DESIGN OF COPPER

SOLVENT EXTRACTION
CONFIGURATIONS

Joseph Kafumbila

The textbook provides the procedure for design static simulation programs using Excel Solver for
optimization on an Excel worksheet. This procedure will allow the design of a simulation program for
all copper solvent extraction configurations. The simulation program will be designed to size a new
plant or track performance of an operating plant.
Design of simulation program of copper solvent extraction configuration using Microsoft Excel Solver
© 2016 Joseph Kafumbila
jokafumbila@hotmail.com

Joseph Kafumbila Page 1
Contents

1. INTRODUCTION..................................................................................................................... 3

2. EQUILIBRIUM LINE SIMULATION MODELS ............................................................................ 6

2.1. EXTRACTION STEP ....................................................................................................................... 6
2.2. STRIPPING STEP ........................................................................................................................ 15

3. EQUILIBRIUM LINE AND MACCABE THIELE DIAGRAM ......................................................... 19

3.1. EQUILIBRIUM LINE..................................................................................................................... 19
3.2. MACCABE THIELE DIAGRAM ....................................................................................................... 21

4. CONSTRAINTS OF COPPER SX-EW PLANT ............................................................................ 28

4.1. EQUILIBRIUM CONSTRAINTS BETWEEN EXTRACTION AND STRIPPING STEPS ............................................ 28
4.2. MAXIMUM VALUE OF EXTRACTANT VOLUME PERCENTAGE................................................................. 28
4.3. FREE ACID CONCENTRATION IN PLS .............................................................................................. 28
4.4. MAXIMUM FREE ACID CONCENTRATION IN SPENT ELECTROLYTE .......................................................... 28
4.5. MINIMUM COPPER CONCENTRATION IN SPENT ELECTROLYTE ............................................................. 29
4.6. MAXIMUM COPPER CONCENTRATION IN ADVANCE ELECTROLYTE ........................................................ 29
4.7. OPTIMUM VALUE OF RATIO OF ORGANIC TO AQUEOUS OF EXTRACTION STEP ......................................... 30
4.8. SATURATION RATIO SR .............................................................................................................. 30

5. SIMULATION PROGRAM USING EXCEL SOLVER PROGRAM ................................................. 32

5.1. DESCRIPTION ........................................................................................................................... 32
5.2. STATIC SIMULATION PROGRAM DESIGN ......................................................................................... 32

6. BIBLIOGRAPHY .................................................................................................................... 75

Joseph Kafumbila Page 2
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/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 equilibrium line of copper solvent extraction using chelating reagents were made. These
simulation models were based either on equilibrium constant of copper solvent extraction chemical reaction [1]
or on extrapolation curves of equilibrium lines of extraction and stripping steps [2]. Simulation model based on
chemical reaction equilibrium constant was required knowledge of phenomenology of chemical reaction.
Currently, most of static simulation programs of copper solvent extraction configuration use equilibrium line
simulation models based on chemical reaction equilibrium constants because it is easy to simulate impact of iron
co-extraction to extraction step and temperature to stripping step. Design of this static simulation program
requires a certain level of knowledge in computer programming. This blocks innovation in design of new reagent
or complex copper solvent extraction configurations because static simulation programs are developed by
extractant suppliers far from plant designers.

Equilibrium line simulation model based on chemical reaction equilibrium constant requires
knowledge of all intermediate chemical reactions. Example of intermediate chemical reactions occurring during
copper solvent extraction with MOC- 45 is the following [1]:

Cu2+ + 2HR ↔ CuR 2 + 2H + (a)

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Cu2+ + (HR)2 ↔ CuR 2 + 2H + (b)

2HR ↔ (HR)2 (c)

HR and (HR)2 are the molecular forms of MOC- 45 extractant in organic phase.

Equilibrium conditions of each chemical reaction are given by mathematical expressions (1), (2), and
(3).

[CuR ]x[H+ ]2
K a =[Cu+22]x[HR]2 (1)

[CuR ]x[H+ ]2
2
K b =[Cu2+ ]x[(HR) 2 (2)
2]

[(HR)2 ]
Kc = (3)
[HR]2

where K a , K b , and K c are respectively chemical reaction equilibrium constants of chemical reactions
(a), (b), and (c).

Static simulation model will be defined by finding the equilibrium constants values using
experimental data of equilibrium lines. It must involve the following mathematical expressions giving mass
balances.

- Copper mass Balance:

Vo
[Cu2+ ]i = [Cu2+ ]f + x [CuR 2 ] (5)
Va

- Oxime radical R mass balance:

[HR]t = [HR] + 2 x [(HR)2 ] + 2 x [CuR 2 ] (6)

- Hydrogen ion mass balance:

Vo
[H + ]f = [H + ]i + 2 x x [CuR 2 ] (7)
Va

Where the indices i, f and t respectively mean initial, final and total. Vo and Va respectively mean
volume of organic and aqueous phases.

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Once the values of chemical reaction equilibrium constants are obtained, the equilibrium line
simulation model will use these mathematical expressions from (1) to (7) to predict the value of copper
concentration in organic phase from the value of copper and free acid concentrations in aqueous and the values
of Va and Vo . This design method of equilibrium line simulation model is used by reagent suppliers and its design
is complex.

For dynamic modeling used in industrial copper solvent extraction plant, plant metallurgists use
extrapolation curves of equilibrium lines [2]. In most cases, the conditions for using these extrapolation
equations are limited to this copper solvent extraction plant.

The goal of this textbook is to give a simple procedure for designing a static simulation program of
copper solvent extraction configuration. This simple procedure will allow designers to quickly have a static
simulation program for complex configuration or new product that have not yet simulation program developed
by supplier. It will also allow plant metallurgists to have a static simulation program for checking plant
performances. This static simulation program uses Excel solver program 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 one cell. Knowledge of the use of Excel Solver is not sufficient. The textbook also gives advice that
prevents static simulation programs to crash when initial data change.

In the second chapter, the textbook offers equilibrium line simulation models of extraction and
stripping steps not requiring knowledge of intermediate chemical reactions. Equilibrium condition of global
chemical reaction is resulted on the assumption that ionic strength varies very little only in aqueous phase. On
the other hand, the ionic strength varies in organic phase. The textbook gives results of experimental tests.
Extraction and stripping equilibrium lines were generated by contacting a series of different volumes of aqueous
phase and stripped organic phase by mechanical stirring. Following attainment of equilibrium after 15 min,
phases were allowed to separate. After phase disengagement, copper was analyzed in raffinate by AAS, whereas
free acid was determined by titration. After more than 10 years of research, the new theory of equilibrium
condition of copper solvent extraction chemical reaction begins to be clear.

In the third and fourth chapters, the textbook also gives theoretical concepts of copper solvent
extraction and industrial constraints which allow, together with equilibrium line simulation models, to design a
static simulation program of simple or complex copper solvent extraction configuration.

In the fifth chapter, the textbook gives the design procedure of the static simulation program of copper
solvent extraction configuration from an example. The procedure involves two options. The first concerns the
designers and the second concerns the plant metallurgists.

Joseph Kafumbila Page 5
2. Equilibrium line simulation models

2.1. Extraction step

2.1.1. 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 (d)
[3]. 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 + (d)

where Cu2+ and H + are copper and hydrogen ionic species in aqueous phase, HR is acid form of
Lix984N extractant, and CuR 2 is copper complex form in organic phase

Thermodynamic equilibrium condition of global chemical reaction (a) is given by the mathematical
expression (8) [4].

μCuR2 + 2μH+ - μCu+2 - 2μHR = 0 (8)

where μρ is chemical potential of species ‘ρ’

Chemical potential of species ‘ρ’ is given by the mathematical expression (9).

Cρ (9)
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 the mathematical expression (9) for all species in the mathematical expression (8)
gives the mathematical expression (10) which is the thermodynamic equilibrium condition.

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[Cueor ] x [Heaq ]2 βCu x βHR 2 γ x γHR 2
= 2 x γ Cu 2= Ke (10)
[Cueaq ] x [HReor ]2 βCuR2 x βH CuR2 x γH

2.1.2. Value of ? ? from molar concentration

2.1.2.1. Definition

The value of thermodynamic equilibrium condition K e from molar concentrations called K e1 is given
by the mathematical expression (11).

[Cueor ]x[Heaq ]2
K e1 = (11)
[Cueaq ]x[HReor ]2

2.1.2.2. Copper molar concentrations in organic and aqueous phases

The values of copper molar concentrations at the steady-state in organic and aqueous phases are
respectively given by the mathematical expressions (12) and (13).

Cue
[Cueor] = 63.55
or
(12)

Cueaq
[Cueaq] = 63.55 (13)

where Cueaq and Cueor are respectively copper concentrations (g/l) in aqueous and organic phases

The mathematical expression (14) gives copper mass balance at the steady-state.

Vaq
Cueor = Cuior + (Cuiaq - Cueaq ) x (14)
Vor

where Cuiaq and Cuior are respectively initial copper concentrations (g/l) in aqueous and organic
phases. Vaq and Vor are respectively volumes of aqueous and organic phases.

2.1.2.3. Free extractant molar concentration in organic phase

The value of free extractant molar concentration in organic phase is given by the mathematical
expression (15).

V% x 0.91 x 1000 Cue
[HReor ] = 100 x 270
or
- 2 x 63.55 (15)

Joseph Kafumbila Page 7
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.

2.1.2.4. 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 (e) and (f).

H2 SO4 ↔ HSO−
4 +H
+
K1ac = 104 (e)

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

If C1 is free sulfuric acid molar concentration in aqueous phase and C2 is molar concentration of anion
SO4−2 associated with copper and buffers in aqueous phase. Sulfuric acid dissociation reaction (e) is complete
because the value of chemical reaction equilibrium constant K1ac is big. Following mass balance comes from
sulfuric dissociation reaction (e).

H2 SO4 HSO4− H+
Initial state C1 0 0
Final state -C1 C1 C1
Mass balance 0 C1 C1

Sulfuric acid dissociation reaction (f) 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 (f). Y is molar concentration of anion HSO4− which goes into dissociation.

HSO4− SO−2
4 H+
Initial state C1 C2 C1
Final state -Y Y Y
Mass balance C1-Y C2+Y C1+Y

Thermodynamic equilibrium condition of sulfuric acid dissociation reaction (f) is given by the
mathematical expression (16). Resolution of the mathematical expression (16) gives second-degree equation.
Hydrogen ion molar concentration in aqueous phase is given by the mathematical expression (17). The value of
molar concentration Y is given by the mathematical expression (18) and the values of constants A and B are
given by the mathematical expressions (19) and (20).

(C2 +Y)(C1 +Y)
K ac
2 = (C1 −Y)
(16)

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e
[Haq ] = C1 + Y (17)

(−A+ √A2 −4 x B)
Y= (18)
2

A = C1 + C2 + K ac
2 (19)

B = C1 x (C2 - K ac
2 ) (20)

From the mathematical expression (18), the value of molar concentration Y 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 ac
2 , the value

of molar concentration Y is lower than zero. In this condition, the value of molar concentration Y in the
mathematical expression (17) 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 Y is greater than zero.

2.1.3. Value of ? ? from chemical activity coefficients

2.1.3.1. Definition

The value of thermodynamic equilibrium condition K e from chemical activity coefficients of species
called K e2 is given by the mathematical expression (21).

βCu x βHR 2 γ x γHR 2
K e2 = x γ Cu (21)
βCuR2 x βH 2 CuR2 x γH
2

The value of K e2 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.

2.1.3.2. Ratio of chemical activity coefficients in aqueous phase

Depending on molar concentrations of species in aqueous phase, three cases are possible [5]:

- 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.

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

2.1.3.3. 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 [4].

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

2.1.4. Observations

Conclusion from preceding observations is that the value of thermodynamic equilibrium condition K e2
is a function of copper concentration in organic phase.

2.1.5. Mathematical relationship between the values of thermodynamic equilibrium
condition and copper concentration in organic phase

2.1.5.1. 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.
- 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 K e1 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 K e1 versus the values of copper concentration in organic phase.

Results show that:

- The values of thermodynamic equilibrium condition K e1 are not the same for steady-state positions of
equilibrium line.
- The value of thermodynamic equilibrium condition K e1 is a linear function of the value of copper
concentration in organic phase.

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- 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 Y is greater or lower than zero respectively.

Table 1: Value of K e1 from equilibrium line data of lab test 1

Lab test 1 Organic Aqueous
Aq Org
K e1
Free
Cu Cu Cu Cu Y C1 C2 H
Lix984N
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

Figure 1: Values of K e1 versus values of copper concentrations in organic phase of lab test 1

2.1.5.2. 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%.

Joseph Kafumbila Page 11
Table 3 gives equilibrium line data from which the values of thermodynamic equilibrium condition
K e1 of each steady-state position are calculated. Figure 2 gives the values of thermodynamic equilibrium
condition K e1 versus the value of copper concentration in organic phase.

Table 2: Element grades 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 4.68 0.53 0.97 1.58 1.64 0.46 .0.02 4.99

Table 3: Value of K e1 from equilibrium line data of lab test 2

Lab test 2 Organic Aqueous
Aq Org
K e1
Free
Cu Cu Cu Cu Y C1 C2 H
Lix984N
g/l g/l moles/l moles/l moles/l moles/l moles/l moles/l moles/l
0.07 1.72 0.027 0.553 0.001 -0.107 0.132 0.229 0.132 1.467
0.12 2.55 0.040 0.526 0.002 -0.107 0.131 0.230 0.131 1.323
0.19 3.36 0.053 0.501 0.003 -0.106 0.130 0.231 0.130 1.186
0.40 4.83 0.076 0.455 0.006 -0.105 0.127 0.234 0.127 0.945
1.55 7.36 0.116 0.375 0.024 -0.093 0.109 0.252 0.109 0.400
3.22 8.60 0.135 0.336 0.051 -0.073 0.083 0.279 0.083 0.161
4.34 8.88 0.140 0.327 0.068 -0.058 0.065 0.297 0.065 0.080

Figure 2: Values of K e1 versus values of copper concentration in organic phase of lab test 2

Results show that:

Joseph Kafumbila Page 12
- 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 Y is lower than zero.

- The value of thermodynamic equilibrium condition K e1 also is a linear function of the value of copper
concentration in organic phase.

2.1.5.3. Observations

In order to get closer to industrial conditions, only the range where molar concentrations Y are lower
than zero will be taken in simulation model. Hydrogen ion concentration in aqueous phase is given now by the
mathematical expression (22). The mathematical expression (23) gives sulfuric acid concentrations in aqueous
phase after copper solvent extraction.

e ACeaq
[Hor ]= (22)
98

e i
Acaq = Acaq + (Cuiaq - Cueaq) x 1,54 (23)

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.

2.1.6. Equilibrium line simulation model of extraction step

The substitution of the mathematical expressions (12), (13), (15) and (22) in the mathematical
expression (11) gives the mathematical expression (24) which gives the value of thermodynamic equilibrium
condition K1e1 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
K1e1 = Cueaq
aq
x [3.3030 x V%−3.0842 x Cue ]2
(24)
org

The value of thermodynamic equilibrium condition K1e1 obtained from the mathematical expression
(24) is plotted versus the values of copper concentration in organic phase in the range where the value of molar
concentration Y is lower than zero using pure copper sulfate aqueous phase. Table 4 gives equilibrium line data
of lab test 1, 3, 4 and 5. Figure 3 gives the value of thermodynamic equilibrium condition K1e1 versus the values
of copper concentration in organic phase. Results show that:

- Initial free acid concentration does not affect the value of line slope.
- The value of line slope is a function only of extractant volume percentage in organic phase.

Joseph Kafumbila Page 13
Line mathematical expression of thermodynamic equilibrium condition obtained from equilibrium line
data has a shape given by the mathematical expression (25).

