6=D6
o G7=D7
o G8=D8
o G9=D9
o G10=D10

- In the excel cells ranged from “H6” to “H10”, type:
o H6=C6
o H7=C7
o H8=C8
o H9=C9
o H10=C10

- In the excel cells ranged from “E6” to “E10”, type:
o I6= IF(G6=0,0,G6*H6)
o I7= IF(G7=0,0,G7*H7)
o I8= IF(G8=0,0,G8*H8)
o I9= IF(G9=0,0,G9*H9)
o I10= IF(G10=0,0,G10*H10)

- In the excel cells ranged from “J6” to “J10”, type:
o J6= G6^2
o J7= G7^2
o J8= G8^2
o J9= G9^2
o J10= G10^2

- In the excel cell “G13”, type “=SUM(G6:G10)”.
- In the excel cell “H13”, type “=SUM(H6:H10)”.

Joseph kafumbila Page 85
- In the excel cell “I13”, type “=SUM(I6:I10)”.
- In the excel cell “J13”, type “=SUM(J6:J10)”.

- In the excel cell “H15”, type “=D15”.
- In the excel cell “H16”, type “=MAX(G6:G10)”.

- In the excel cell “H19” (φ2), type “=(H15*I13-G13*H13)/(H15*J13-G13^2)”.
- In the excel cell “H20” (π2), type “=(H13*J13-G13*I13)/(H15*J13-G13^2)”.

Equation (124) gives the mathematical expression of Cuaq = f(Cuor ) regression line.

Cuaq = φ2 * Cuor + π2 (124)

Small Table (C)

- In the excel cell “E23” (φ3), type “=(D19*H19+1)/(2*H19)”.
- In the excel cell “E24” (π3), type “=(D20*H19-H20)/(2*H19)”.

Equation (125) gives the mathematical expression of orthogonal regression line.

Cuor = φ3 * Cuaq + π3 (125)

Small Table (D)

- In the excel cells ranged from “C29” to “C33”, type:
o C29=if(C6=0,0,C6)
o C30= if(C7=0,0,C7)
o C31= if(C8=0,0,C8)
o C32= if(C9=0,0,C9)
o C33= if(C10=0,0,C10)

- In the excel cells ranged from “D29” to “D33”, type:
o D29= if(C29=0,0,C29*D$19+D$20)
o D30= if(C30=0,0,C30*D$19+D$20)
o D31= if(C31=0,0,C31*D$19+D$20)
o D32= if(C32=0,0,C32*D$19+D$20)
o D33= if(C33=0,0,C33*D$19+D$20)

- In the excel cells ranged from “F29” to “F33”, type:
o F29=if(D6=0,0,D6)
o F30= if(D7=0,0,D7)
o F31= if(D8=0,0,D8)
o F32= if(D9=0,0,D9)
o F33= if(D10=0,0,D10)

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- In the excel cells ranged from “E29” to “E33”, type:
o E29= if(F29=0,0,F29*H$19+H$20)
o E30= if(F30=0,0,F30*H$19+H$20)
o E31= if(F31=0,0,F31*H$19+H$20)
o E32= if(F32=0,0,F32*H$19+H$20)
o E33= if(F33=0,0,F33*H$19+H$20)

- In the excel cells ranged from “G29” to “G33”, type:
o G29= if(C6=0,0,(D6+E$23*C6-E$24)/(2*E$23))
o G30= if(C7=0,0,(D7+E$23*C7-E$24)/(2*E$23))
o G31= if(C8=0,0,(D8+E$23*C8-E$24)/(2*E$23))
o G32= if(C9=0,0,(D9+E$23*C9-E$24)/(2*E$23))
o G33= if(C10=0,0,(D10+E$23*C10-E$24)/(2*E$23))

- In the excel cells ranged from “H29” to “H33”, type:
o H29= if(C6=0,0,(E$24+D6+E$23*C6)/2)
o H30= if(C7=0,0,(E$24+D7+E$23*C7)/2)
o H31= if(C8=0,0,(E$24+D8+E$23*C8)/2)
o H32= if(C9=0,0,(E$24+D9+E$23*C9)/2)
o H33= if(C10=0,0,(E$24+D10+E$23*C10)/2)

- In the excel cell “H35”, type “=1/E23”.

