Design of Copper Solvent Extraction Configurations

Joseph Kafumbila
Process Designer
Design of Copper solvent extraction

configurations
Copyright 2015 Joseph Kafumbila

www.jokafumbila@hotmail.com
www.linkedin.com
Content
1.
2.
Preface...
Modeling and Isotherm of copper solvent extraction..
1.1. Extraction step.
1.1.1.
Modeling of extraction..
1.1.2.
Isotherm of extraction..
1.1.3.
Maximum copper concentration in the organic phase..
1.2. Stripping step..
1.2.1.
Modeling of stripping
1.2.2.
Isotherm of stripping step.
1.2.3.
Minimum copper concentration in the stripped organic
Mass balance of copper solvent extraction.
2.1. Scheme of stage on the extraction and the stripping step.
2.2. Flow parameters of copper solvent extraction.
2.3. Equations of mass balance of copper solvent extraction..
2.3.1.
Extraction step.
2.3.2.
Stripping step
2.3.3.
Equilibrium constraints between the extraction and the stripping steps
2.4. Mixing efficiency..
2.4.1.
Description of mixing efficiency
2.4.2.
Flow parameters
2.4.3.
Correlations of concentrations of copper..
2.4.4.
Industrial data of mixing efficiency
2.5. MacCabe Thiele diagram..
2.5.1.
Extraction step.
2.5.2.
Stripping step
Simulation of solvent extraction scheme.
3.1. Constraints of copper SX/EW configuration...
3.1.1
Maximum value of V% in the organic phase.
3.1.2.
PLS and spent electrolytes temperature.
3.1.3.
Free acid concentration in the PLS
3.1.4.
Maximum concentration of free acid in the spent electrolyte.
3.1.5.
Minimum concentration of copper in the spent electrolyte
3.1.6.
Maximum concentration of copper in the advance electrolyte...
3.1.7.
Minimum value of ..
3.1.8.
Maximum value of ..
3.2. Optimum value of volume percentage of extractant in the organic.
3.2.1.
Constraints
3.2.2.
Maximum extraction efficiency..
3.2.3.
Saturation of organic phase with the copper.
3.3. Procedure of copper solvent extraction simulation..
3.3.1.
Plant description..
3.3.2.
Simulation procedure
References.
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Joseph Kafumbila | Process designer-2015
Preface
The aim of this paper is to present a simple method of simulation based on the realistic
theory of copper solvent extraction and easy to use on an Excel spreadsheet for any complex
scheme. This method is intended for designers of copper solvent extraction plants.
In the first chapter, this paper gives the equilibrium correlations on the extraction and the
stripping step of copper solvent extraction using the extractant Lix984N. This extractant is
chosen because it is the most used in the metallurgy of copper. The equilibrium correlation on
the extraction step is based on the thermodynamic property of chemical reaction of copper
solvent extraction. The equilibrium correlation on the stripping step is based on the
characteristics of isotherm curves. In this chapter, the procedure of construction of isotherms
curves is given for the extraction and stripping steps. The equilibrium correlation on the
extraction step gives also the mathematical expression for the calculation of maximum load value.
In the second chapter, this paper gives the conservation equations of volume and mass in
the copper solvent extraction plant, the values of parameters such as the extraction and the
stripping efficiencies, the equilibrium constraints between the extraction and the stripping steps,
the mathematical expressions of mixing efficiencies, and MacCabe Thiele diagram of extraction
and stripping steps.
In the last chapter, it gives the limitations of values of design criteria and the simulation
procedure of copper solvent extraction using the equilibrium correlations developed in the first
chapter.
1. Modeling and isotherm of copper solvent extraction

1.1.
Extraction step
1.1.1.
Modeling of extraction
The extraction stage depends on the kinetics of mass transfer between both phases
(organic and aqueous) and the transfer is stopped when the copper is reached the thermodynamic
equilibrium in both phases.
The Lix 984N is the mixing of aldoxime and ketoxime extractants and the copper solvent
extraction by Lix 984N is followed the chemical reaction (a) [1].
+ 2HR
(a)
where
and
are the ionic species of copper and hydrogen in the aqueous phase, HR is the
acid form of Lix 984N and
is the Copper complex form in the organic phase.
The equilibrium condition of chemical reaction (a) is given by the mathematical
expression (1) [2].
+
Where
(1)
=0
is the chemical or electrochemical potential of species i.
The chemical potential of species I is given by the mathematical expression (2).