K1e1 =D x Cueor + E (25)

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 i i i
Acaq 5 g/l Acaq 15 g/l Acaq 10 g/l Acaq 20 g/l
V% 20 % V% 20 % V% 15 % V% 15 %
Cueaq Cueor Cueaq Cueor Cueaq Cueor Cueaq Cueor
0.04 0.80 0.10 0.80 0.10 0.80 0.27 0.78
0.09 1.58 0.23 1.56 0.24 1.60 0.48 1.50
0.35 3.83 0.76 3.63 0.94 3.60 1.56 3.24
1.19 6.76 2.00 6.01 2.58 5.40 3.30 4.68
3.38 9.26 4.20 7.80 4.70 6.58 5.16 5.62
5.92 10.45 6.30 9.00 6.58 7.06 6.80 6.20
6.92 10.80 7.10 9.30

Figure 3: Values of K1 versus the values of copper concentrations in organic phase from equilibrium line data of
lab tests 1, 3, 4, and 5

The values of constants D and E are functions of extractant volume percentage. Mathematical
expressions giving the values of constants D and C are extrapolation curves of the value of constants D and C
obtained at different values of extractant volume percentage in the range of 8-32%. Equilibrium line simulation
model of extraction step is given by the mathematical expression (26). Thermodynamic equilibrium conditions
of K 2e1 and K1e1 given by the mathematical expressions (26) and (24) are equals for each steady-state position of
equilibrium line.

Joseph Kafumbila Page 14
K12 =(-28.511 x v%(−1.746) ) x Cueor+ 11.711 x v%(−0.646) (26)

2.2. Stripping step

2.2.1. 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 (g) which is the
reverse reaction of copper extraction chemical reaction.

CuR 2 + 2H + ↔ Cu2+ + 2HR (g)

The mathematical expression (27) gives the thermodynamic equilibrium condition.

[Cueor ] x [Heaq ]2 βCu x βHR 2 γ x γHR 2
= 2 x γ Cu 2= Ks (27)
[Cueaq ] x [HReor ]2 βCuR2 x βH CuR2 x γH

2.2.2. Simulation with equilibrium line model of extraction step

Thermodynamic equilibrium condition of extraction and stripping steps are similar. Equilibrium line
simulation model of extraction step is used to simulate equilibrium line of stripping step. Test conditions of lab
test 6 of stripping step are the following:

- Initial copper concentration in aqueous phase: 35 g/l
- Initial free acid concentration in aqueous phase: 180 g/l.
- Copper concentration in loaded organic: 15.98 g/l.
- Extractant: Lix984N.
- Extractant volume percentage in organic: 32%.

Table 5 gives equilibrium line data and the values of copper concentration in organic phase from
equilibrium line simulation model of extraction step. Figure 4 gives the values of copper concentration in
aqueous phase from equilibrium line data and Extraction step simulation model versus the values of copper
concentration in organic phase

Results show that there is a gap between the values of copper concentration from experimental data
and equilibrium line simulation model of extraction step. The gap is due probably to the difference of ionic
strength between extraction and stripping aqueous phases.

Joseph Kafumbila Page 15
Table 5: Copper concentration in organic simulated with extraction step simulation model

Equilibrium line data Model
Aqueous Organic Aqueous
Cu (g/l) Cu (g/l) Cu (g/l)
37.24 4.45 22.14
39.61 4.74 23.89
41.58 4.90 24.89
47.63 5.71 29.99
49.74 5.84 30.83
53.95 6.42 34.68

Figure 4: Copper concentration from equilibrium line data and Extraction step simulation model in aqueous
phase versus copper concentration in organic phase of lab test 6

2.2.3. Equilibrium line simulation model of stripping step

Table 6 gives equilibrium line data and the values of thermodynamic equilibrium condition K s1 of lab
test 6. Figure 5 gives the value of thermodynamic equilibrium condition K s1 versus the values of copper
concentration in organic phase.

Results show that:

Joseph Kafumbila Page 16
- The value of thermodynamic equilibrium condition K s1 is a linear function of the values of copper
concentration in organic phase.
- Accuracy of the value of thermodynamic equilibrium condition K s1 depends on accuracy in chemical
analysis of copper concentration in aqueous phase.
- The value of molar concentration Y is lower than zero. So, line slope is a function of extractant volume
percentage only. The values of K1s1 is given by the mathematical expression (28).

Cueorg [Aceaq ]2
K1s1 = x (28)
Cueaq [3.3030 x V%−3.0842 x Cueorg ]2

Table 6: Value of K s1 from equilibrium line data of lab test 6

Lab test 1 Organic Aqueous
Aq Org
K s1
Free
Cu Cu Cu Cu Y C1 C2 H
Lix984N
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 5: Values of K s1 versus the values of copper concentration in organic phase of lab test 6

Line mathematical expression of thermodynamic equilibrium condition obtained from equilibrium line
data has a shape given by the mathematical expression (29).

Joseph Kafumbila Page 17
K1s1 =F x Cueor + G (29)

The values of constants D and E are functions of extractant volume percentage. Mathematical
expressions giving the values of constants D and C are extrapolation curves of the value of constants D and C
obtained at different values of extractant volume percentage in the range 8-32%. Equilibrium line simulation
model of stripping step is given by the mathematical expression (30). Thermodynamic equilibrium conditions of
K 2s1 and K1s1 given by the mathematical expressions (30) and (28) are equals for each steady-state position of
equilibrium line.

K 2s1 =(4.8579 x 10−3x v% - 0.19183) x Cueor + 11.365 x v%(−0.85) (30)

Joseph Kafumbila Page 18
3. Equilibrium line and MacCabe Thiele diagram

3.1. Equilibrium line

3.1.1. Description

Equilibrium line gives the distribution of dissolved component, between two phases. In the case of
copper solvent extraction, it shows how copper distributes between aqueous and organic phases under the
different conditions experienced in the process. Equilibrium line data are obtained from lab test or by computer
modeling.

3.1.2. Computer modeling of equilibrium line

Thermodynamic equilibrium conditions given by the mathematical expressions (24) and (26) for
extraction step and by the mathematical expression (28) and (30) for stripping step are used for computer
modeling of extraction and stripping equilibrium lines respectively. Copper and free acid concentrations in initial
aqueous phase and also extractant volume percentage in organic phase are data which must be known for
computer modeling of equilibrium lines.

Thermodynamic equilibrium conditions K1e1 and K 2e1 for extraction step and K1s1 and K 2s1 for stripping
step are rearranged to have copper concentration in aqueous phase on one side and copper concentration in
organic phase on the other side. It appears two news equilibrium corrections α1 and α2 for extraction step and
π1 and π2 for stripping step. The mathematical expressions of news equilibrium corrections are given by the
mathematical expressions (31) and (32) for extraction step and (33) and (34) for stripping step. At the steady-
state, the equilibrium corrections α1 and α2 are equals for extraction step and π1 and π2 are equals for stripping
step.

[Aciaq +(Cuiaq −Cueaq ) x 1.54]2 (31)
α1 = Cueaq

[−28.511 x v%(−1.746) x Cueor +11.711 x v%(−0.646) ] x (3.303 x V%−3.0842 x Cueor )2 (32)
α2 = Cueor

[Aciaq +(Cuiaq −Cueaq ) x 1.54]2 (33)
π1 = Cueaq

[(4.8579 x 10−3 x v% − 0.19183) x Cueor +11.365 x v%(−0.85) ]x(3.303 x V% − 3.0842 x Cueor )2 (34)
π2 = Cueor

Joseph Kafumbila Page 19
There are two ways for computer modeling of equilibrium line. The first way is started from the
known value of copper concentration in aqueous phase from which copper concentration in organic phase is
calculated. Grouping of equilibrium corrections α1 and α2 of extraction step or π1 and π2 of stripping step gives
a cubic equation as a function of copper concentration in organic phase.

The second way is started from the known value of copper concentration in organic phase from which
copper concentration in aqueous phase is calculated. Grouping of equilibrium corrections α1 and α2 of extraction
step or π1 and π2 of stripping step gives a second-degree equation as a function of copper concentration in
aqueous phase.

For extraction step, the value of copper concentration in aqueous phase is given by the mathematical
expression (35) where the values of constants H and J are given by the mathematical expression (36) and (37).

−H−√H2 −4 x J
Cueaq = (35)
2

i
H = -1.299 x Acaq – 2 x Cuiaq – 0.422 x α2 (36)

i
J = (0.644 x Acaq + Cuiaq )2 (37)

For stripping step, the value of copper concentration in aqueous phase is given by the mathematical
expression (38) where the values of constants L and M are given by the mathematical expressions (39) and (40).

−L−√L2 −4 x M
Cueaq = 2
(38)

i
L = -1.299 x Acaq – 2 x Cuiaq – 0.422 x π2 (39)

i
M = (0.644 x Acaq + Cuiaq )2 (40)

3.1.3. Maximum loading

Maximum loading (ML) is the value of copper concentration in organic phase corresponding to the
value of initial copper concentration in aqueous phase on equilibrium line at the steady-state.

Maximum loading is a function of the values of copper and free acid concentrations in aqueous phase
and also extractant volume percentage in organic phase. The value of maximum loading is given by the first
away method for computer modeling of equilibrium line in which the value of copper concentration in aqueous
phase at steady-state is the value of initial copper concentration Cuiaq . The value of equilibrium correlation α1 is
changed to α1ML . The value of equilibrium correlation α1ML is given by the mathematical expression (41).

Joseph Kafumbila Page 20
[Aciaq ]2 (41)
α1ML = Cuiaq

3.1.4. Absolute maximum loading

Absolute maximum loading is the value of maximum loading when the value of initial free acid
concentration in aqueous phase is zero. Therefore, the values of equilibrium correlations α1 and α2 are also
zeros. The value of absolute maximum loading (AML) comes from equilibrium correlation α2 and is given by
the mathematical expression (42). The value of absolute maximum loading is not a linear function of extractant
volume percentage.

AML = 0.4108 x (V%)1.1 (42)

3.2. MacCabe Thiele diagram

3.2.1. Stage scheme of extraction and stripping steps

Extraction and stripping steps of copper solvent extraction are frequently carried out at industrial scale
with mixer-settlers. This equipment includes a mixer in one stage or two stages in series to disperse one phase
into other to provide interfacial contact for mass transfer, followed by a settler to allow phases to coalesce and
separate.

3.2.1.1. Extraction step

Figure 6 gives scheme of stage of rank ‘n’ of extraction step in cascade configuration. Stage of rank
n−1 n+1
‘n’ of extraction step receives aqueous phase Eaq from stage of rank ‘n-1’ and organic phase Eor from stage of
n n
rank ‘n+1’. Stage of rank ‘n’ produces aqueous phase Eaq and organic phase Eor .

Figure 6: Scheme of stage of rank ‘n’ of extraction step

Joseph Kafumbila Page 21
o
For cascade configuration containing ‘m’ stages, stage of rank ‘1’ receives PLS (Eaq ) and produces
1 m+1
Loaded organic LOe (Eor ). Stage of rank ‘m’ receives stripped organic SOe (Eor ) and produces raffinate Raf
m
(Eaq ).

3.2.1.2. Stripping step

Figure 7 gives scheme of stage of rank ‘n’ of stripping steps in cascade configuration. Stage of rank
n+1 n−1
‘n’ of stripping step receives aqueous phase Saq from stage of rank ‘n+1’ and organic phase Sor from stage of
n n
rank ‘n-1’. Stage of rank ‘n’ produces aqueous phase Saq and organic phase Sor .

0
For cascade configuration containing ‘p’ stages, stage of rank ‘1’ receives loaded organic LOs (Sor )
1 p+1
and produces advance electrolyte AD (Saq ). Stage of rank ‘p’ receives spent electrolyte SP (Saq ) and produces
p
stripped organic SOs (Sor ).

Figure 7: Scheme of stage of rank ‘n’ of stripping step

3.2.2. Parameters and designation

3.2.2.1. Stage of rank ‘n’

Each aqueous phase leaving stage of rank ‘n’ of extraction or stripping step is characterized by the
following independent parameters:

n
- Vaq : Flowrate (m3/h).

- Cunaq : Copper concentration (g/l).
n
- Acaq : Free acid concentration (g/l).
-
Each organic phase leaving stage of rank ‘n’ of extraction or stripping step is characterized by the
following independent parameters:

Joseph Kafumbila Page 22
n
- Vor : Flowrate (m3/h).
- Cunor : Copper concentration (g/l).
- v%n : Extractant volume percentage in organic phase (%).

The important parameters of stage of rank ‘n’ of extraction and stripping are:

- Ratios Rne and Rns are ratios of organic to aqueous flowrates of extraction and stripping stage of rank ‘n’
respectively.

- Parameters Mefen and Mefsn are respectively mixer efficiency of stage of rank ‘n’ of extraction and
stripping steps.

3.2.2.2. Cascade

The important parameters of cascade configuration are:

- Ratios Rce and Rcs are respectively ratios of organic to aqueous flowrates of extraction and stripping
cascade.
- Parameter v%c is extractant volume percentage in organic phase (%) of cascade.
- Parameters Effec and Effsc are respectively extraction and stripping efficiency of cascade.
- Parameter Cut is net copper transfer from organic phase to copper electrolyte per 1% of extractant
volume percentage of stripping cascade.

3.2.3. Mass balance

3.2.3.1. Extraction step

Stage of rank ‘n’

Conservation of copper mass flowrate at stage of rank ‘n’ is given by the mathematical expression
(43). The value of ratio Rne of stage of rank ‘n’ is given by the mathematical expression (44). The value of free
acid concentration in outlet aqueous phase of stage of rank ‘n’ is given the mathematical expression (45).

n
Vaq x Cun−1 n n+1 n n n n
aq + Vor x Cuor = Vaq x Cuaq + Vor x Cuor (43)

Vn Cun n−1
aq −Cuaq
Rne = Vnor = Cun+1 −Cun (44)
aq or or

n n−1
Acaq = Acaq + (Cun−1 n
aq - Cuaq ) x 1.54 (45)

Joseph Kafumbila Page 23
Cascade

Conservation of copper mass flowrate of cascade is given by the mathematical expression (46). The
value of ratio of Rce of cascade is given by the mathematical expression (47). The value of free acid
concentration in outlet aqueous phase of cascade is given by the mathematical expression (48). Copper
extraction efficiency of cascade is given by the mathematical expression (49).

c c c c
Vaq x PLS + Vor x SOe = Vaq x Raf + Vor x LOe (46)

Vc PLS−Raf
Rce = Vcor = LO (47)
aq e −SOe

m 0
Acaq = Acaq + (PLS-Raf) x 1.54 (48)

(PLS−Raf)
Effec = PLS
x 100 (49)

3.2.3.2. Stripping step

Stage of rank ‘n’

Conservation of copper mass flowrate of stage of rank ‘n’ is given by the mathematical expression
(50). The value of ratio Rns is given by the mathematical expression (51). The value of free acid concentration in
outlet aqueous phase of stage of rank ‘n’ is given by the mathematical expression (52).

n
Vor x Cun−1 n n+1 n n n n
or + Vaq x Cuaq = Vor x Cuor + Vaq x Cuaq (50)

Vn Cun n+1
aq −Cuaq
Rns = or
= (51)
Vn
aq Cun−1 n
or −Cuor

n n+1
Acaq = Acaq + (Cun+1 n
aq - Cuaq ) x 1.54 (52)

Cascade

Conservation of copper mass flowrate of cascade is given by the mathematical expression (53). The
value of ratio Rcs is given by the mathematical expression (54). The value of free acid concentration in outlet
aqueous phase of cascade is given by the mathematical expression (55). Copper stripping efficiency of cascade is
given by the mathematical expression (56). Net copper transfer from organic phase to aqueous phase is given by
the mathematical expression (57).