Figure (32) present the new coordinates of points on extraction step.

Figure 32: Graphic representation of Table (32) results

Equation (126) gives the advance ratio O/A obtained with the concentrations of copper in the
streams.
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1
O/AADA =φ (126)
3

Where “𝑂/𝐴𝐴𝐷𝐴 ” is the advance ratio obtained with the concentrations of copper in the streams.

 Stripping step

Table (32) gives the new coordinates on stripping step using the procedure explained in chapter
(extraction step). Figure (33) present the new coordinates of points on stripping step.

A B C D E F G H I J
1
2 Table 33 Orthogonal regression coordinates on stripping step
3
4 Table A 𝐂𝐮𝐨𝐫 =f(𝐂𝐮𝐚𝐪 ) Table B 𝐂𝐮𝐚𝐪 =f(𝐂𝐮𝐨𝐫 )
5 Cuaq Cuor Cuaq *Cuor [Cuaq ]2 Cuor Cuaq Cuaq *Cuor [Cuor ]2
6 A1 55.60 12.30 683.88 3091.36 12.30 55.60 683.88 151.29
7 C1 43.80 6.00 262.80 1918.14 6.00 43.80 262.80 36.00
8 C2 42.00 5.30 222.60 1764.00 5.30 42.00 222.60 28.09
9 C3 0.00 0.00 0.00 0.00 0.00 0.00
10 C4 0.00 0.00 0.00 0.00 0.00 0.00
11
12 ΣCuaq ΣCuor ΣCuaq *Cuor Σ[Cuaq ]2 ΣCuor ΣCuaq ΣCuaq *Cuor Σ[Cuor ]2
13 141.40 23.60 1169.28 6773.8 23.60 141.40 1169.28 215.38
14
15 n 3 n 3
16 Max 55.60 Max 12.30
17
18 Y=f(x) coefficients X=f(Y) coefficients
19 φ1 0.522 φ2 1.915
20 π1 -16.719 π2 32.067
21
22 Table C Orthogonal coefficients
23 φ3 0.522
24 π3 -16.731
25
26 Table D New coordinates
27 Y=f(x) X=f(Y) Orthogonal
28 Cuaq Cucor Cucaq Cuor Cucaq Cucor
29 A1 55.60 12.28 55.62 12.30 55.61 12.29
30 C1 43.80 6.13 43.56 6.00 43.68 6.06
31 C2 42.00 5.19 42.22 5.30 42.11 5.24
32 C3 0.00 0.00 0.00 0.00 0.00 0.00
33 C4 0.00 0.00 0.00 0.00 0.00 0.00
34
35 O/AADA 1.916

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Figure 33: Graphic representation of Table (5) results

 Observation

By observing the results after data correction, the regression line having the value of slope
coming from the advance ratio O/AADF is far from coincide with the regression line whose slope comes
from the advance ratio O/AADA . This means that the flowrate measurement is not correct. In this
condition, the orthogonal regression line is adopted as the method for data correction.

8.2.2. Copper mass balance

8.2.2.1. Concept

After data correction operation, the values of copper concentrations in loaded organic and
stripped organic remain the measurement values. Equations (127), (128), (129) and (130) give the new
concentrations of copper in the PLS, raffinate, advance electrolyte and spent electrolyte with the
measurement values of copper concentrations in the loaded organic and stripped organic. Notice that
when the stripping step has one stage, the values of “φ” and “π” are given by mathematical expression of
straight line passing through points “A” and “B” having measurement coordinates.

CuM
LO −π
CuPLS = (127)
φ

CuM
SO −π
CuRaf = (128)
φ

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CuM
LO −π
CuAD = (129)
φ

CuM
SO −π
CuSE = (130)
φ

𝑀 𝑀
Where “𝐶𝑢𝐿𝑂 ” and “𝐶𝑢𝑠𝑂 ” are respectively the measurement values of concentrations of copper in loaded and
stripped organic.