= RTln(
(2)
where is the chemical activity coefficient of species I, I is the concentration of specie I in

mol/l, R is the perfect gases constant and T is the temperature.
The substitution of expression (2) for all species in the expression (1) gives the expression
(3).
[
] [
] [
] [
=[
] [
]
]
=K
(3)
The value of K coming from the molar concentrations of species is given by the
expression (4).
[
] [
K =[
] [
]
]
(4)
The molar concentrations of copper at equilibrium in organic and aqueous phases are
respectively obtained by the expressions (5), (6) and (7).
4
[
]=
(5)
=
[
+(
)x
(6)
(7)
]=
where
is the concentration of copper (g/l) in the aqueous phase at equilibrium,
is the
initial concentration (g/l) of copper in the aqueous phase,
is the initial concentration (g/l)
of copper in the organic phase,
is the concentration of copper (g/l) in the organic phase at
equilibrium,
is the volume of aqueous phase and
is the volume of organic phase.
The molar concentration of free extractant in the organic phase is calculated from the
mathematical expression (8).
[
] =
(8)
-2x
where V% is the volume percentage of extractant in the organic phase, the value 0.91 is the
density of extractant, and the value 270 is the mass molar of extractant.
The sulphuric acid dissociation is followed the reactions (b) and (c).
+
+
K1 =
(b)
K2 = 1.25
(c)
If C1 (mol/l) is the concentration of free sulphuric acid in the aqueous phase and C2
(mol/l) is the concentration of
anions associated to the salts in aqueous phase. The
dissociation reaction (b) is complete because K1 is big. The following mass balance comes from
the dissociation of reaction (b).
Initial state
Final state
Mass balance
C1
-C1
0
0
C1
C1
0
C1
C1
The second dissociation reaction (c) is not complete because K2 is not big enough. The
following mass balance comes from the second dissociation reaction where X is the molar
quantity of
goes into the dissociation.
Initial state
Final state
Mass balance
C1
-X
C1-X
C2
X
C2-X
C1
X
C1+X
The chemical reaction constant of second dissociation reaction is given by the expression (9).
K2 =
(9)
From the expression (9), the quantity X becomes zero when the concentration C2 is more
than K2. Therefore, at equilibrium, the concentration of hydrogen ion in aqueous phase is given
by the expression (10) which take account only the dissociation reaction (b). The expression (11)
gives the sulphuric acid concentration at equilibrium in the aqueous phase.
[
(10)
]=
=
where
+(
(11)
) x 1,54
is the concentration (g/l) of sulphuric acid in the aqueous phase at equilibrium and
is the initial concentration (g/l) of sulphuric acid in the aqueous phase.
The substitution of expressions (5), (7), (8) and (10) in the expression (4) gives the
expression (12) which gives the K value as function of volume percentage of extractant in the
organic phase and the concentrations of species (g/l) in the organic and aqueous phases.
K=
x[
]
]
(12)
The value of K coming from the coefficients of chemical activities of species is given by
the mathematical expression (13).
K=
[
[
] [
] [
]
]
(13)
The value of K is the multiplication of two ratios. The first ratio is the ratio of
coefficients of chemical activities of species in the organic phase and the second ratio is the ratio
of coefficients of chemical activities of species in the aqueous phase.
In the organic phase, it has been observed that the ratio of coefficients of chemical
activities of species is a function of copper concentration in the organic phase [2].
In the aqueous phase, when the concentrations of species are lower than 1 mol/l, the
values of coefficients of chemical activities approach 1 [3]. On the extraction step, the molar
concentrations of copper and free acid are generally lower than 1 mol/l, the value of ratio of
coefficients of chemical activities in the aqueous phase approach 1.
The consequence of these assumptions is that, on the extraction step, the value of K from
mathematical expression (12) is a function of concentration of copper the in the organic phase.
The chosen example from which the values of K obtained from the expression (12) are
plotted on the graph versus the concentrations of copper in the organic phase at equilibrium is
resumed in the BASF Redbook [4]. The initial aqueous phase contains 2.5 g/l of Copper at pH
1.8. The organic phase is constituted by 8.7 % of Lix 984N in Escaid 100. The initial organic
phase contains 1.8 g/l of copper. Table 1 gives the concentrations of copper obtained in the
laboratory in the organic and the aqueous phases at equilibrium. Figure 1 gives the value of K
coming from expression (12) versus the concentration of copper in the organic phase. The results
show that the value of K is the linear function of concentration of copper in the organic phase.
This linear thermodynamic property on extraction step is applied on the results obtained
in the laboratory with the extractant Lix 984N at different volume percentage of extractant and
given the empirical modeling on the extraction step. This modeling is given by the mathematical
expression (14).
K=[3.4657xLn(v%)-13.524]x(
(14)
) + [-1.553xLn(v%) + 6.4051]
Table 1: Extraction isotherm experimental data
g/l
0.070
0.090
0.170
0.280
0.510
1.240
1.940
g/l
2.040
2.280
2.980
3.280
3.700
4.190
4.350
2,00
K value
1,60
1,20
0,80
0,40
R = 0,9834
0,00
2,00
2,50
3,00
3,50
4,00
4,50
Organic phase : Metal concentration (g/l)
Figure 1: valuesof K versus the concentrations of copper in the organic phase