Joseph Kafumbila Page 24
c c c c
Vor x LOs + Vaq x SP = Vor x SOs + Vaq x AD (53)

Vc AD−SP
Rcs = Vcor = LO (54)
aq s −SOs

1 p+1 p+1
Acaq = Acaq + (Cuaq - Cu1aq) x 1.54 (55)

(LOs −SOs )
Effsc = LOs
x 100 (56)

(LOs −SOs ) AD−SP (57)
Cut = V%c
= V%c x Rc (g/l/v%)
s

3.2.4. MacCabe Thiele diagram

3.2.4.1. Extraction step

MacCabe Thiele diagram of stage of rank ‘n’ of extraction step is shown in Figure 8. The Point ‘An ’
gives feed coordinates, the Point ‘B n ’ gives outlet coordinates and the Point ‘C n ’ gives outlet equilibrium
coordinates. Triangle ‘E n B n – B n Dn – Dn E n ’ gives MacCabe Thiele diagram of stage of rank ‘n’ of extraction
step.

Slope of line ‘E n Dn ’ is given by the mathematical expression (58). Slope of line ‘An B n ’ is given by
the mathematical expression (59).

Cun n+1
or −Cuor 1
Slope ‘E n Dn ’= = (58)
Cuaq −Cun
n−1
aq Rne

Cun −Cun+1 1
Slope ‘An B n ’= Cunor −Cuor
n−1 = - Rn (59)
aq aq e

Copper concentrations in aqueous and organic phases, leaving stage of rank ‘n’ are given by the
mathematical expressions (60) and (61).

Mefn Mefn
Cunaq= Cun(aq/e) x 100
e
+ Cun−1
aq x (1- 100
e
) (60)

Mefn Mefn
Cunor= Cun(or/e) x 100
e
+ Cun+1
or x (1- 100
e
) (61)

Joseph Kafumbila Page 25
Figure 8: MacCabe Thiele diagram of stage of rank ‘n’ of extraction step

3.2.4.2. Stripping step

MacCabe Thiele diagram of stage of rank ‘n’ of stripping step is shown in Figure 9. The Point ‘An ’
gives feed coordinates, the Point ‘B n ’ gives outlet coordinates and the Point ‘C n ’ gives outlet equilibrium
coordinates. Triangle ‘Dn B n – B n E n – E n Dn ’ gives MacCabe Thiele diagram of stage of rank ‘n’ of stripping
step.

Slope of line ‘E n Dn ’ is given by the mathematical expression (62). Slope of line ‘An B n ’ is given by
the mathematical expression (63).

Cun−1 −Cun 1
Slope E n Dn = Cunor −Cun+1
or
= Rn (62)
aq aq s

Cun−1 −Cun 1
Slope An B n = Cun+1
or or
−Cun
= - Rn (63)
aq aq s

Copper concentrations in aqueous and organic phases, leaving stage of rank ‘n’ are given by the
mathematical expressions (64) and (65).

Mefn Mefn
Cunaq= Cun(aq/e) x 100
s
+ Cun+1
aq x (1- 100
s
) (64)

Joseph Kafumbila Page 26
Mefn Mefn
Cunor= Cun(or/e) x 100
s
+ Cun−1
or x (1- 100
s
) (65)

Figure 9: MacCabe diagram of stage of rank ‘n’ of stripping step

Joseph Kafumbila Page 27
4. Constraints of copper SX-EW plant

4.1. Equilibrium constraints between extraction and stripping steps

In copper solvent extraction plant having extraction step containing one or more cascades and
stripping step containing one or more cascades, equilibrium constraints between extraction and stripping steps
are given by the mathematical expressions (66) and (67).

LOe = LOs (66)

SOe = SOs (67)

4.2. Maximum value of extractant volume percentage

Organic phase is constituted with extractant and diluent. Extractant is organic compound which
extracts metal from aqueous phase. Diluent is organic liquid in which extractant is dissolved. In the industrial
practices, the maximum value of extractant volume percentage in organic phase in copper solvent extraction is
between 30 – 33% [6]. Organic phase viscosity increases with increasing of extractant volume percentage in
organic phase.

4.3. Free acid concentration in PLS

Free acid concentration in PLS depends on leaching technique. Free acid concentration in PLS can go
from 0.5 to 80 g/l.

4.4. Maximum free acid concentration in spent electrolyte

The value of maximum free acid concentration in spent electrolyte is 180 g/l. This value of maximum
free acid concentration is fixed by anode corrosion rate in EW circuit. It has been observed that increasing of
free acid concentration in copper electrolyte increases disconnection of PbO2 to Pb metallic. Therefore, it
increases anode corrosion rate [7].

Joseph Kafumbila Page 28
4.5. Minimum copper concentration in spent electrolyte

In copper EW circuit, limiting current density is current density beyond which copper powder is
produced. The value of limiting current density increases with increasing copper concentration in copper
electrolyte. Critical current density is current density beyond which copper cathode structure starts to be
granular. It has been observed that the value of critical current density is 35% of limiting current density [8].

The maximum value of current density in copper EW circuit is fixed by anode corrosion rate due to
oxygen evolution on anode. Evolution of oxygen gas on anode increases with increasing current density.
Increasing of oxygen evolution on anode also increases unhooking of PbO2 on anode. The maximum value of
current density, which allows to anodes to have a life of 5 years is 320 A/m2. In the presence of cobalt in copper
electrolyte at the level of 100 mg/l (cobalt stabilizes PbO2 on anode), the maximum value of current density can
reach 370 A/m2. The value of maximum current density must be lower than critical current density of copper
concentration in spent electrolyte. It has been observed that the minimum value of copper concentration in spent
electrolyte which respects this constraint is 30 g/l. In the industrial practice, the value of copper concentration in
spent electrolyte is varied between 30 and 35 g/l.

4.6. Maximum copper concentration in advance electrolyte

In the past time, ratio Rcs /Rce was fixed. This ratio is the enrichment factor of copper concentration
from leach solution to copper electrolyte. Under this condition, copper concentration in advance electrolyte
increases with increasing amount of copper transferred. The value of maximum copper concentration in advance
electrolyte is reached when copper concentration in loaded organic reaches the value of maximum loading (ML).
Copper concentration in advance electrolyte is given by the mathematical expression (68)

Rc
AD = SP + Rcs x (PLS – Raf) (68)
e

Currently, copper tankhouse consists of two parts; the first, called scavenger cells, is treating advance
electrolyte to oxidize soluble organic phase coming with advance electrolyte. The second, called commercial
cells, is treating mixture of outlet electrolyte from scavenger cells and recycled electrolyte from commercial
cells. Design of copper tankhouse is done such as flowrate of copper electrolyte to commercial cells is 4 times
greater than advance electrolyte flowrate to scavenger cells. This means that 20% of cells in copper tankhouse
work as scavenger cells. Maximum copper concentration drop across cell is fixed at 3 g/l because copper
electrolyte flowrate in conventional cell is fixed by cathode face velocity for a better quality of copper cathode
surface. In the industrial practice, cathode face velocity is 0.10 m3/hrs. per m2 of total cathode area in the cell [9].

Copper concentration in spent electrolyte is fixed at 35 g/l. In this condition, copper concentration
drop between spent and advance electrolytes is 15 g/l and maximum copper concentration in advance electrolyte

Joseph Kafumbila Page 29
is 50 g/l. These conditions give smallest size of copper tankhouse. The value of ratio Rcs is given by the
mathematical expression (69).

(AD−SP)
Rcs = Rce x (PLS−Raf) (69)

4.7. Optimum value of ratio of organic to aqueous of extraction step

Ratios Rce and Rcs are external ratios. Internal ratio is ratio of volume flowrates inside of mixer. When
the value of internal ratio (O/A) is greater than 1.1, aqueous phase is dispersed in organic phase. Mixer works in
organic continuity regime. On the other side, when ratio (A/O) is greater than 1.1, organic phase is dispersed in
aqueous phase. Mixer works in aqueous continuity regime. It has been observed that crud formation decreases
when mixer works in organic continuity regime [10]. Therefore, all mixers of extraction and stripping steps
work in organic continuity regime and the optimum value of ratio Rce is now 1.1 which gives smallest size of
mixer and settler without any organic or aqueous stage recycle.

4.8. Saturation ratio SR

Currently, saturation of organic phase with copper (high value of (LO/ML) is important parameter in
design of copper solvent extraction plant. This parameter takes into account good use of organic phase (high
value of Net copper transfer) and also rejection of iron from organic phase.

In copper solvent extraction, iron is transferred to copper electrowinning circuit by physical
entrainment. In addition, Ferric is transferred by chemical entrainment. Studies on iron transfer show that the
average of iron chemical entrainment is between 35 to 60% of total entrainment [11]. Iron presence in copper
electrolyte causes reduction of current efficiency. Maximum iron concentration in copper electrolyte is 2.5g/l
which will give current efficiency greater than 90%. Copper electrolyte bleed is used to maintain this iron level
in electrolyte. Increasing of flowrate of copper electrolyte bleed increases cost of cobalt reagent which is added
to copper EW circuit.

In all copper solvent extraction plants having cascade configuration with two stages to extraction step,
it has been observed that iron concentration in loaded organic out of stage of rank 1 is lower than iron
concentration in partially loaded organic out of stage of rank 2. This effect is called ‘crowding’ [11].

LO
The value of ratio ( ) is a new constraint called saturation ratio ‘SR’. This constraint is applicable to
ML

all copper solvent extraction configurations (2Ex1S, 2Ex2S, 3Ex1S, series-parallel, interlaced, double series-
parallel and others). The mathematical expression (70) gives the value of saturation ratio.

Joseph Kafumbila Page 30
LO
SR = x 100 (%) (70)
ML

Joseph Kafumbila Page 31
5. Simulation program using Excel solver
program

5.1. Description

Simulation program is done on Excel spreadsheet in format of Excel solver program. 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.

First step of static simulation program design is creation of simulation program table on Excel
spreadsheet. Simulation program table is made with three small tables which are table of extraction step, table of
stripping step, and table of simulation program constraint. In simulation program table, data have red color,
solver constraints have blue color and solver constraints have green color.

There are two static simulation program options for each copper solvent extraction configuration. For
each option of each copper solvent extraction configuration, there is a static simulation program table. Two
options are:

- Option 1: Unknown parameter in copper solvent extraction simulation program is extractant volume
percentage in organic phase. This static simulation program is for designer of copper solvent extraction
configuration.

- Option 2: Unknown parameters in copper solvent extraction simulation program are extractant volume
percentage, saturation ratio, and mixer efficiencies of extraction and stripping steps for existing plant.
This simulation program is for plant metallurgist.

5.2. Static simulation program design

5.2.1. General

In this book for good understanding, static simulation program design will be done step by step using
a conventional configuration containing two stages in cascade to extraction step and two stages in cascade to
stripping step as an example.

Joseph Kafumbila Page 32
5.2.2. Option 1

. In this option, unknown parameter is extractant volume percentage. Table 7 gives data of chosen
example for explanation of simulation program conception.

Table7: 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 PLS Cu g/l 7
Acid concentration in PLS PLS Ac g/l 1.96
Ratio O/A Rce 1.1
Saturation ratio SR % 80
Number of extraction stage 2
Stage of rank 1 mixer efficiency Mefe1 % 92
Stage of rank 2 mixer efficiency Mefe2 % 95
Stripping step
Copper concentration in spent electrolyte SP Cu g/l 35
Acid concentration in spent electrolyte SP Ac g/l 180
Copper concentration in advance electrolyte AD Cu g/l 50
Number of stripping stage 2
Stage of rank 1 mixer efficiency Mefs1 % 98
Stage of rank 2 mixer efficiency Mefs2 % 85

Static simulation program table of option 1 of 2Ex2S configuration is given in Table 8 as it appears on
Excel Microsoft spreadsheet. Data from Table 7 have red color.

In extraction table, designation αn2 , H n and J n are respectively the values of equilibrium correlation ?2
and constants H and J of stage of rank ‘n’ for calculating the value of copper concentration in aqueous phase
from the value of copper concentration in organic phase. Designation An , C n , Dn and E n are the Points A, B, C,
and D from extraction step MacCabe Thiele diagram of stage of rank ‘n’.

In stripping table, designation πn2 , Ln and M n are respectively the values of equilibrium correlation ?2
and constants L and M of stage of rank ‘n’ for calculating the value of copper concentration in aqueous phase
from the value of copper concentration in organic phase. Designation An , C n , Dn and E n are the Points A, B, C,
and D from stripping step MacCabe Thiele diagram of stage of rank ‘n’.

5.2.2.1. Extraction step

Data

Simulation program design is started with solver variables of data. These solver variables will be data
of all mathematical expressions of extraction step.

Joseph Kafumbila Page 33
- In the cell ‘F6’ of solver variable of PLS flowrate (PLS flow), enter the number giving the value of PLS
flowrate data that is in the cell ‘C6’.
- In the cell ‘F7’ of solver variable of PLS copper concentration (PLS Cu), enter the number giving the value
of PLS copper concentration data that is in the cell ‘C7’.
- In the cell ‘F8’ of solver variable of PLS free acid concentration (PLS Ac), enter the number giving the
value of PLS acid concentration data that is in the cell ‘C8’.
- In the cell ‘F9’ of solver variable of saturation ratio (SR), enter the number giving the value of saturation
ratio data that is in the cell ‘C9’.
- In the cell ‘F10’ of solver variable of ratio (Rce ), enter the number giving the value of ratio (Rce ) data that is
in the cell ‘C10’.
- In the cell ‘F11’ of solver variable of mixer efficiency ( Mefe1 ), enter the number giving the value of mixer
efficiency ( Mefe1 ) that is in the cell ‘C11’.
- In the cell ‘F12’ of solver variable of mixer efficiency (Mefe2 ), enter the number giving the value of mixer
efficiency (Mefe2 ) that is in the cell ‘C12’.

Solver constraints of solver variables of extraction step data are the following:

- In the cell ‘I6’, enter formula: ‘=F6-C6’.
- In the cell ‘I7’, enter formula: ‘=F7-C7’.
- In the cell ‘I8’, enter formula: ‘=F8-C8’.
- In the cell ‘I9’, enter formula: ‘=F9-C9’.
- In the cell ‘I10’, enter formula: ‘=F10-C10’.
- In the cell ‘I11’, enter formula: ‘=F11-C11’.
- In the cell ‘I12’, enter formula: ‘=F12-C12’.

Starting value

The starting value of extractant volume percentage of simulation program is random number between
1 and 32%. The starting value of extractant volume percentage is used in all mathematical expression of
extraction step as extraction volume percentage data. The optimum value of extractant volume percentage is
known at the end of simulation program by running Excel Solver program. The starting value of extractant
volume percentage is the expected value of extractant volume percentage for those who have experience. For this
case, chosen starting value is 25%.

- In the cell ‘F15’, enter the number ‘25’.

General

The value of organic flowrate is in the cell ‘C18’. This value is given by the mathematical expression
(47) where the values of ratio (Rce ) is in the cell ‘F10’ and PLS flowrate is in the cell ‘F6’.

Joseph Kafumbila Page 34
- In the cell ‘C18’, enter formula: ‘=F10*F6’.

The value of absolute maximum loading is in the cell ‘C19’. This value is given by the mathematical
expression (42) where the value of extractant volume percentage is in the cell ‘F15’.

- In the cell ‘C19’, enter formula: ‘=0.4108*F15^(1.1)’.

The value of maximum loading is solver variable because resolution of cubic equation is complicated.
The value of maximum loading is in the cell ‘F21’. The starting value of maximum loading is the value of
absolute maximum loading.

- In the cell ‘F21’, enter the number ’14.170’.

Solver constraint of the value of maximum loading is that the values of equilibrium correlations α1ML
and α2 must be equals. Solver constraint of the value of maximum loading is in the cell ‘I21’. The value of
equilibrium correlation α1ML is in the cell ‘B21’ and is given by the mathematical expression (41). The value of
equilibrium correlation α2 is in the cell ‘C21’ and is given by the mathematical expression (32) where the value
of copper concentration in organic phase at the steady-state is the value of maximum loading.