8.2.2.2. Application to SX plant

Table (34) gives the new concentrations of copper in the streams after data correction with the
orthogonal regression line method. Table (35) gives the new concentrations of copper in the streams after
mass balance operation.

Table 34: Coordinates of points after correction with orthogonal regression line

Extraction Strip
Cuaq (g/L) Cuor (g/L) Cuaq (g/L) Cuor (g/L)
A1 38.72 12.36 55.61 12.29
C1 28.74 10.06 43.68 6.06
C2 17.33 7.42 42.11 5.24
C3 9.21 5.55

Table 35: Coordinates of points after mass balance

Extraction Strip
Cuaq (g/L) Cuor (g/L) Cuaq (g/L) Cuor (g/L)
A1 38.45 12.30 55.63 12.30
C1 28.74 10.06 43.68 6.06
C2 17.33 7.42 42.22 5.30
C3 8.12 5.30

8.3. Solvent extraction plant parameters

8.3.1. Concept

There are a number of solvent plant parameters which help to evaluate the performance of
copper solvent extraction and can be determined after data correction and copper mass balance
operations. These parameters are determined in a regular basis in copper solvent extraction plant. These
parameters are:

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 Maximum loading;
 Extractant volume percent;
 Copper recovery;
 Copper net transfer;
 Percentage to maximum loading;
 Stage efficiencies.

Maximum loading, extractant volume percent, copper recovery, copper net transfer and
percentage to maximum loading can be determined by using explanation described in chapter (612).
Determining of stage efficiencies requires the first getting the coordinates of the equilibrium points.

8.3.2. Stage efficiencies

8.3.2.1. Concept

The concentrations of copper in the outlet aqueous and organic of stage approach equilibrium,
but it do not reach it because of residence time, present of impurities, impeller power and impeller type.
The stage efficiencies are used to measure how close to equilibrium each stage gets.

The next step is determining the concentrations of copper in organic and aqueous of points “D”
(Figures (10) and (12)) for each stage. Point “D” is the intercession of the line having the slope “-φ” and
passing through point “B” and the distribution isotherm line.

8.3.2.2. Straight line passing through points D and B

According to Figures (10) and (12), equations (131) and (132) give the mathematical expressions
of the straight line passing through point “B” and having the slope “-φ” respectively on extraction and
stripping steps.

Cuor = - φ * Cuaq + (YA + φ * XC ) (131)

Cuor = - φ * Cuaq + (YC + φ * XA ) (132)

8.3.2.3. Distribution isotherms

 Without computer program

In this case there is not a computer program, PLS and spent electrolyte solutions having
concentrations of copper and free acid after data correction and mass balance operations are prepared.
Extraction and stripping isotherms are constructed using the laboratory scale test method using Plant

Joseph kafumbila Page 91
stripped organic on extraction step and plant loaded organic on stripping step. The maximum loading
using the prepared PLS must be obtained during the laboratory scale test on extraction step.

The extrapolation curves of extraction and stripping isotherms are obtained using equations (133)
and (134) respectively.

Ln(Cueor ) = Δ * [ln(Cueaq )]2 + Ω * ln(Cueaq )+ ξ (133)

Where “Δ”, “Ω” and “ξ” are the constants.

Cueor = δ * [Cueaq ]2 + θ * Cueaq + υ (134)

Where “δ”, “θ” and “υ” are the constants.

 With computer program

The extraction and stripping isotherms are constructed using the concentrations of copper and
free acid in PLS and spent electrolyte after data correction and mass balance in form of point coordinates.
The extrapolation curves of extraction and stripping isotherms are obtained using equations (133) and
(134) respectively.

8.3.2.4. Determining of stage efficiencies

The explanation of the procedure for determining stage efficiencies is done through an example.
Figure (34) gives a flow diagram of pilot plant with data. The configuration of copper solvent extraction is
triple series with two stages on stripping step.