1.1.2. Isotherm of extraction step
The isotherm curve of extraction step is the repartition of copper between the aqueous
and the organic phases at equilibrium. The equilibrium correlations of extraction step given by
the expression (12) and (14) are used for the construction of curve of isotherm of extraction step.
The copper and the free acid concentrations in the PLS and also the concentration of extractant
in the organic phase are the data which must be known for the construction of isotherm curve of
extraction step.
The equilibrium corrections
and
are rearranged to have the concentration of
copper in aqueous phase on one side and the concentration of copper in the organic phase on
the other side. It appears two news equilibrium corrections
and
. The mathematical
expressions of news equilibrium corrections are given by the expressions (15) and (16). At
equilibrium, the values of equilibrium correlations and are equals.
=
(15)
(16)
There is two ways to make the isotherm curve of extraction step. The first way is started
from the known value of concentration of copper in the aqueous phase at equilibrium from
which the concentration of copper in the organic phase is calculated. The second way is started
from the known value of concentration of copper in the organic phase at equilibrium from which
the concentration of copper in aqueous phase is calculated.
The first way
When the values of concentrations of copper and free acid in the PLS, the concentration
of copper in the aqueous phase at equilibrium, and the volume percentage of extractant in the
organic phase are introduced in the mathematical expressions of equilibrium correlations
and
, the value of
is a constant. However, the value of
is a function of concentration of
copper in the organic phase. The combination of
and
gives a cubic equation of
concentration of copper in the organic phase at equilibrium. The resolution of this type of
equation is not easy. The simply way to find the value of concentration of copper in the organic
phase is to use the goal seek Microsoft Excel application. This method is explained through an
example.
The chosen example to make the curve of isotherm of extraction step comes from Table
1. The value of concentration of copper at equilibrium is 0.090 g/l.
The procedure for the calculation of concentration of copper in the organic phase at
equilibrium with 0.090 g/l of concentration of copper in aqueous phase on the Microsoft Excel
spreadsheet using Goal Seek application follows this step:
-
On the Microsoft spreadsheet, type 0.09 of copper concentration in the aqueous

phase in the cell B5.
Type 1 (not =1) of concentration of copper in the organic phase in the cell C5.
The value 1 of concentration of copper in the organic phase is starting random
number.
Use the mathematical expression (15) to calculate the value of
in the cell D5.
Use the mathematical expression (16) to calculate the value of
in the cell E5.
Calculate the value of - in cell F5.
The results are shown in Table 2 which gives a small part of Microsoft spreadsheet.
At this level, the Goal Seek Microsoft Excel application is used to find the value of
concentration of copper in the organic phase. The application of Goal Seek follows this step:
On the Data tab, in the Data tools group, click What-if Analysis and then, in the list,
click Goal Seek. The Goal Seek box opens.
In the Set cell field, type F5.
In the "To value" field, type 0.
In the "By changing" cell field, type C5.
Click Ok. Excel displays the solution in both the spreadsheet and the Goal Seek Status
dialog box.
Click Ok.
Table 2: Microsoft Excel spreadsheet with the starting random value of concentration of copper
in the organic phase
A
1
2
3
4
5
6
7
g/l
0.09
g/l
1
307.93
1548.16
-1240.22
At this level, it appears Table 3 which gives the value of concentration of copper in the
organic phase at equilibrium.
Table 3: Microsoft Excel spreadsheet with the value of concentration of copper in the organic
phase at equilibrium
A
1
2
3
4
5
6
7
g/l
0.09
g/l
2.266
307.93
307.93
0.00
This first way to have the value of concentration of copper in the organic phase from the
value of concentration of copper in aqueous phase is applied to all value of concentration of
copper in the aqueous phase from Table 1. The results are shown in Table 4.
Table 4: Results of isotherm of extraction step using the first way
g/l
0.070
0.090
0.170
0.280
0.510
1.240
1.940
V%
%
8.7
8.7
8.7
8.7
8.7
8.7
8.7
g/l
2.5
2.5
2.5
2.5
2.5
2.5
2.5
g/l
1.553
1.553
1.553
1.553
1.553
1.553
1.553
g/l
2.045
2.266
2.820
3.229
3.667
4.162
4.318
4.01 102
3.08 102
155.48
88.28
41.81
9.84
3.01
4.01 102
3.08 102
155.48
88.28
41.81
9.84
3.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
The second way