- In the cell ‘B21’, enter formula: ‘=F8^2/F7’.
- In the cell ‘C21’, enter formula: ‘=((-28.511*F15^(-1.746)*F21+11.711*F15^(-0.646))*(3.303*F15-
3.0842*F21)^2)/F21’.
- In the cell ‘I21’, enter formula: ‘=B21-C21’.

Extraction stage 1

The value of copper concentration in organic phase of the Point E1 is in the cell ‘C28’ and is the value
of loaded organic. The value of loaded organic is given by the mathematical expression (70) where the values of
saturation ratio (SR) is in the cell ‘F9’ and the value of maximum loading is in the cell ‘F21’.

- In cell ‘C28’, enter formula: ‘=F9*F21/100’.

The value of copper concentration in aqueous phase of the Point E1 is in the cell ‘D28’ and is the
value of copper concentration in PLS which is in the cell ‘F7’.

- In the cell ‘D28’, enter formula: ‘=F7’

The value of copper concentration in organic phase of the Point C1 is solver variable and is in the cell
‘F29’. In the cell ‘F29’, enter a random number between the values of copper concentration in organic phase of

Joseph Kafumbila Page 35
the Point E1 and the value of maximum loading. The starting value of copper concentration in organic phase of
the Point C1 is the first whole number above the value of copper concentration in organic phase of the Point E1 .
In this case, a random number is 12.

- In the Cell ‘F29’, enter the number ‘12’.
- In the cell ‘C29’, enter formula: ‘=F29’

The value of copper concentration in aqueous phase of the Point C1 is in the cell ‘D29’. This value is
given by the mathematical expression (35) where the value of constant H1 is in the cell ‘C26’ and the value of
constant J1 is in the cell ‘D26’. The value of constant H1 is given by the mathematical expression (36) where the
value of initial free acid concentration is in the cell ‘F8’, the value of initial copper concentration is in the cell
‘F7’, and the value of equilibrium correlation α12 is in the cell ‘B26’. The value of equilibrium correlation α12 is
given by the mathematical expression (32) where the value of extractant volume percentage is in the cell ‘F15’
and the value of copper concentration in organic phase is in the cell ‘C29’.

- In the cell ‘B26’, enter formula: ‘=((-28.511*F15^(-1.746)*C29+11.711*F15^(-0.646))*(3.303*F15-
3.0842*C29)^(2))/C29’.
- In the cell ‘C26’, enter formula: ‘=-1.299*F8-2*F7-0.422*B26’.

The value of constant J1 is given by the mathematical expression (37) where initial free acid
concentration is in the cell ‘F8’ and initial copper concentration is in the cell ‘F7’.

- In the cell ‘D26’, enter formula: ‘=(0.644*F8+F7)^(2)’.
- In the cell ‘D29’, enter formula: ‘=[-C26-(C26^(2)-4*D26)^(0.5)]/2’.

. The values of copper concentrations in aqueous phase of the Points E1 and A1 are equals. The value
of copper concentration in aqueous phase of the Point A1 is in the cell ‘D32’.

- In the cell ‘D32’, enter formula: ‘=D28’.

The value of copper concentration in aqueous phase of the Point B1 is in the cell ‘D30’. This value is
given by the mathematical expression (60) where the value of Cu1(aq/e) is the value of copper concentration in
aqueous phase of the Point C1 , the value of Cu0aq is the value of copper concentration in aqueous phase of the
Point A1 and the value of mixer efficiency of stage of rank 1 is in the cell ‘F11’.

- In the ‘D30’, enter formula: ‘=D29*F11/100 + D32*(1-F11/100)’.

The value of copper concentration in organic phase of the Point B1 is in the cell ‘C30’. This value is
given by the mathematical expression (59) where the value of ratio (Rce ) is in the cell ‘F10’, the value of Cu1or is

Joseph Kafumbila Page 36
the value of copper concentration in organic phase of the Point B1 , the value of Cu2or is changed by the value of
Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu1aq is the value
of copper concentration in aqueous phase of the Point B1 and the value of Cu0aq is changed by the value of
Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 .

- In the cell ‘C30’, enter formula: ‘=C29+(1/F10)*(D29-D30)’.

The value of copper concentration in organic phase of the Point A1 is in the cell ‘C32’. This value is
given by the mathematical (59) where the value of ratio (Rce ) is in the cell ‘F10’, the value of Cu1or is changed by
the value of Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu2or
is the value of copper concentration in organic phase of the Point A1 , the value of Cu1aq is changed by the value
of Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 and the value of Cu0aq is
the value of copper concentration in aqueous phase of the Point A1 .

- In the cell ‘C32’, enter formula: ‘=C29+(1/F10)*(D29-D32)’.

The values of copper concentrations in organic phase of the Points D1 and A1 are equals. The value of
copper concentration in organic phase of the Point D1 is in the cell ‘C31’.

- In the cell ‘C31’, enter formula: ‘=C32’.

The values of copper concentration in aqueous phase of the Points B1 and D1 are equals. The value of
copper concentration in aqueous phase of the Point D1 is in the cell ‘D31’.

- In the cell ‘D31’, enter formula: ‘=D30’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C1 is that the value of copper concentrations in organic phase of the Points B1 and E1 must be equals. The
value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I29’.

- In the cell ‘I29’, enter formula: ‘=C30-C28’.

Extraction stage 2

The value of copper concentration in organic phase of the Point E 2 is in the cell ‘C38’. This value is
the value of copper concentration in organic phase of the Point D1 .

- In the cell ‘C38’, enter formula: ‘=C31’.

Joseph Kafumbila Page 37
The value of copper concentration in aqueous phase of the Point E 2 is in the cell ‘D38’. This value is
the value of copper concentration in aqueous phase of the Point D1 .

- In the cell ‘D38’, enter formula: ‘=D31’

The value of copper concentration in organic phase of the Point C 2 is solver variable. This value is in
the cell ‘F39’. In the cell ‘F39’, enter a random number between the values of copper concentration in organic
phase of the Point E 2 and the value of copper concentration in organic phase of the Point C1 . The starting value
of copper concentration in organic phase of the Point C 2 is the first whole number above the value of copper
concentration in organic phase of the Point E 2 . In this case, the random number is 8.

- In the Cell ‘F39’, enter number ‘8’.
- In the cell ‘C39’, enter formula: ‘=F39’

The value of copper concentration in aqueous phase of the Point C 2 is in the cell ‘D39’. This value is
given by the mathematical expression (35) where the value of constant H 2 is in the cell ‘C36’ and the value of
constant J 2 is in the cell ‘D36’. The value of constant H 2 is given by the mathematical expression (36) where the
value of initial free acid concentration is in the cell ‘F8’, the value of initial copper concentration is in the cell
‘F7’, and the value of equilibrium correlation α22 is in the cell ‘B36’. The value of equilibrium correlation α22 is
given by the mathematical expression (32) where the value of extractant volume percentage is in the cell ‘F15’
and the value of copper concentration in organic phase is in the cell ‘C39’.

- In the cell ‘B36’, enter formula: ‘=((-28.511*F15^(-1.746)*C39+11.711*F15^(-0.646))*(3.303*F15-
3.0842*C39)^(2))/C39’.
- In the cell ‘C36’, enter formula: ‘=-1.299*F8-2*F7-0.422*B36’.

The value of constant J 2 is given by the mathematical expression (37) where initial free acid
concentration is in the cell ‘F8’ and initial copper concentration is in the cell ‘F7’.

- In the cell ‘D36’, enter formula: ‘=(0.644*F8+F7)^(2)’.
- In the cell ‘D39’, enter formula: ‘=[-C36-(C36^(2)-4*D36)^(0.5)]/2’.

. The values of copper concentrations in aqueous phase of the Points E 2 and A2 are equals. The value
of copper concentration in aqueous phase of the Point A2 is in the cell ‘D42’.

- In the cell ‘D42’, enter formula: ‘=D38’.

The value of copper concentration in aqueous phase of the Point B 2 is in the cell ‘D40’. This value is
given by the mathematical expression (60) where the value of Cu2(aq/e) is the value of copper concentration in

Joseph Kafumbila Page 38
aqueous phase of the Point C 2 , the value of Cu1aq is the value of copper concentration in aqueous phase of the
Point A2 and the value of mixer efficiency of stage of rank 2 is in the cell ‘F12’.

- In the ‘D40’, enter formula: ‘=D39*F12/100 + D42*(1-F12/100)’.

The value of copper concentration in organic phase of the Point B 2 is in the cell ‘C40’. This value is
given by the mathematical expression (59) where the value of ratio (Rce ) is in the cell ‘F10’, the value of Cu2or is
the value of copper concentration in organic phase of the Point B 2 , the value of Cu3or is changed by the value of
Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu2aq is the value
of copper concentration in aqueous phase of the Point B 2 and the value of Cu1aq is changed by the value of
Cu2aq/e which is the value of copper concentration in aqueous phase of the Point C 2 .

- In the cell ‘C40’, enter formula: ‘=C39+(1/F10)*(D39-D40)’.

The value of copper concentration in organic phase of the Point A2 is in the cell ‘C42’. This value is
given by the mathematical (59) where the value of ratio (Rce ) is in the cell ‘F10’, the value of Cu2or is changed by
the value of Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu3or
is the value of copper concentration in organic phase of the Point A2 , the value of Cu2aq is changed by the value
of Cu2aq/e which is the value of copper concentration in aqueous phase of the Point C 2 and the value of Cu1aq is
the value of copper concentration in aqueous phase of the Point A2 .

- In the cell ‘C42’, enter formula: ‘=C39+(1/F10)*(D39-D42)’.

The values of copper concentrations in organic phase of the Points D2 and A2 are equals. The value of
copper concentration in organic phase of the Point D2 is in the cell ‘C41’.

- In the cell ‘C41’, enter formula: ‘=C42’.

The values of copper concentration in aqueous phase of the Points B 2 and D2 are equals. The value of
copper concentration in aqueous phase of the Point D2 is in the cell ‘D41’.

- In the cell ‘D41’, enter formula: ‘=D40’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C 2 is that the value of copper concentrations in organic phase of the Points B 2 and E 2 must be equals. The
value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I39’.

- In the cell ‘I39’, enter formula: ‘=C40-C38’.

Joseph Kafumbila Page 39
Performance

The value of free acid concentration in raffinate is in the cell ‘C45’. This value is given by the
0
mathematical expression (48) where the value of Acaq is in the cell ‘F8’, the value of PLS is in the cell ‘F7’ and
the value of Raf is in the cell ‘D41’.

- In the cell ‘C45’, enter formula: ‘=F8 + (F7-D41)*1.54’.

The value of copper extraction efficiency is in the cell ‘C46’. This value is given by the mathematical
expression (49) where the value of PLS is in the cell ‘F7’ and the value of Raf is in the cell ‘D41’.

- In the cell ‘C46’, enter formula: ‘=(F7-D41)/F7*100’

5.2.2.2. Stripping step

Data

Design of simulation program is started with solver variables of stripping step data. These solver
variables will be data of all mathematical expressions of stripping step.

- In the cell ‘F52’ of solver variable of spent electrolyte copper concentration (SP Cu), enter the number
giving the value of spent electrolyte copper concentration data that is in the cell ‘C52’.
- In the cell ‘F53’ of solver variable of spent electrolyte free acid concentration (SP Ac), enter the number
giving the value of spent electrolyte free acid concentration data that is in the cell ‘C53’.
- In the cell ‘F54’ of solver variable of advance electrolyte copper concentration (AD Cu), enter the number
giving the value of advance electrolyte copper concentration data that is in the cell ‘C54’.
- In the cell ‘F55’ of solver variable of mixer efficiency of stage of rank 1 (Mefs1 ), enter the number giving
the value of stage of rank 1 mixer efficiency data that is in the cell ‘C55’.
- In the cell ‘F56’ of solver variable of mixer efficiency of stage of rank 2 (Mefs2 ), enter the number giving
the value of stage of rank 2 the mixer efficiency data that is in the cell ‘C56’.

Solver constraints of solver variables of data of stripping step are the following:

- In the cell ‘I52’, enter formula ‘=F52-C52’.
- In the cell ‘I53’, enter formula ‘=F53-C53’.
- In the cell ‘I54’, enter formula ‘=F54-C54’.
- In the cell ‘I55’, enter formula ‘=F55-C55’.
- In the cell ‘I56’, enter formula ‘=F56-C56’.

Joseph Kafumbila Page 40
General

The value of ratio (Rcs ) is in the cell ‘C59’. This value is given by the mathematical expression (54)
where value of AD is in the cell ‘F54’, the value of SP is in the cell ‘F52’, the value of LOs is changed by the
value of LOe which is in the cell ‘C28’ and the value of SOs is changed by the value of SOe which is in the cell
‘C41’. These changes follow the mathematical expressions (66) and (67).

- In the cell ‘C59’, enter formula: ‘=(F54-F52)/(C28-C41)’.

The value of spent electrolyte flowrate is in the cell ‘C60’. This value is given by the mathematical
expression (54) where the value of ratio (Rcs ) is in the cell ‘C59’ and the value of organic flowrate is in the cell
‘C18’.

- In the cell ‘C60’, enter formula: ‘=C18/C59’.

Stripping stage 1

The value of copper concentration in organic phase of the Point D1 is in the cell ‘C66’. This value is
the value of copper concentration in organic phase of the Point E1 of extraction step (loaded organic).

- In the cell ‘C66’, enter formula: ‘=C28’

The value of copper concentration in aqueous phase of the Point D1 is in the cell ‘D66’. This value is
the advance electrolyte copper concentration which is in the cell ‘F54’.

- In the cell ‘D66’, enter formula: ‘=F54’

The value of copper concentration in organic phase of the Point C1 is solver variable and is in the cell
‘F67’. The starting value of copper concentration in organic phase of the Point C1 is half the value of copper
concentration in organic phase of the Point D1 . In this case, half the value is 5.668.

- In the Cell ‘F67’, enter number ‘5.668’.
- In the cell ‘C67’, enter formula: ‘=F67’

The value of copper concentration in aqueous phase of the Point C1 is in the cell ‘D67’. This value is
given by the mathematical expression (38) where the value of constant L1 is in the cell ‘C64’ and the value of
constant M1 is in the cell ‘D64’. The value of constant L1 is given by the mathematical expression (39) where the
value of initial free acid concentration is in the cell ‘F53’, the value of initial copper concentration is in the cell
‘F52’, and the value of equilibrium correlation π12 is in the cell ‘B64’. The value of equilibrium correlation π12 is

Joseph Kafumbila Page 41
given by the mathematical expression (34) where the value of extractant volume percentage is in the cell ‘F15’
and the value of copper concentration in organic phase is in the cell ‘C67’.

- In the cell ‘B64’, enter formula: ‘=(((4.8579*10^(-3)*F15-0.19183)*C67+11.365*F15^(-
0.85))*(3.303*F15-3.0842*C67)^(2))/C67’.
- In the cell ‘C64’, enter formula: ‘=-1.299*F53-2*F52-0.422*B64’.

The value of constant M1 is given by the mathematical expression (40) where initial free acid
concentration is in the cell ‘F53’ and initial copper concentration is in the cell ‘F52’.

- In the cell ‘D64’, enter formula: ‘=(0.644*F53+F52)^(2)’.
- In the cell ‘D67’, enter formula: ‘=[-C64-(C64^(2)-4*D64)^(0.5)]/2’.

. The values of copper concentrations in organic phase of the Points D1 and A1 are equals. The value
of copper concentration in organic phase of the Point A1 is in the cell ‘C70’.

- In the cell ‘C70’, enter formula: ‘=C66’.