Figure (35) gives pilot plant flow diagram with after data correction and mass balance. Table (36)
gives the concentrations of copper in organic and aqueous of extraction isotherm. The extraction isotherm
is obtained using method explained in chapter (4.3.) and data from Figure (35). Table (37) gives the
concentrations of copper in organic and aqueous of stripping step isotherm. The stripping isotherm is
obtained using method explained in chapter (4.3.) and data from Figure (35).

Table 36: Predicted Extraction isotherm

Cueaq (g/L) 4.321 2.880 1.920 0.960 0.480 0.240 0.120 0.060
Cueor (g/L) 11.231 10.885 10.333 9.108 7.677 6.140 4.600 3.190

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Figure 34: Flow diagram of copper solvent extraction of pilot plant

Figure 35: Flow diagram of copper solvent extraction of pilot plant after correction of data

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Table 37: Predicted stripping isotherm

Cueaq (g/L) 43.00 40.00 37.00 34.00 31.00 28.00
Cueor (g/L) 3.312 3.084 2.857 2.630 2.402 2.174

Equations (135) and (136) give extrapolation curves obtained using Excel trendline program on
extraction and stripping steps.

Ln(Cueor ) = -0.0583 * [ln(Cueaq )]2 + 0.2121 * ln(Cueaq ) + 2.2272 (135)

Cueor = -1.130 * 10−5 * [Cueaq ]2 + 7.667 * 10−2 * Cueaq + 3.590 * 10−2 (136)

Table (38), as it appears on Microsoft Excel spreadsheet, gives the stage efficiencies on extraction
and stripping steps.

A B C D E F G H
1
2 Table 38 Stage efficiencies
3
4 Extraction step
5 φ 1.654
6 Cuaq Cuor
e
7 A1 4.321 9.722 Effaq -1 73.10 %
e
8 C1 2.839 7.272 Effaq -2 80.01 %
e
9 C2 1.013 4.251 Effaq -3 94.49 %
10 C3 0.158 2.838
11
12 Cueaq Cueor-1 Cueor-2 constraints
13 D1 2.294 10.62 10.62 0.000
14 D2 0.556 8.03 8.03 0.000
15 D3 0.108 4.33 4.33 0.000
16
17 Stripping step
18 φ 0.768
19 Cuaq Cuor
e
20 A1 39.40 9.722 Effaq -1 79.33 %
e
21 C1 32.64 4.527 Effaq -2 85.61 %
22 C2 30.44 2.838
23
24 Cueaq Cueor-1 Cueor-2 constraints
25 D1 41.17 3.17 3.17 0.000
26 D2 33.01 2.55 2.55 0.000
27

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The data in red color come from Figure (35). The data in blue color are the solver variables. The
procedure of determining the stage efficiencies is the following:

Extraction step

- In the excel cell “C13” (solver variable), type number “2.839” (starting value - Aqueous copper
concentration of point “C1”).
- In the excel cell “C14” (solver variable), type number “1.013” (starting value - Aqueous copper
concentration of point “C2”).
- In the excel cell “C15” (solver variable), type number “0.158” (starting value - Aqueous copper
concentration of point “C3”).

- In the excel cell “D13”, type “=-C$5*C13+(D7+C$5*C8)” (Equation (93) of stage 1).
- In the excel cell “D14”, type “=-C$5*C14+(D8+C$5*C9)” (Equation (93) of stage 2).
- In the excel cell “D15”, type “=-C$5*C15+(D9+C$5*C10)” (Equation (93) of stage 3).

- In the excel cell “E13”, type “=EXP(-0,0583*(LN(C13))^2+0,2121*LN(C13)+2,2272)”.
- In the excel cell “E14”, type “=EXP(-0,0583*(LN(C14))^2+0,2121*LN(C14)+2,2272)”.
- In the excel cell “E15”, type “=EXP(-0,0583*(LN(C15))^2+0,2121*LN(C15)+2,2272)”.