When the values of concentrations of copper and free acid in the PLS, the concentration
of copper in the organic phase at equilibrium, and the volume percentage of extractant are
introduced in the mathematical expressions of equilibrium correlations
and , the value of
is a constant. The value of is a function of concentration of copper in the aqueous phase.
The combination of
and
gives a 2nd degree equation of concentration of copper in the
aqueous phase at equilibrium. The form of this 2nd degree equation is given by the mathematical
expression (17).
A
+B
(17)
+C=0
The mathematical expressions (18), (19) and (20) give the values of constants A, B and C
of the 2nd degree equation.
A = 2.3716
(18)
B = -(3.08x
+ 4.7432x
(19)
(20)
C=
The concentration of copper in the aqueous phase is given by the mathematical

expression (21).
=
(21)
The value of is given by the mathematical expression (22).

=
4AC
(22)
The selected data to explain the second way for the construction of isotherm curve on the
extraction step comes from Table 4. The values of concentration of copper in the aqueous
obtained from the values of concentration of copper in the organic phase from Table 4 are in
Table 5. The curve of isotherm on the extraction step is plotted with the data from Table 1 and
Table 4 in Figure 2.
10
Table 5: Extraction isotherm established from copper concentration in organic phase

g/l
2.05
2.27
2.82
3.23
3.67
4.16
4.32
V%
%
8.7
8.7
8.7
8.7
8.7
8.7
8.7
A
g/l
2.5
2.5
2.5
2.5
2.5
2.5
2.5
g/l
1.553
1.553
1.553
1.553
1.553
1.553
1.553
102
4.01
3.08 102
1.55 102
88.3
41.8
9.84
3.01
2.37
2.37
2.37
2.37
2.37
2.37
2.37
C
102
-4.17
-3.25 102
-1.72 102
-1.05 102
-58.5
-26.5
-19.6
29.19
29.19
29.19
29.19
29.19
29.19
29.19
105
1.74
1.05 105
2.93 104
1.07 104
3.14 103
4.24 102
1.09 102
g/l
0.07
0.09
0.17
0.28
0.51
1.24
1.94
5,0
4,5
MAC
Organic phase, Copper (g/l)
4,0
3,5
3,0
experimental values
2,5
Modeling
2,0
1,5
1,0
0,5
0,0
0,0
0,5
1,0
1,5
2,0
2,5
3,0
Aqueous phase, copper (g/l)

Figure 2: Isotherm curve of extraction step for PLS containing 2.5 g/l of copper and 1.553 g/l
free acid in contact with the organic phase containing 8.7% of Lix984N
1.1.3. Maximum copper concentration in the organic phase
The point MAC on Figure 2 is the coordinate of maximum concentration of copper in
organic phase at equilibrium with the concentration of copper in the PLS. The maximum
concentration of copper in the organic phase (MAC) is a function of concentrations of copper
and free acid in the PLS and also the volume percentage of extractant in the organic phase. The
values of equilibrium correlations
and
are equals at equilibrium for the maximum
concentration of copper in the organic. The mathematical expressions of correlations
and
are given by the expressions (23) and (24) respectively.
11
(23)
= (3.4657xLn(V%)-13.524)x(
(24)
) +(-1.553xLn(V%)+6.4051)
When the concentration of free acid in the PLS is zero, the values of
and
are zero.
The maximum concentration of copper in the organic phase (MAC) becomes the maximum load
(ML). The maximum load organic is function only of volume percentage of extractant in the
organic phase. The value of ML comes from the mathematical expression of equilibrium
correlation . From the mathematical expression (25), the value of ML is calculated.
=-(
(25)
Figure 3 gives the value of maximum load versus the volume percentage of extractant in
the organic phase.
25,0
Maximum load, ML (g/l)
20,0
15,0
10,0
5,0
0,0
10,0
15,0
20,0
25,0
30,0
Organic phase, V% of Lix984N
Figure 3: Maximum load versus volume percentage of extraction in the organic phase
1.2.
Stripping step
1.2.1. Modeling of stripping