The value of copper concentration in organic phase of the Point B1 is in the cell ‘C68’. This value is
given by the mathematical expression (65) where the value of Cu1(or/e) is the value of copper concentration in
organic phase of the Point C1 , the value of Cu0or is the value of copper concentration in organic phase of the Point
A1 and the value of mixer efficiency of stage of rank 1 is in the cell ‘F55’.

- In the ‘C68’, enter formula: ‘=C67*F55/100 + C70*(1-F55/100)’.

The value of copper concentration in aqueous phase of the Point B1 is in the cell ‘D68’. This value is
given by the mathematical expression (63) where the value of ratio (Rc? ) is in the cell ‘C59’, the value of Cu1or is
the value of copper concentration in organic phase of the Point B1 , the value of Cu0or is changed by the value of
Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu1aq is the value
of copper concentration in aqueous phase of the Point B1 and the value of Cu2aq is changed by the value of
Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 .

- In the cell ‘D68’, enter formula: ‘=D67-C59*(C68-C67)’.

The value of copper concentration in aqueous phase of the Point A1 is in the cell ‘D70’. This value is
given by the mathematical (63) where the value of ratio (Rce ) is in the cell ‘F59’, the value of Cu1or is changed by
the value of Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu0or
is the value of copper concentration in organic phase of the Point A1 , the value of Cu1aq is changed by the value

Joseph Kafumbila Page 42
of Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 and the value of Cu2aq is
the value of copper concentration in aqueous phase of the Point A1 .

- In the cell ‘D70’, enter formula: ‘=D67-C59*(C70-C67)’.

The values of copper concentrations in aqueous phase of the Points E1 and A1 are equals. The value of
copper concentration in organic phase of the Point E1 is in the cell ‘D69’.

- In the cell ‘D69’, enter formula: ‘=D70’.

The values of copper concentration in organic phase of the Points B1 and E1 are equals. The value of
copper concentration in aqueous phase of the Point E1 is in the cell ‘C69’.

- In the cell ‘C69’, enter formula: ‘=C68’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C1 is that the value of copper concentrations in aqueous phase of the Points B1 and D1 must be equals. The
value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I67’.

- In the cell ‘I67’, enter formula: ‘=D68-D66’.

Stripping stage 2

The value of copper concentration in organic phase of the Points D2 and E1 are equals. The value of
copper concentration in organic phase of the Point D2 is in the cell ‘C76’

- In the cell ‘C76’, enter formula: ‘=C69’.

The value of copper concentration in aqueous phase of the Points D2 and E1 are equals. The value of
copper concentration in aqueous phase of the Point D2 is in the cell ‘D76’

- In the cell ‘D76’, enter formula: ‘=D69’

The value of copper concentration in organic phase of the Point C 2 is solver variable and is in the cell
‘F77’. The starting value of copper concentration in organic phase of the Point C 2 is two-thirds the value of
copper concentration in organic phase of the Point D2 . In this case, two-thirds the value is 3.854.

- In the Cell ‘F77’, enter the number ‘3.854’.
- In the cell ‘C77’, enter formula: ‘=F77’

Joseph Kafumbila Page 43
The value of copper concentration in aqueous phase of the Point C 2 is in the cell ‘D77’. This value is
given by the mathematical expression (38) where the value of constant L2 is in the cell ‘C74’ and the value of
constant M 2 is in the cell ‘D74’. The value of constant L2 is given by the mathematical expression (39) where the
value of initial free acid concentration is in the cell ‘F53’, the value of initial copper concentration is in the cell
‘F52’, and the value of equilibrium correlation π22 is in the cell ‘B74’. The value of equilibrium correlation π22 is
given by the mathematical expression (34) where the value of extractant volume percentage is in the cell ‘F15’
and the value of copper concentration in organic phase is in the cell ‘C77’.

- In the cell ‘B74’, enter formula: ‘=(((4.8579*10^(-3)*F15-0.19183)*C77+11.365*F15^(-
0.85))*(3.303*F15-3.0842*C77)^(2))/C77’.
- In the cell ‘C74’, enter formula: ‘=-1.299*F53-2*F52-0.422*B74’.

The value of constant M 2 is given by the mathematical expression (40) where initial free acid
concentration is in the cell ‘F53’ and initial copper concentration is in the cell ‘F52’.

- In the cell ‘D74’, enter formula: ‘=(0.644*F53+F52)^(2)’.
- In the cell ‘D77’, enter formula: ‘=[-C74-(C74^(2)-4*D74)^(0.5)]/2’.

. The values of copper concentrations in organic phase of the Points D2 and A2 are equals. The value
of copper concentration in organic phase of the Point A2 is in the cell ‘C80’.

- In the cell ‘C80’, enter formula: ‘=C76’.

The value of copper concentration in organic phase of the Point B 2 is in the cell ‘C78’. It is given by
the mathematical expression (65) where the value of Cu2(or/e) is the value of copper concentration in organic
phase of the Point C 2 , the value of Cu1or is the value of copper concentration in organic phase of the Point A2 and
the value of mixer efficiency of stage of rank 2 is in the cell ‘F56’.

- In the ‘C78’, enter formula: ‘=C77*F56/100 + C80*(1-F56/100)’.

The value of copper concentration in aqueous phase of the Point B 2 is in the cell ‘D78’. This value is
given by the mathematical expression (63) where the value of ratio (Rc? ) is in the cell ‘C59’, the value of Cu2or is
the value of copper concentration in organic phase of the Point B 2 , the value of Cu1or is changed by the value of
Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu2aq is the value
of copper concentration in aqueous phase of the Point B 2 and the value of Cu3aq is changed by the value of
Cu2aq/e which is value of copper concentration in aqueous phase of the Point C 2 .

- In the cell ‘D78’, enter formula: ‘=D77-C59*(C78-C77)’.

Joseph Kafumbila Page 44
The value of copper concentration in aqueous phase of the Point A2 is in the cell ‘D80’. This value is
given by the mathematical (63) where the value of ratio (Rce ) is in the cell ‘F59’, the value of Cu2or is changed by
the value of Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu1or
is the value of copper concentration in organic phase of the Point A2 , the value of Cu2aq is changed by the value
of Cu2aq/e which is the value of copper concentration in aqueous phase of the Point C 2 and the value of Cu3aq is
the value of copper concentration in aqueous phase of the Point A2 .

- In the cell ‘D80’, enter formula: ‘=D77-C59*(C80-C77)’.

The values of copper concentrations in aqueous phase of the Points E 2 and A2 are equals. The value of
copper concentration in organic phase of the Point E 2 is in the cell ‘D79’.

- In the cell ‘D79’, enter formula: ‘=D80’.

The values of copper concentration in organic phase of the Points B 2 and E 2 are equals. The value of
copper concentration in aqueous phase of the Point E 2 is in the cell ‘C79’.

- In the cell ‘C79’, enter formula: ‘=C78’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C is that the value of copper concentrations in aqueous phase of the Points B 2 and D2 must be equals. The
2

value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I77’.

- In the cell ‘I77’, enter formula: ‘=D78-D76’.

Performance

The value of stripping copper efficiency is in the cell ‘C83’. This value is given by the mathematical
expression (56) where the value of LOs is in the cell ‘C66’ and the value of SOs is in the cell ‘C79’.

- In the cell ‘C83’, enter formula: ‘=(C66-C79)/C66*100’

The value of net copper transfer is in the cell ‘C84’. This value is given by the mathematical
expression (57) where the value of LOs is in the cell ‘C66’, the value of SOs is in the cell ‘C79’ and the value of
the extractant volume percentage is in the cell ‘F15’.

- In the cell ‘C84’, enter formula: ‘=(C66-C79)/F15’

Joseph Kafumbila Page 45
5.2.2.3. Simulation program constraint

The value of simulation program constraint is in the cell ‘I88’. Simulation program constraint is that
copper concentrations in stripped organic of extraction and stripping steps must be equals. This simulation
program constraint is the set objective of Excel solver program.

- In the cell ‘I88’, entre formula: ‘=C79-C41’

At this level, it appears Table 9 as it appears on Excel Microsoft spreadsheet. Table 9 gives results of
static simulation program with the starting values of extractant volume percentage, maximum loading, copper
concentration in organic phase of the Points C1 and C 2 of extraction step, and copper concentration in the organic
phase of the Points C1 and C 2 of stripping step. Solver variables have blue color and solver constraints have
green color.

5.2.2.4. 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 ‘I88’ 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 reference for each solver variable (in blue color in
Table 9). Separate 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 cell reference of PLS flowrate solver constraint (in green
color in Table 9).
c. Click the ‘relationship’ ‘=’, in the ‘Constraint’ box, type the number ‘0’.
d. Click ‘Add’ for the second solver constraint. When the last solver constraint is added (cell
‘I77’), 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’.

At this level, it appears Table 10 as it appears on Excel Microsoft spreadsheet. Table 10 gives results
of static simulation program with the optimum values of extractant volume percentage, maximum loading,
copper concentration in organic phase of the Points C1 and C 2 of extraction step, and copper concentration in the
organic phase of the Points C1 and C 2 of stripping step.

Joseph Kafumbila Page 46
A B C D E F G H I J
1
2 Table 8 Simulation program table for option 1 (part 1)
3
4 Extraction step
5 Data Solver variables Solver constraints
6 PLSflow 400 m3/h PLSflow m3/h PLSflow
7 PLS Cu 7.00 g/l PLS Cu g/l PLS Cu
8 PLS Ac 1.96 g/l PLS Ac g/l PLS Ac
9 SR 80 % SR % SR
10 Rce 1.1 Rce Rce
11 Mefe1 92 % Mefe1 % Mefe1
12 Mefe2 95 % Mefe2 % Mefe2
13
14 Starting value
15 V% %
16
17 General Solver variables Solver constraints
18 Orgflow m3/h
19 AML g/l
20 α1ML α2
21 ML g/l ML
22
23
24 Stage 1 Solver variables Solver constraints
25 α12 H1 J1
26
27 Cuor Cuaq
28 E1
29 C1 C1 Cuor g/l C1 Cuor
30 B1
31 D1
32 A1
33
34 Stage 2 Solver variables Solver constraints
35 α22 H2 J2
36
37 Cuor Cuaq
38 E2
39 C2 C 2 Cuor g/l C 2 Cuor
40 B2
41 D2
42 A2
43
44 Performance
45 Raf Ac g/l
46 Eff1c %
47

Joseph Kafumbila Page 47
A B C D E F G H I J
47
48 Table 8 Simulation program table for option 1 (part 2)
49
50 Stripping step
51 Data Solver variables Solver constraints
52 SP Cu 35 g/l SP Cu g/l SP Cu
53 SP Ac 180 g/l SP Ac g/l SP Ac
54 AD Cu 50 g/l AD Cu g/l AD Cu
55 Mefs1 98 % Mefs1 % Mefs1
56 Mefs2 85 % Mefs2 % Mefs2
57
58 General
59 R?s
60 SPflow m3/h
61
62 Stage 1 Solver variables Solver constraints
63 π12 L1 M1
64
65 Cuor Cuaq
66 D1
67 C1 C1 Cuor g/l C1 Cuor
68 B1
69 E1
70 A1
71
72 Stage 2 Solver variables Solver constraints
73 π22 L2 M2
74
75 Cuor Cuaq
2
76 D
77 C2 C 2 Cuor g/l C 2 Cuor
78 B2
79 E2
80 A2
81
82 Performance
83 Effs? %
84 Cut g/l/v%
85
86 Simulation constraint
87
88 Set objective
89

Joseph Kafumbila Page 48
A B C D E F G H I J
1
2 Table 9 Simulation program table for option 1 (part 1)
3
4 Extraction step
5 Data Solver variables Solver constraints
6 PLSflow 400 m3/h PLSflow 400 m3/h PLSflow 0.000
7 PLS Cu 7.00 g/l PLS Cu 7.00 g/l PLS Cu 0.000
8 PLS Ac 1.96 g/l PLS Ac 1.96 g/l PLS Ac 0.000
9 SR 80 % SR 80 % SR 0.000
10 Rce 1.1 Rce 1.1 Rce 0.000
11 Mefe1 92 % Mefe1 92 % Mefe1 0.000
12 Mefe2 95 % Mefe2 95 % Mefe2 0.000
13
14 Starting value
15 V% 25 %
16
17 General Solver variables Solver constraints
18 Orgflow 440.00 m3/h
19 AML 14.170 g/l
20 α1ML α2
21 0.549 -0.020 ML 14.170 g/l ML 0.568
22
23
24 Stage 1 Solver variables Solver constraints
25 α12 H1 J1
26 38.76 -32.90 68.26
27 Cuor Cuaq
28 E1 11.336 7.000
29 C1 12.000 2.225 C1 Cuor 12.000 g/l C1 Cuor 0.317
30 B1 11.653 2.607
31 D1 7.659 2.607
32 A1 7.659 7.000
33
34 Stage 2 Solver variables Solver constraints
35 α22 H2 J2
36 267.09 - 68.26
129.26
37 Cuor Cuaq
38 E2 7.659 2.607
39 C2 8.000 0.530 C 2 Cuor 8.000 g/l C 2 Cuor 0.246
40 B2 7.906 0.634
41 D2 6.112 0.634
42 A2 6.112 2.607
43
44 Performance
45 Raf Ac 11.763 g/l
46 Eff1c 90.94 %
47

Joseph Kafumbila Page 49
A B C D E F G H I J
47
48 Table 9 Simulation program table for option 1 (part 2)
49
50 Stripping step
51 Data Solver variables Solver constraints
52 SP Cu 35 g/l SP Cu 35 g/l SP Cu 0.000
53 SP Ac 180 g/l SP Ac 180 g/l SP Ac 0.000
54 AD Cu 50 g/l AD Cu 50 g/l AD Cu 0.000
55 Mefs1 98 % Mefs1 98 % Mefs1 0.000
56 Mefs2 85 % Mefs2 85 % Mefs2 0.000
57
58 General
59 R?s 2.871
60 SPflow 153.24 m3/h
61
62 Stage 1 Solver variables Solver constraints
63 π12 L1 M1
64 225.54 -410.39 22776.9
65 Cuor Cuaq
66 D1 11.336 50.00
67 C1 5.668 66.17 C1 Cuor 5.668 g/l C1 Cuor 15.843
68 B1 5.781 65.84
69 E1 5.781 49.89
70 A1 11.336 49.89
71
72 Stage 2 Solver variables Solver constraints
73 π22 L2 M2
74 603.53 -558.51 22776.9
75 Cuor Cuaq
76 D2 5.781 49.89
77 C2 3.854 44.29 C 2 Cuor 3.854 g/l C 2 Cuor -6.430
78 B2 4.143 43.46
79 E2 4.143 38.76
80 A2 5.781 38.76
81
82 Performance
83 Effs? 63.45 %
84 Cut 0.29 g/l/v%
85
86 Simulation constraint
87
88 Set objective -1.969
89

Joseph Kafumbila Page 50
A B C D E F G H I J
1
2 Table 10 Simulation program table for option 1 (part 1)
3
4 Extraction step
5 Data Solver variables Solver constraints
6 PLSflow 400 m3/h PLSflow 400 m3/h PLSflow 0.000
7 PLS Cu 7.00 g/l PLS Cu 7.00 g/l PLS Cu 0.000
8 PLS Ac 1.96 g/l PLS Ac 1.96 g/l PLS Ac 0.000
9 SR 80 % SR 80 % SR 0.000
10 Rce 1.1 Rce 1.1 Rce 0.000
11 Mefe1 92 % Mefe1 92 % Mefe1 0.000
12 Mefe2 95 % Mefe2 95 % Mefe2 0.000
13
14 Starting value
15 V% 19.93 %
16
17 General Solver variables Solver constraints
18 Orgflow 440.00 m3/h
19 AML 11.041 g/l
20 α1ML α2
21 0.549 0.549 ML 11.001 g/l ML 0.000
22
23
24 Stage 1 Solver variables Solver constraints
25 α12 H1 J1
26 44.44 -35.30 68.26
27 Cuor Cuaq
28 E1 8.801 7.000
29 C1 9.161 2.053 C1 Cuor 9.161 g/l C1 Cuor 0.000
30 B1 8.801 2.449
31 D1 4.663 2.449
32 A1 4.663 7.000
33
34 Stage 2 Solver variables Solver constraints
35 α22 H2 J2
36 529.17 - 68.26
239.86
37 Cuor Cuaq
38 E2 4.663 2.449
39 C2 4.762 0.285 C 2 Cuor 4.762 g/l C 2 Cuor 0.000
40 B2 4.663 0.393
41 D2 2.795 0.393
42 A2 2.795 2.449
43
44 Performance
45 Raf Ac 12.135 g/l
46 Eff1c 94.38 %
47