- In the excel cell “F13”, type “=D13-E13” (solver constraint of stage 1).
- In the excel cell “F14”, type “=D14-E14” (solver constraint of stage 2).
- In the excel cell “F15”, type “=D15-E15” (solver constraint of stage 3).

- In the excel cell “G7”, type “=(C7-C8)/(C7-C13)*100”.
- In the excel cell “G8”, type “=(C8-C9)/(C8-C14)*100”.
- In the excel cell “G7”, type “=(C9-C10)/(C9-C15)*100”.

Stripping step

- In the excel cell “C25” (solver variable), type number “39.40” (starting value - Aqueous copper
concentration of point “A1”).
- In the excel cell “C26” (solver variable), type number “32.64” (starting value - Aqueous copper
concentration of point “A2”).

- In the excel cell “D25”, type “=-C$18*C25+(D21+C$18*C20)”.
- In the excel cell “D36”, type “=-C$18*C26+(D22+C$18*C21)”.

- In the excel cell “E25”, type “=-1,146*10^-5*C25^2+7,671*10^-2*C25+3,599*10^-2”.
- In the excel cell “E26”, type “=-1,146*10^-5*C26^2+7,671*10^-2*C26+3,599*10^-2”.

- In the excel cell “F25”, type “=D25-E25” (solver constraint of stage 1).
- In the excel cell “F26”, type “=D25-E25” (solver constraint of stage 2).

Joseph kafumbila Page 95
- In the excel cell “G20”, type “=(C20-C21)/(C25-C21)*100”.
- In the excel cell “G21”, type “=(C21-C22)/(C26-C22)*100”.

Solver program

Excel solver program execution is as follows:

1) On the ‘Data’, in the ‘Analysis group’ click solver (if the solver command is not available, you
must activate the solver add-in).
2) In the ‘Set objective’ box, enter the cell reference ‘F13’ of simulation program constraint.
3) Click ‘Value of’ and then type the number ‘0’ in the box.
4) In the ‘By Changing Variable Cells’ box, enter the reference (C13, C14, C15, C25 and C26)
for each solver variable (blue color). Separate the references with commas (English version).
5) In the ‘Subject to the constraints’ box, enter solver constraints by doing the following:
a. In the ‘Solver Parameters’ dialog box, click ‘Add’.
b. In the ‘Cell Reference’ box, enter the cell reference “F14” solver constraint (green color).
c. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
d. In the ‘Solver Parameters’ dialog box, click ‘Add’.
e. In the ‘Cell Reference’ box, enter the cell reference “F15” solver constraint (green color).
f. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
g. In the ‘Solver Parameters’ dialog box, click ‘Add’.
h. In the ‘Cell Reference’ box, enter the cell reference “F25” solver constraint (green color).
i. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
j. In the ‘Solver Parameters’ dialog box, click ‘Add’.
k. In the ‘Cell Reference’ box, enter the cell reference “F26” solver constraint (green color).
l. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
m. Click ‘OK’ to return to ‘Solver Parameters’ dialog box.
6) Click ‘Solve’. To keep the solution values on the worksheet, in the ‘Solver Results’ dialog box,
click ‘Keep solver solution’.

Figures (36) and (37) give MacCabe-Thiele diagram on extraction and stripping steps after data
correction and mass balance operations.

Joseph kafumbila Page 96
Figure 36: MacCabe-Thiele diagram on extraction step

Figure 37: MacCabe-Thiele diagram on stripping step

Joseph kafumbila Page 97
References

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4. C.M. Moreno, J.R. Pérez-correa, A. Otero, Dynamic modelling of copper solvent extraction
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crud treatment at Bwana Mkubwa solvent extraction plant, ISEC 2008.

15. Andersen T.N. Adamson D.L. and Richards K.J., The corrosion of lead anodes in copper
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16. K. Kafumbila, Design of copper electrowinning circuit using conventional cells, Technical
report, Researchgate, 2017.

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21. Cognis corporation, Solvent extraction process, US patent – US2004/0103756 A1, June
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