The modeling of extraction step cant be applied to the stripping step because of the
assumption on the values of coefficients of chemical activities in the aqueous phase, which
approach the value 1, is not applicable to the stripping step. The thermodynamic considerations
in the stripping step show that the ratio of coefficients of chemical activities in the aqueous phase
is a function of ionic strength and the concentration of acid in the aqueous phase [2].
12
On the other hand, the results of isotherm curve on stripping step from laboratory show
that the copper concentration in the organic phase is a linear function of ratio of concentrations
of copper and free acid in the aqueous phase at equilibrium in the range of 30 to 60 g/l of copper
and 140 to 200 g/l of free acid in the aqueous phase.
The chosen example from which the values of concentration of copper in the organic
phase are plotted versus the ratio of concentrations of copper and free acid in the aqueous phase
is resumed in the BASF Redbook [4]. The spent electrolyte contains 30.7 g/l of copper and 190
g/l of free acid. The organic phase is constituted by 8.7 % of Lix 984N in Escaid 100. The loaded
organic phase contains 3.9 g/l of copper. Table 6 gives the concentrations of copper the in the
organic and aqueous phases at equilibrium obtained in the laboratory.
Figure 4 shows the graph of concentrations of copper in organic phase versus the ratio of
concentration of copper and free acid in the aqueous phase. The results show the concentration
of copper in the organic phase is a linear function of ratio of concentrations of copper and free
acid in the aqueous phase.
The equilibrium correlation obtained on the results of isotherm curves of stripping step
from the laboratory is applied on the results of isotherm curves of stripping step using the
extractant Lix 984N for different value of volume percentage of extractant in the organic phase
and given the empirical modeling of stripping step. The modeling of stripping step is given by the
expression (26).
=(
xV% + 0.6183)x(
)+(
xV% +
(26)
Table 6: experimental data of isotherm curve of stripping step
g/l
51.3
43.2
37.7
33.8
32.3
31.2
g/l
1.76
1.38
1.21
1.07
1.01
0.98
13
Organic phase : Cu (g/l)
1,8
1,6
1,4
1,2
1
R = 0,9969
0,8
0,15
0,2
0,25
0,3
0,35
Aqueous phase : Ratio Cu/acid
Figure 4: Concentration of copper in organic phase versus the ratio of concentrations of copper
and free acidin the aqueous phase.
1.2.2. Isotherm of stripping step
The isotherm curve of stripping step is the repartition of copper between the aqueous
and organic phases after stripping. The stripping equilibrium correlation given by the
mathematical expressions (14) is used for the construction of isotherm curve on the stripping
step. The concentration of copper and free acid in the spent electrolyte and also the
concentration of extractant in the organic phase must be known for the construction of isotherm
curve on the stripping step.
There is two ways to construct the isotherm curve on the stripping step. The first way is
started from the concentration of copper in the aqueous at equilibrium from which the
concentration of copper in the organic phase is calculated. The second way is started from the
concentration of copper in the organic phase at equilibrium from which the concentration of
copper in aqueous phase is calculated.
First way:
It is easy to calculate the value of concentration of copper in the organic phase from the
concentration of copper in the aqueous phase using the mathematical expression (26). The
following example is chosen for the construction of isotherm curve on the stripping step.
The data for construction of isotherm curve on the stripping step come from Table 6.
The results are shown in Table 7.
14
Table 7: Concentration of copper in the organic phase on the stripping step

V%
%
8.7
8.7
8.7
8.7
8.7
8.7
g/l
51.3
43.2
37.7
33.8
32.3
31.2
g/l
30.7
30.7
30.7
30.7
30.7
30.7
g/l
190
190
190
190
190
190
g/l
1.746
1.397
1.188
1.052
1.001
0.965
The second way