Joseph Kafumbila Page 51
A B C D E F G H I J
47
48 Table 10 Simulation program table for option 1 (part 2)
49
50 Stripping step
51 Data Solver variables Solver constraints
52 SP Cu 35 g/l SP Cu 35 g/l SP Cu 0.000
53 SP Ac 180 g/l SP Ac 180 g/l SP Ac 0.000
54 AD Cu 50 g/l AD Cu 50 g/l AD Cu 0.000
55 Mefs1 98 % Mefs1 98 % Mefs1 0.000
56 Mefs2 85 % Mefs2 85 % Mefs2 0.000
57
58 General
59 R?s 2.497
60 SPflow 176.18 m3/h
61
62 Stage 1 Solver variables Solver constraints
63 π12 L1 M1
64 472.99 -503.42 22776.9
65 Cuor Cuaq
66 D1 8.801 50.00
67 C1 3.545 50.26 C1 Cuor 3.545 g/l C1 Cuor 0.000
68 B1 3.650 50.00
69 E1 3.650 37.14
70 A1 8.801 37.14
71
72 Stage 2 Solver variables Solver constraints
73 π22 L2 M2
74 807.74 -644.69 22776.9
75 Cuor Cuaq
76 D2 3.650 37.14
77 C2 2.644 37.51 C 2 Cuor 2.644 g/l C 2 Cuor 0.000
78 B2 2.795 37.14
79 E2 2.795 35.00
80 A2 3.650 35.00
81
82 Performance
83 Effs? 68.25 %
84 Cut 0.30 g/l/v%
85
86 Simulation constraint
87
88 Set objective 0.000
89

Joseph Kafumbila Page 52
Simulation program of option 1 of copper solvent extraction configuration (2Ex2S) is done. For this
option 1, data (having red color) will be changed only for others simulations.

5.2.3. Option 2

. In this option, unknown parameters are extractant volume percentage, saturation ratio, mixer
efficiencies of stages of rank 1 and 2 of extraction and stripping steps. Table 11 gives data of chosen example for
explanation of simulation program design.

Table 11: Data of copper solvent extraction configuration of option 2

Description Symbol Unity Value
Extraction step
PLS flowrate PLS flow m3/h 700
Copper concentration in PLS PLS Cu g/l 6.0
Acid concentration in PLS PLS Ac g/l 1.96
Ratio Rce Rce 1.07
Maximum loading ML g/l 10.5
Raffinate from stage of rank 1 Raf E1 g/l 2.00
Raffinate from stage of rank 2 Raf E2 g/l 0.43
Number of extraction stage 2
Stripping step
Copper concentration in spent electrolyte SP Cu g/l 35
Acid concentration in spent electrolyte SP Ac g/l 190
Copper concentration in advance electrolyte AD Cu g/l 50
Number of stripping stage 2
Stripped organic of stage of rank 1 SO S1 g/l 3.60
Stripped organic of stage of rank 2 SO S2 g/l 2.59

Simulation program table for option 2 of 2Ex2S configuration is given in Table 12 as it appears on
Excel Microsoft spreadsheet. Data from Table 11 have red color.

In extraction table, designation αn2 , H n and J n are respectively the values of equilibrium correlation ?2
and constants H and J of stage of rank ‘n’ for calculating the value of copper concentration in aqueous phase
from the value of copper concentration in organic phase. Designation An , C n , Dn and E n are the Points A, B, C,
and D from extraction step MacCabe Thiele diagram of stage of rank ‘n’.

In stripping table, designation πn2 , Ln and M n are respectively the values of equilibrium correlation ?2
and constants L and M of stage of rank ‘n’ for calculating the value of copper concentration in aqueous phase
from the value of copper concentration in organic phase. Designation An , C n , Dn and E n are the Points A, B, C,
and D from stripping step MacCabe Thiele diagram of stage of rank ‘n’.

Plant constraints of extraction and stripping steps are simulation program results to match with plant
data.

Joseph Kafumbila Page 53
5.2.3.1. Extraction step

Data

Simulation program design is started with solver variables of data. These solver variables will be data
of all mathematical expressions of extraction step.

- In the cell ‘F6’ of solver variable of PLS flowrate (PLS flow), enter the number giving the value of PLS
flow data that is in the cell ‘C6’.
- In the cell ‘F7’ of solver variable of PLS copper concentration (PLS Cu), enter the number giving the value
of PLS copper concentration data that is in the cell ‘C7’.
- In the cell ‘F8’ of solver variable of PLS free acid concentration (PLS Ac), enter the number giving the
value of PLS free acid concentration data that is in the cell ‘C8’.
- In the cell ‘F9’ of solver variable of ratio (Rce ), enter the number giving the value of ratio ( Rce ) data that is
in the cell ‘C9’.

Solver constraints of solver variables of extraction step data are the following:

- In the cell ‘I6’, enter formula: ‘=F6-C6’.
- In the cell ‘I7’, enter formula: ‘=F7-C7’.
- In the cell ‘I8’, enter formula: ‘=F8-C8’.
- In the cell ‘I9’, enter formula: ‘=F9-C9’.

Starting values

The starting value of extractant volume percentage of simulation program is in the cell ‘F12’. This
value is the expected value of extractant volume percentage. For this case, the expected value of extractant
volume percentage is 20%.

- In the cell ‘F12’, enter the number ‘20’.

The starting value of saturation ratio of simulation program is in the cell ‘F13’. This value is the
expected value of saturation ratio. For this case, the expected value of saturation ratio is 70%.

- In the cell ‘F13’, enter the number ‘70’.

The starting value of mixer efficiency of stage of rank 1 of simulation program is in the cell ‘F14’.
This value is the expected value of mixer efficiency of stage of rank 1. For this case, the expected value is 90%.

- In the cell ‘F14’, enter the number ‘90’.

Joseph Kafumbila Page 54
The starting value of mixer efficiency of stage of rank 2 of simulation program is in the cell ‘F15’.
This value is the expected value of mixer efficiency of stage of rank 2. For this case, the expected value is 90%.

- In the cell ‘F15’, enter the number ‘90’.

General

The value of organic flowrate is in the cell ‘C18’. This value is given by the mathematical expression
(47) where the values of ratio (Rce ) is in the cell ‘F9’ and PLS flowrate is in the cell ‘F6’.

- In the cell ‘C18’, enter formula: ‘=F9*F6’.

The value of absolute maximum loading is in the cell ‘C19’. This value is given by the mathematical
expression (42) where the value of extractant volume percentage is in the cell ‘F12’.

- In the cell ‘C19’, enter formula: ‘=0.4108*F12^(1.1)’.

The value of maximum loading is solver variable because resolution of cubic equation is complicated
and is in the cell ‘F21’. The starting value of maximum loading is the value of absolute maximum loading.

- In the cell ‘F21’, enter the number ’11.086’.

Solver constraint of the value of maximum loading is that the value of equilibrium correlations α1ML
and α2 must be equals. Solver constraint of the value of maximum loading is in the cell ‘I21’. The value of
equilibrium correlation α1ML is in the cell ‘B21’ and is given by the mathematical expression (41). The value of
equilibrium correlation α2 is in the cell ‘C21’ and is given by the mathematical expression (32) where the value
of copper concentration in organic phase at the steady-state is the value of maximum loading.

- In the cell ‘B21’, enter formula: ‘=F8^2/F7’.
- In the cell ‘C21’, enter formula: ‘=((-28.511*F12^(-1.746)*F21+11.711*F12^(-0.646))*(3.303*F12-
3.0842*F21)^2)/F21’.
- In the cell ‘I21’, enter formula: ‘=B21-C21’.

Extraction stage 1

The value of copper concentration in organic phase of the Point E1 is in the cell ‘C28’ and is the value
of loaded organic. The value of loaded organic is given by the mathematical expression (70) where the values of
saturation ratio (SR) is in the cell ‘F13’ and the value of maximum loading is in the cell ‘F21’.

Joseph Kafumbila Page 55
- In cell ‘C28’, enter formula: ‘=F13*F21/100’.

The value of copper concentration in aqueous phase of the Point E1 is in the cell ‘D28’ and is the
value of copper concentration in PLS which is in the cell ‘F7’.

- In the cell ‘D28’, enter formula: ‘=F7’

The value of copper concentration in organic phase of the Point C1 is solver variable. This value is in
the cell ‘F29’. In the cell ‘F29’, enter a random number between the values of copper concentration in organic
phase of the Point E1 and the value of maximum loading. The starting value of copper concentration in organic
phase of the Point C1 is the first whole number above the value of copper concentration in organic phase of the
Point E1 . In this case, the random number is 8.

- In the Cell ‘F29’, enter number ‘8’.
- In the cell ‘C29’, enter formula: ‘=F29’

The value of copper concentration in aqueous phase of the Point C1 is in the cell ‘D29’. This value is
given by the mathematical expression (35) where the value of constant H1 is in the cell ‘C26’ and the value of
constant J1 is in the cell ‘D26’. The value of constant H1 is given by the mathematical expression (36) where the
value of initial free acid concentration is in the cell ‘F8’, the value of initial copper concentration is in the cell
‘F7’, and the value of equilibrium correlation α12 is in the cell ‘B26’. The value of equilibrium correlation α12 is
given by the mathematical expression (32) where the value of extractant volume percentage is in the cell ‘F12’
and the value of copper concentration in organic phase is in the cell ‘C29’.

- In the cell ‘B26’, enter formula: ‘=((-28.511*F12^(-1.746)*C29+11.711*F12^(-0.646))*(3.303*F12-
3.0842*C29)^(2))/C29’.
- In the cell ‘C26’, enter formula: ‘=-1.299*F8-2*F7-0.422*B26’.

The value of constant J1 is given by the mathematical expression (37) where initial free acid
concentration is in the cell ‘F8’ and initial copper concentration is in the cell ‘F7’.

- In the cell ‘D26’, enter formula: ‘=(0.644*F8+F7)^(2)’.
- In the cell ‘D29’, enter formula: ‘=[-C26-(C26^(2)-4*D26)^(0.5)]/2’.

. The values of copper concentrations in aqueous phase of the Points E1 and A1 are equals. The value
of copper concentration in aqueous phase of the Point A1 is in the cell ‘D32’.

- In the cell ‘D32’, enter formula: ‘=D28’.

Joseph Kafumbila Page 56
The value of copper concentration in aqueous phase of the Point B1 is in the cell ‘D30’. This value is
given by the mathematical expression (60) where the value of Cu1(aq/e) is the value of copper concentration in
aqueous phase of the Point C1 , the value of Cu0aq is the value of copper concentration in aqueous phase of the
Point A1 and the value of mixer efficiency of stage of rank 1 is in the cell ‘F14’.

- In the ‘D30’, enter formula: ‘=D29*F14/100 + D32*(1-F14/100)’.

The value of copper concentration in organic phase of the Point B1 is in the cell ‘C30’. This value is
given by the mathematical expression (59) where the value of ratio (Rce ) is in the cell ‘F9’, the value of Cu1or is
the value of copper concentration in organic phase of the Point B1 , the value of Cu2or is changed by the value of
Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu1aq is the value
of copper concentration in aqueous phase of the Point B1 and the value of Cu0aq is changed by the value of
Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 .

- In the cell ‘C30’, enter formula: ‘=C29+(1/F9)*(D29-D30)’.

The value of copper concentration in organic phase of the Point A1 is in the cell ‘C32’. This value is
given by the mathematical (59) where the value of ratio (Rce ) is in the cell ‘F9’, the value of Cu1or is changed by
the value of Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu2or
is the value of copper concentration in organic phase of the Point A1 , the value of Cu1aq is changed by the value
of Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 and the value of Cu0aq is
the value of copper concentration in aqueous phase of the Point A1 .

- In the cell ‘C32’, enter formula: ‘=C29+(1/F9)*(D29-D32)’.

The values of copper concentrations in organic phase of the Points D1 and A1 are equals. The value of
copper concentration in organic phase of the Point D1 is in the cell ‘C31’.

- In the cell ‘C31’, enter formula: ‘=C32’.

The values of copper concentration in aqueous phase of the Points B1 and D1 are equals. The value of
copper concentration in aqueous phase of the Point D1 is in the cell ‘D31’.

- In the cell ‘D31’, enter formula: ‘=D30’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C is that the value of copper concentrations in organic phase of the Points B1 and E1 must be equals. The
1

value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I29’.

Joseph Kafumbila Page 57
- In the cell ‘I29’, enter formula: ‘=C30-C28’.

Extraction stage 2

The value of copper concentration in organic phase of the Point E 2 is in the cell ‘C38’. This value is
the value of copper concentration in organic phase of the Point D1 .

- In the cell ‘C38’, enter formula: ‘=C31’.

The value of copper concentration in aqueous phase of the Point E 2 is in the cell ‘D38’. This value is
the value of copper concentration in aqueous phase of the Point D1 .

- In the cell ‘D38’, enter formula: ‘=D31’

The value of copper concentration in organic phase of the Point C 2 is solver variable. This value is in
the cell ‘F39’. In the cell ‘F39’, enter a random number between the values of copper concentration in the
organic phase of the Point E 2 and the value of copper concentration in organic phase of the Point C1 . The
starting value of copper concentration in organic phase of the Point C 2 is the first whole number above the value
of copper concentration in organic phase of the Point E 2 . In this case, the random number is 4.

- In the Cell ‘F39’, enter the number ‘4’.
- In the cell ‘C39’, enter formula: ‘=F39’

The value of copper concentration in aqueous phase of the Point C 2 is in the cell ‘D39’. This value is
given by the mathematical expression (35) where the value of constant H 2 is in the cell ‘C36’ and the value of
constant J 2 is in the cell ‘D36’. The value of constant H 2 is given by the mathematical expression (36) where the
value of initial free acid concentration is in the cell ‘F8’, the value of initial copper concentration is in the cell
‘F7’, and the value of equilibrium correlation α22 is in the cell ‘B36’. The value of equilibrium correlation α22 is
given by the mathematical expression (32) where the value of extractant volume percentage is in the cell ‘F12’
and the value of copper concentration in organic phase is in the cell ‘C39’.

- In the cell ‘B36’, enter formula: ‘=((-28.511*F12^(-1.746)*C39+11.711*F12^(-0.646))*(3.303*F12-
3.0842*C39)^(2))/C39’.
- In the cell ‘C36’, enter formula: ‘=-1.299*F8-2*F7-0.422*B36’.

The value of constant J 2 is given by the mathematical expression (37) where initial free acid
concentration is in the cell ‘F8’ and initial copper concentration is in the cell ‘F7’.

- In the cell ‘D36’, enter formula: ‘=(0.644*F8+F7)^(2)’.

Joseph Kafumbila Page 58
- In the cell ‘D39’, enter formula: ‘=[-C36-(C36^(2)-4*D36)^(0.5)]/2’.

. The values of copper concentrations in aqueous phase of the Points E 2 and A2 are equals. The value
of copper concentration in aqueous phase of the Point A2 is in the cell ‘D42’.

- In the cell ‘D42’, enter formula: ‘=D38’.

The value of copper concentration in aqueous phase of the Point B 2 is in the cell ‘D40’. This value is
given by the mathematical expression (60) where the value of Cu2(aq/e) is the value of copper concentration in
aqueous phase of the Point C 2 , the value of Cu1aq is the value of copper concentration in aqueous phase of the
Point A2 and the value of mixer efficiency of stage of rank 2 is in the cell ‘F15’.

- In the ‘D40’, enter formula: ‘=D39*F15/100 + D42*(1-F15/100)’.

The value of copper concentration in organic phase of the Point B 2 is in the cell ‘C40’. This value is
given by the mathematical expression (59) where the value of ratio (Rce ) is in the cell ‘F9’, the value of Cu2or is
the value of copper concentration in organic phase of the Point B 2 , the value of Cu3or is changed by the value of
Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu2aq is the value
of copper concentration in aqueous phase of the Point B 2 and the value of Cu1aq is changed by the value of
Cu2aq/e which is the value of copper concentration in aqueous phase of the Point C 2 .

- In the cell ‘C40’, enter formula: ‘=C39+(1/F9)*(D39-D40)’.

The value of copper concentration in organic phase of the Point A2 is in the cell ‘C42’. This value is
given by the mathematical (59) where the value of ratio (Rce ) is in the cell ‘F9’, the value of Cu2or is changed by
the value of Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu3or
is the value of copper concentration in organic phase of the Point A2 , the value of Cu2aq is changed by the value
of Cu2aq/e which is the value of copper concentration in aqueous phase of the Point C 2 and the value of Cu1aq is
the value of copper concentration in aqueous phase of the Point A2 .

- In the cell ‘C42’, enter formula: ‘=C39+(1/F9)*(D39-D42)’.

The values of copper concentrations in organic phase of the Points D2 and A2 are equals. The value of
copper concentration in organic phase of the Point D2 is in the cell ‘C41’.

- In the cell ‘C41’, enter formula: ‘=C42’.

Joseph Kafumbila Page 59
The values of copper concentration in aqueous phase of the Points B 2 and D2 are equals. The value of
copper concentration in aqueous phase of the Point D2 is in the cell ‘D41’.

- In the cell ‘D41’, enter formula: ‘=D40’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C 2 is that the value of copper concentrations in organic phase of the Points B 2 and E 2 must be equals. The
value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I39’.

- In the cell ‘I39’, enter formula: ‘=C40-C38’.

Plant constraints

Plant constraints are simulation program results to match with plant data. The plant data of maximum
loading come from lab test by contacting stripped organic with PLS aqueous phase (follow procedure). Plants
data of extraction step are the value of maximum loading that is in the cell ‘C45’, the value of copper
concentration in raffinate of stage of rank 1 that is in the cell ‘C46’ and the value of copper concentration in
raffinate of stage of rank 2 that is in the cell ‘C47’.

- In the cell ‘F45’ of maximum loading plant constraint, enter formula: ‘=F21’
- In the cell ‘F46’ of raffinate E1 plant constraint, enter formula: ‘=D31’
- In the cell ‘F47’ of raffinate E2 plant constraint, enter formula: ‘=D41’

Solver constraints of plants constraints of extraction step are the following:

- In the cell ‘I45’, enter formula: ‘=F45-C45’.
- In the cell ‘I46’, enter formula: ‘=F46-C45’.
- In the cell ‘I47’, enter formula: ‘=F47-C47’.

Performance

The value of free acid concentration in raffinate is in the cell ‘C50’. This value is given by the
0
mathematical expression (48) where the value of Acaq is in the cell ‘F8’, the value of PLS is in the cell ‘F7’ and
the value of Raf is in the cell ‘D41’.

- In the cell ‘C50’, enter formula: ‘=F8 + (F7-D41)*1.54’.

The value of copper extraction efficiency is in the cell ‘C51’. This value is given by the mathematical
expression (49) where the value of PLS is in the cell ‘F7’ and the value of Raf is in the cell ‘D41’.

Joseph Kafumbila Page 60
- In the cell ‘C51’, enter formula: ‘=(F7-D41)/F7*100’

5.2.3.2. Stripping step

Data

Design of simulation program is started with solver variables of data of stripping step. These solver
variables are data of all mathematical expressions of stripping step.

- In the cell ‘F57’ of solver variable of spent electrolyte copper concentration (SP Cu), enter the number
giving the value of spent electrolyte copper concentration data that is in the cell ‘C57’.
- In the cell ‘F58’ of solver variable of spent electrolyte free acid concentration (SP Ac), enter the number
giving the value of spent electrolyte free acid concentration data that is in the cell ‘C58’.
- In the cell ‘F59’ of solver variable of advance electrolyte copper concentration (AD Cu), enter the number
giving the value of advance electrolyte copper concentration data that is in the cell ‘C59’.

Solver constraints of solver variables of data of stripping step are the following:

- In the cell ‘I57’, enter formula ‘=F57-C57’.
- In the cell ‘I58’, enter formula ‘=F58-C58’.
- In the cell ‘I59’, enter formula ‘=F59-C59’.

Starting values

The starting value of mixer efficiency of stage of rank 1 of simulation program is in the cell ‘F62’.
This value is the expected value of mixer efficiency of stage of rank 1. For this case, the expected starting value
is 90%.

- In the cell ‘F62’, enter the number ‘90’.

The starting value of mixer efficiency of stage of rank 2 of simulation program is in the cell ‘F63’.
This value is the expected value of mixer efficiency of stage of rank 2. For this case, the expected starting value
is 90%.

- In the cell ‘F63’, enter the number ‘90’.

General

The value of ratio (Rcs ) is in the cell ‘C66’. This value is given by the mathematical expression (54)
where value of AD is in the cell ‘F59’, the value of SP is in the cell ‘F57’, the value of LOs is changed by the

Joseph Kafumbila Page 61
value of LOe which is in the cell ‘C28’ and the value of SOs is changed by the value of SOe which is in the cell
‘C41’. These changes follow the mathematical expressions (66) and (67).

- In the cell ‘C66’, enter formula: ‘=(F59-F57)/(C28-C41)

The value of spent electrolyte flowrate is in the cell ‘C67’. This value is given by the mathematical
expression (54) where the value of ratio (Rcs ) is in the cell ‘C66’ and the value of organic flowrate is in the cell
‘C18’.

- In the cell ‘C67’, enter formula: ‘=C18/C66’

Stripping stage 1

The value of copper concentration in organic phase of the Point D1 is in the cell ‘C73’. This value is
the value of copper concentration in organic phase of the Point E1 of extraction step.

- In the cell ‘C73’, enter formula: ‘=C28’

The value of copper concentration in aqueous phase of the Point D1 is in the cell ‘D73’. This value is
the copper concentration of advance electrolyte which is in the cell ‘F59’.

- In the cell ‘D73’, enter formula: ‘=F59’

The value of copper concentration in organic phase of the Point C1 is solver variable and is in the cell
‘F74’. The starting value of copper concentration in organic phase of the Point C1 is half the value of copper
concentration in organic phase of the Point D1 . In this case, half the value is 3.88.

- In the Cell ‘F74’, enter the number ‘3.88’.
- In the cell ‘C74’, enter formula: ‘=F74’

The value of copper concentration in aqueous phase of the Point C1 is in the cell ‘D74’. This value is
given by the mathematical expression (38) where the value of constant L1 is in the cell ‘C71’ and the value of
constant M1 is in the cell ‘D71’. The value of constant L1 is given by the mathematical expression (39) where the
value of initial free acid concentration is in the cell ‘F58’, the value of initial copper concentration is in the cell
‘F57’, and the value of equilibrium correlation π12 is in the cell ‘B71’. The value of equilibrium correlation π12 is
given by the mathematical expression (34) where the value of extractant volume percentage is in the cell ‘F12’
and the value of copper concentration in organic phase is in the cell ‘C74’.

Joseph Kafumbila Page 62
- In the cell ‘B71’, enter formula: ‘=(((4.8579*10^(-3)*F12-0.19183)*C74+11.365*F12^(-
0.85))*(3.303*F12-3.0842*C74)^(2))/C74’.
- In the cell ‘C71’, enter formula: ‘=-1.299*F58-2*F57-0.422*B71’.

The value of constant M1 is given by the mathematical expression (40) where initial free acid
concentration is in the cell ‘F58’ and initial copper concentration is in the cell ‘F57’.

- In the cell ‘D71’, enter formula: ‘=(0.644*F58+F57)^(2)’.
- In the cell ‘D74’, enter formula: ‘=[-C71-(C71^(2)-4*D71)^(0.5)]/2’.

. The values of copper concentrations in organic phase of the Points D1 and A1 are equals. The value
of copper concentration in organic phase of the Point A1 is in the cell ‘C77’.

- In the cell ‘C77’, enter formula: ‘=C73’.

The value of copper concentration in organic phase of the Point B1 is in the cell ‘C75’. This value is
given by the mathematical expression (65) where the value of Cu1(or/e) is the value of copper concentration in
organic phase of the Point C1 , the value of Cu0or is the value of copper concentration in organic phase of the Point
A1 and the value of mixer efficiency of stage of rank 1 is in the cell ‘F62’.

- In the ‘C75’, enter formula: ‘=C74*F62/100 + C77*(1-F62/100)’.

The value of copper concentration in aqueous phase of the Point B1 is in the cell ‘D75’. This value is
given by the mathematical expression (63) where the value of ratio (Rc? ) is in the cell ‘C66’, the value of Cu1or is
the value of copper concentration in organic phase of the Point B1 , the value of Cu0or is changed by the value of
Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu1aq is the value
of copper concentration in aqueous phase of the Point B1 and the value of Cu2aq is changed by the value of
Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 .

- In the cell ‘D75’, enter formula: ‘=D74-C66*(C75-C74)’.

The value of copper concentration in aqueous phase of the Point A1 is in the cell ‘D77’. This value is
given by the mathematical (63) where the value of ratio (Rce ) is in the cell ‘F66’, the value of Cu1or is changed by
the value of Cu1or/e which is the value of copper concentration in organic phase of the Point C1 , the value of Cu0or
is the value of copper concentration in organic phase of the Point A1 , the value of Cu1aq is changed by the value
of Cu1aq/e which is the value of copper concentration in aqueous phase of the Point C1 and the value of Cu2aq is
the value of copper concentration in aqueous phase of the Point A1 .

- In the cell ‘D77’, enter formula: ‘=D74-C66*(C77-C74)’.

Joseph Kafumbila Page 63
The values of copper concentrations in aqueous phase of the Points E1 and A1 are equals. The value of
copper concentration in organic phase of the Point E1 is in the cell ‘D76’.

- In the cell ‘D76’, enter formula: ‘=D77’.

The values of copper concentration in organic phase of the Points B1 and E1 are equals. The value of
copper concentration in aqueous phase of the Point E1 is in the cell ‘C76’.

- In the cell ‘C76’, enter formula: ‘=C75’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C1 is that the value of copper concentrations in aqueous phase of the Points B1 and D1 must be equals. The
value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I74’.

- In the cell ‘I74’, enter formula: ‘=D75-D73’.

Stripping stage 2

The value of copper concentration in organic phase of the Point D2 and E1 are equals. The value of
copper concentration in organic phase of the Point D2 is in the cell ‘C83’

- In the cell ‘C83’, enter formula: ‘=C76’.

The value of copper concentration in aqueous phase of the Point D2 and E1 are equals. The value of
copper concentration in aqueous phase of the Point D2 is in the cell ‘D83’

- In the cell ‘D83’, enter formula: ‘=D76’

The value of copper concentration in organic phase of the Point C 2 is solver variable and is in the cell
‘F84’. The starting value of copper concentration in organic phase of the Point C 2 is two-thirds the value of
copper concentration in organic phase of point D2 . In this case, two-thirds the value is 2.845.

- In the Cell ‘F84’, enter the number ‘2.845’.
- In the cell ‘C84’, enter formula: ‘=F84’

The value of copper concentration in aqueous phase of the Point C 2 is in the cell ‘D84’. This value is
given by the mathematical expression (38) where the value of constant L2 is in the cell ‘C81’ and the value of
constant M 2 is in the cell ‘D81’. The value of constant L2 is given by the mathematical expression (39) where the

Joseph Kafumbila Page 64
value of initial free acid concentration is in the cell ‘F58’, the value of initial copper concentration is in the cell
‘F57’, and the value of equilibrium correlation π22 is in the cell ‘B81’. The value of equilibrium correlation π22 is
given by the mathematical expression (34) where the value of extractant volume percentage is in the cell ‘F12’
and the value of copper concentration in organic phase is in the cell ‘C84’.

- In the cell ‘B81’, enter formula: ‘=(((4.8579*10^(-3)*F12-0.19183)*C84+11.365*F12^(-
0.85))*(3.303*F12-3.0842*C84)^(2))/C84’.
- In the cell ‘C81’, enter formula: ‘=-1.299*F58-2*F57-0.422*B81’.

The value of constant M 2 is given by the mathematical expression (40) where initial free acid
concentration is in the cell ‘F58’ and initial copper concentration is in the cell ‘F57’.

- In the cell ‘D81’, enter formula: ‘=(0.644*F58+F57)^(2)’.
- In the cell ‘D84’, enter formula: ‘=[-C81-(C81^(2)-4*D81)^(0.5)]/2’.

. The values of copper concentrations in organic phase of the Points D2 and A2 are equals. The value
of copper concentration in organic phase of the Point A2 is in the cell ‘C87’.

- In the cell ‘C87’, enter formula: ‘=C83’.

The value of copper concentration in organic phase of the Point B 2 is in the cell ‘C85’. This value is
given by the mathematical expression (65) where the value of Cu2(or/e) is the value of copper concentration in
organic phase of the Point C 2 , the value of Cu1or is the value of copper concentration in organic phase of the
Point A2 and the value of mixer efficiency of stage of rank 2 is in the cell ‘F63’.

- In the ‘C85’, enter formula: ‘=C84*F63/100 + C87*(1-F63/100)’.

The value of copper concentration in aqueous phase of the Point B 2 is in the cell ‘D85’. This value is
given by the mathematical expression (63) where the value of ratio (Rc? ) is in the cell ‘C66’, the value of Cu2or is
the value of copper concentration in organic phase of the Point B 2 , the value of Cu1or is changed by the value of
Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu2aq is the value
of copper concentration in aqueous phase of the Point B 2 and the value of Cu3aq is changed by the value of
Cu2aq/e which is the value of copper concentration in aqueous phase of the Point C 2 .

- In the cell ‘D85’, enter formula: ‘=D84-C66*(C85-C84)’.

The value of copper concentration in aqueous phase of the Point A2 is in the cell ‘D87’. This value is
given by the mathematical (63) where the value of ratio (Rce ) is in the cell ‘F66’, the value of Cu2or is changed by
the value of Cu2or/e which is the value of copper concentration in organic phase of the Point C 2 , the value of Cu1or

Joseph Kafumbila Page 65
is the value of copper concentration in organic phase of the Point A2 , the value of Cu2aq is changed by the value
of Cu2aq/e which is the value of copper concentration in aqueous phase of the Point C 2 and the value of Cu3aq is
the value of copper concentration in aqueous phase of the Point A2 .

- In the cell ‘D87’, enter formula: ‘=D84-C66*(C87-C84)’.

The values of copper concentrations in aqueous phase of the Points E 2 and A2 are equals. The value of
copper concentration in organic phase of the Point E 2 is in the cell ‘D86’.

- In the cell ‘D86’, enter formula: ‘=D87’.

The values of copper concentration in organic phase of the Points B 2 and E 2 are equals. The value of
copper concentration in aqueous phase of the Point E 2 is in the cell ‘C86’.

- In the cell ‘C86’, enter formula: ‘=C85’.

Solver constraint of solver variable which is the value of copper concentration in organic phase of the
Point C is that the value of copper concentrations in aqueous phase of the Points B 2 and D2 must be equals. The
2

value of solver constraint of the value of copper concentration in organic phase is in the cell ‘I84’.

- In the cell ‘I84’, enter formula: ‘=D85-D83’.

Plant constraints

Plant constraints are simulation program results to match with plant data. Plant data of stripping step
are the value of copper concentration in stripped organic of stage of rank 1 that is in the cell ‘C90’ and the value
of copper concentration in stripped organic of stage of rank 2 that is in the cell ‘C91’.

- In the cell ‘F90’ of plant constraint of stripped organic ?1 , enter formula: ‘=C76’.
- In the cell ‘F91’ of plant constraint of stripped organic ?2 , enter formula: ‘=C86’.

Solver constraints of plant constraints of stripping step are the following:

- In the cell ‘I90’, enter formula ‘=F90-C90’.
- In the cell ‘I91’, enter formula ‘=F91-C91’.

Joseph Kafumbila Page 66
Performances

The value of copper stripping efficiency is in the cell ‘C94’. This value is given by the mathematical
expression (55) where the value of LOs is in the cell ‘C73’ and the value of SOs is in the cell ‘C86’.

- In the cell ‘C84’, enter formula: ‘=(C73-C86)/C73*100’

The value of net copper transfer is in the cell ‘C95’. This value is given by the mathematical
expression (56) where the value of LOs is in the cell ‘C73’, the value of SOs is in the cell ‘C86’ and the value of
extractant volume percentage is in the cell ‘F12’.

- In the cell ‘C95’, enter formula: ‘=(C73-C86)/F12’

5.2.3.3. Simulation constraint

The value of simulation program constraint is in the cell ‘I99’. Simulation program constraint is that
the copper concentrations in stripped organic of extraction and stripping steps must be equals. This simulation
program constraint is the set objective of Excel solver program.

- In the cell ‘I99’, entre formula: ‘=C86-C41’

At this level, it appears Table 13 as it appears on Excel Microsoft spreadsheet. Table 13 gives results
of simulation program with the starting values of extractant volume percentage, saturation ratio, maximum
loading, copper concentration in organic phase of the Point C1 and C 2 of extraction step and copper
concentration in organic phase of the Point C1 and C 2 of stripping step and mixer efficiencies of stage of rank 1
and 2 of extraction and stripping steps. Simulation results are not matched with plant data. Solver variables have
blue color and solver constraints have green color.

5.2.3.4. 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 ‘I99’ 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 for each solver variable (blue color in
Table 13). 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’.

Joseph Kafumbila Page 67
b. In the ‘Cell Reference’ box, enter the cell reference of PLS flowrate solver constraint (green
color in Table 13).
c. Click the ‘relationship’ ‘=‘, in the ‘Constraint’ box, type the number ‘0’.
d. Click ‘Add’ for the second solver constraint. When the last solver constraint is added (cell
‘I91’), 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’.

At this level, it appears Table 14 as it appears on Excel Microsoft spreadsheet. Table 14 gives results
of simulation program with the optimum value of the starting values. Plant data are matched with simulation
results.

Simulation program of copper solvent extraction configuration (2Ex2S) of option 2 is done. For this
option 2, data (in red color) will be changed only for others simulations.

Joseph Kafumbila Page 68
A B C D E F G H I J
1
2 Table 12 Simulation program table option 2 (part1)
3
4 Extraction step
5 Data Solver variables Solver constraints
6 PLSflow 700.0 m3/h PLSflow m3/h PLSflow
7 PLS Cu 6.00 g/l PLS Cu g/l PLS Cu
8 PLS Ac 1.96 g/l PLS Ac g/l PLS Ac
9 Rce 1.07 Rce Rce
10
11 Starting values
12 V% %
13 SR %
14 Mefe1 %
15 Mefe2 %
16
17 General
18 Orgflow m3/h
19 AML g/l
20 α1ML α2
21 ML g/l ML
22
23
24 Stage 1 Solver variables Solver constraints
25 α12 H1 J1
26
27 Cuor Cuaq
1
28 E
29 C1 C1 Cuor g/l C1 Cuor
30 B1
31 D1
32 A1
33
34 Stage 2 Solver variables Solver constraints
35 α22 H2 J2
36
37 Cuor Cuaq
2
38 E
39 C2 C 2 Cuor g/l C 2 Cuor
40 B2
41 D2
42 A2
43
44 Plant data Plant constraints Solver constraints
45 ML 10.50 g/l ML g/l ML
46 Raf E1 2.00 g/l Raf E1 g/l Raf E1
47 Raf E2 0.43 g/l Raf E2 g/l Raf E2
48
49 Performance
50 Raf Ac g/l
51 Effec %
52

Joseph Kafumbila Page 69
A B C D E F G H I J
52
53 Table 12 Simulation program table option 2 (part2)
54
55 Stripping step
56 Data Solver variables Solver constraints
57 SP Cu 35 g/l SP Cu g/l SP Cu
58 SP Ac 190 g/l SP Ac g/l SP Ac
59 AD Cu 50 g/l AD Cu g/l AD Cu
60
61 Starting values
62 Mefs1 %
63 Mefs2 %
64
65 General
66 Rcs
67 SPflow m3/h
68
69 Stage 1 Solver variables Solver constraints
70 π12 L1 M1
71
72 Cuor Cuaq
73 D1
74 C1 C1 Cuor g/l C1 Cuor
75 B1
76 E1
77 A1
78
79 Stage 2 Solver variables Solver constraints
80 π22 L2 M2
81
82 Cuor Cuaq
2
83 D
84 C2 C 2 Cuor g/l C 2 Cuor
85 B2
86 E2
87 A2
88
89 Plant data Plant constraints Solver constraints
90 SO S1 3.60 g/l SO S1 g/l SO S1
91 SO S2 2.59 g/l SO S2 g/l SO S2
92
93 Performance
94 Effs? %
95 Cut g/l/v%
96
97 Simulation constraint
98
99 Set objective
100

Joseph Kafumbila Page 70
A B C D E F G H I J
1
2 Table 13 Simulation program table option 2 (part1)
3
4 Extraction step
5 Data Solver variables Solver constraints
6 PLSflow 700.0 m3/h PLSflow 700.0 m3/h PLSflow 0.000
7 PLS Cu 6.00 g/l PLS Cu 6.00 g/l PLS Cu 0.000
8 PLS Ac 1.96 g/l PLS Ac 1.96 g/l PLS Ac 0.000
9 Rce 1.07 Rce 1.07 Rce 0.000
10
11 Starting values
12 V% 20 %
13 SR 70 %
14 Mefe1 90 %
15 Mefe2 90 %
16
17 General
18 Orgflow 746.67 m3/h
19 AML 11.086 g/l
20 α1ML α2
21 0.640 -0.022 ML 11.086 g/l ML 0.662
22
23
24 Stage 1 Solver variables Solver constraints
25 α12 H1 J1
26 100.74 -57.06 52.74
27 Cuor Cuaq
28 E1 7.760 6.000
29 C1 8.000 0.940 C1 Cuor 8.000 g/l C1 Cuor -0.235
30 B1 7.526 1.446
31 D1 3.256 1.446
32 A1 3.256 6.000
33
34 Stage 2 Solver variables Solver constraints
35 α22 H2 J2
36 779.80 - 52.74
343.62
37 Cuor Cuaq
38 E2 3.256 1.446
39 C2 4.000 0.154 C 2 Cuor 4.000 g/l C 2 Cuor 0.623
40 B2 3.879 0.283
41 D2 2.789 0.283
42 A2 2.789 1.446
43
44 Plant data Plant constraints Solver constraints
45 ML 10.50 g/l ML 11.086 g/l ML 0.586
46 Raf E1 2.00 g/l Raf E1 1.446 g/l Raf E1 -0.554
47 Raf E2 0.43 g/l Raf E2 0.283 g/l Raf E2 -0.147
48
49 Performance
50 Raf Ac 10.765 g/l
51 Effec 95.29 %
52

Joseph Kafumbila Page 71
A B C D E F G H I J
52
53 Table 13 Simulation program table option 2 (part2)
54
55 Stripping step
56 Data Solver variables Solver constraints
57 SP Cu 35 g/l SP Cu 35 g/l SP Cu 0.000
58 SP Ac 190 g/l SP Ac 190 g/l SP Ac 0.000
59 AD Cu 50 g/l AD Cu 50 g/l AD Cu 0.000
60
61 Starting values
62 Mefs1 90.00 %
63 Mefs2 90.00 %
64
65 General
66 Rcs 3.017
67 SPflow 247.48 m3/h
68
69 Stage 1 Solver variables Solver constraints
70 π12 L1 M1
71 394.64 -483.35 24762.2
72 Cuor Cuaq
73 D1 7.760 50.00
74 C1 3.880 58.25 C1 Cuor 3.880 g/l C1 Cuor 7.080
75 B1 4.268 57.08
76 E1 4.268 46.54
77 A1 7.760 46.54
78
79 Stage 2 Solver variables Solver constraints
80 π22 L2 M2
81 716.63 -619.23 24762.2
82 Cuor Cuaq
83 D2 4.268 46.54
84 C2 2.845 42.97 C 2 Cuor 2.845 g/l C 2 Cuor -4.002
85 B2 2.987 42.54
86 E2 2.987 38.68
87 A2 4.268 38.68
88
89 Plant data Plant constraints Solver constraints
90 SO S1 3.60 g/l SO S1 4.268 g/l SO S1 0.668
91 SO S2 2.59 g/l SO S2 2.987 g/l SO S2 0.397
92
93 Performance
94 Effs? 61.50 %
95 Cut 0.24 g/l/v%
96
97 Simulation constraint
98
99 Set objective 0.199
100

Joseph Kafumbila Page 72
A B C D E F G H I J
1
2 Table 14 Simulation program table option 2 (part1)
3
4 Extraction step
5 Data Solver variables Solver constraints
6 PLSflow 700.0 m3/h PLSflow 700.0 m3/h PLSflow 0.000
7 PLS Cu 6.00 g/l PLS Cu 6.00 g/l PLS Cu 0.000
8 PLS Ac 1.96 g/l PLS Ac 1.96 g/l PLS Ac 0.000
9 Rce 1.07 Rce 1.07 Rce 0.000
10
11 Starting values
12 V% 19.11 %
13 SR 74.40 %
14 Mefe1 86.71 %
15 Mefe2 87.05 %
16
17 General
18 Orgflow 746.67 m3/h
19 AML 10.544 g/l
20 α1ML α2
21 0.640 0.640 ML 10.500 g/l ML 0.000
22
23
24 Stage 1 Solver variables Solver constraints
25 α12 H1 J1
26 58.94 -39.42 52.74
27 Cuor Cuaq
28 E1 7.812 6.000
29 C1 8.387 1.387 C1 Cuor 8.387 g/l C1 Cuor 0.000
30 B1 7.812 2.000
31 D1 4.062 2.000
32 A1 4.062 6.000
33
34 Stage 2 Solver variables Solver constraints
35 α22 H2 J2
36 602.07 - 52.74
268.62
37 Cuor Cuaq
38 E2 4.062 2.000
39 C2 4.281 0.196 C 2 Cuor 4.281 g/l C 2 Cuor 0.000
40 B2 4.062 0.430
41 D2 2.590 0.430
42 A2 2.590 2.000
43
44 Plant data Plant constraints Solver constraints
45 ML 10.50 g/l ML 10.50 g/l ML 0.000
46 Raf E1 2.00 g/l Raf E1 2.00 g/l Raf E1 0.000
47 Raf E2 0.43 g/l Raf E2 0.43 g/l Raf E2 0.000
48
49 Performance
50 Raf Ac 10.538 g/l
51 Effec 92.83 %
52

Joseph Kafumbila Page 73
A B C D E F G H I J
52
53 Table 14 Simulation program table option 2 (part2)
54
55 Stripping step
56 Data Solver variables Solver constraints
57 SP Cu 35 g/l SP Cu 35 g/l SP Cu 0.000
58 SP Ac 190 g/l SP Ac 190 g/l SP Ac 0.000
59 AD Cu 50 g/l AD Cu 50 g/l AD Cu 0.000
60
61 Starting values
62 Mefs1 92.52 %
63 Mefs2 86.61 %
64
65 General
66 Rcs 2.873
67 SPflow 259.93 m3/h
68
69 Stage 1 Solver variables Solver constraints
70 π12 L1 M1
71 521.10 -536.72 24762.2
72 Cuor Cuaq
73 D1 7.812 50.00
74 C1 3.259 50.98 C1 Cuor 3.259 g/l C1 Cuor 0.000
75 B1 3.600 50.00
76 E1 3.600 37.90
77 A1 7.812 37.90
78
79 Stage 2 Solver variables Solver constraints
80 π22 L2 M2
81 870.22 -684.04 24762.2
82 Cuor Cuaq
83 D2 3.600 37.90
84 C2 2.434 38.35 C 2 Cuor 2.434 g/l C 2 Cuor 0.000
85 B2 2.590 37.90
86 E2 2.590 35.00
87 A2 3.600 35.00
88
89 Plant data Plant constraints Solver constraints
90 SO S1 3.60 g/l SO S1 3.60 g/l SO S1 0.000
91 SO S2 2.59 g/l SO S2 2.59 g/l SO S2 0.000
92
93 Performance
94 Effs? 66.85 %
95 Cut 0.27 g/l/v%
96
97 Simulation constraint
98
99 Set objective 0.000
100

Joseph Kafumbila Page 74
6. Bibliography
1. Alguacil F.J., Modelling copper solvent extraction from acidic sulphate using MOC 45, Rev.Metal
Madrid, 1998, p381-384.
2. Komulainen T.,Pekkla P., Ramtala A. and Jämsa-Jounela S., Dynamic modeling of an industrial copper
solvent extraction process, Hydrometallurgy 81, 2006, p52-61.
3. Hossen Aminian, Modélisation et simulation des opérations d’extraction par solvant et d’électrolyse du
Cuivre, thèse, université de Laval, Canada, 1999.
4. Gerald L. Bauer and Thomas W. Chapman, Measurement and correlation of solvent extraction
equilibria. The extraction of Copper by kelex 100, Metallurgical transaction B, 1976.
5. AMEL A., Etude thermodynamique de l’extraction des Métaux de transition par la Salicylidèneaniline,
thèse, Université Mohamed Khider, 2013.
6. Ritcey G.M., Ashbrook A.W., Solvent extraction: principles and application of process metallurgy, Part
I, Elsevier, 1984.
7. Jeffers T.H, Groves R.D, Minimizing lead contamination in Copper produced by solvent extraction –
electrowinning, Salt Lake City Research Center.
8. Winand R., Electrocristallisation. Théorie et application, Journal de physique IV, 1994.
9. Beukes N.T. and Badenhorst J., Copper electrowinning; theoretical and practical design,
Hydrometallurgy conference, SAIMM, 2009.
10. Liu Jiarshe, Lan Zhuo Yue, Qiu Guarr Zhou, Wang Diarr Zuo, Mechanism of crud formation in Copper
solvent extraction, journal CSUT, Vol 9, 2002.
11. Hans Hein, Importance of a wash stage in Copper solvent extraction, HydroCopper, 2005.

Design of copper electrowinning circuit using conventional cells

The improvement in the leaching and solvent extraction technologies continues to increase the
importance of copper electrowinning in the word copper production. The quality of copper deposit
has been improved dramatically by the introduction of the permanent cathode technology. The paper
gives a method of designing the copper electrowinning circuit of a plant having L/SX/EW technology
and using conventional cells with stainless steel cathode blanks. The method is based on the number
of overhead crane revolutions per day and per overhead crane between cells and stripping machine of
the existing copper electrowinning plants. The paper gives also the simulation procedure of copper
electrolyte flowrates of the new and old copper electrowinning circuit.

https://fr.scribd.com/document/339612505/Design-of-Copper-Electrowinning-Circuit-using-
Conventional-cells

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