The mathematical expression (27) gives the concentration of copper in the aqueous phase
as a function of concentration of copper in the organic phase.
(27)
where is a function of concentration of copper in the organic phase and volume percentage of
extractant in the organic phase. The mathematical expression (28) gives the value of .
(28)
The data from Table 7 are used for the construction of isotherm curve on the stripping
step for the second way. The results are shown in the Table 8.
Table 8: Copper concentration in the aqueous phase
g/l
1.75
1.40
1.19
1.05
1.00
0.97
V%
%
8.7
8.7
8.7
8.7
8.7
8.7
g/l
30.7
30.7
30.7
30.7
30.7
30.7
g/l
190
190
190
190
190
190
0.324
0.253
0.210
0.182
0.172
0.165
g/l
51.30
43.20
37.70
33.80
32.30
31.20
The curve of isotherm on the stripping step is plotted with the results from Table 6 and
Table 7 on Figure 5.
15
2,00
1,80
1,60
Organic phase, Cu (g/l)
1,40
1,20
1,00
0,80
Modeling
MIC
experimental data
MIC
0,60
0,40
0,20
0,00
30,0
35,0
40,0
45,0
50,0
55,0
Aqueous phase, Cu (g/l)

Figure 5: Isotherm curve of stripping step plotted from results from Table 6 and Table 7.
1.2.3. Minimum copper concentration in the stripped organic
The point MIC on Figure 5 is the coordinate of minimum concentration of copper in
organic phase at equilibrium with the spent electrolyte. The minimum concentration of copper in
the organic phase (MIC) is a function of concentrations of copper and free acid in the spent
electrolyte and also the volume percentage of extractant in the organic phase. The mathematical
expression (29) gives the value of MIC.
= (-6.295x10-3xV% + 0.6183)x(
) + (1.39x10-3xV% + 5.94x10-3)
(29)
16
2. Mass balance of copper solvent extraction

2.1.
Scheme of stage on the extraction and the stripping step
The extraction and stripping steps of copper solvent are frequently carried out at
industrial scale with the mixer-settlers. This equipment includes a mixer in one stage or two
stages in series to disperse one phase into the other to provide interfacial contact for mass
transfer, followed by the settler to allow the phases to coalesce and separate. Figure 6 and 7 give
the scheme of stage of rank n on the extraction and the stripping steps in the cascade
configuration.
En
Figure 6: The scheme of the stage n on the extraction step

The stage of rank n on the extraction step receives the aqueous phase
from stage
of rank n-1 and the organic phase
from the stage of rank n+1. The stage of rank n
produces the aqueous phase
and the organic phase
. In the extraction installation
containing m stages in cascade configuration, the stage of rank 1 receives the PLS ( ) and
produces the Loaded organic
( ). The last stage of rank m receives the stripped organic
(
) and produces the raffinate Raf ( ).
Sn
Figure 7: The scheme of stage of rank n on the stripping stage step

The stage of rank n on stripping step receives the aqueous phase
from stage of
rank n+1 and the organic phase
from stage of rank n-1. The stage of rank n produces
17
the aqueous phase

and the organic phase
. In the stripping installation containing p
stages in cascade configuration, the stage of rank 1 receives the loaded organic
( ) and
produces the advance electrolyte AD ( ). The last stage of rank p receives the spent
electrolyte SP (
) and produces the stripped organic
( ).
2.2.
Flow parameters of copper solvent extraction
Each aqueous phase leaving the stage of rank n on the extraction or the stripping step
is characterized by the following independent parameters:
-
= volumetric flow rate (m3/h).

= concentration of copper (g/l).
= concentration of free acid (g/l).
The mass flow rates of copper and free acid leaving the stage of rank n on the
extraction or the stripping step are given by the mathematical expressions (30) and (31)
respectively.
=
(kg/h)
(30)
(kg/h)
(31)
Each organic phase leaving the stage of rank n on the extraction or the stripping step is
characterized by the following independent parameters:
-

= volume percentage of extractant in the organic phase (%).
The mass flow rate of copper leaving the stage of rank n on the extraction or the
stripping is given by the mathematical expression (32).
=
2.3.
(32)
(kg/h)
Equations of mass balance of copper solvent extraction
2.3.1. Extraction step

Stage of rank n on the extraction step
On the extraction step, the mass balance equations are the following:
-
The conservation of volumetric flow of aqueous phase at the stage of rank n is given
by the mathematical expression (33).
=
(33)
The conservation of volumetric flow of organic phase at the stage of rank n is given by
18
(34)
=
-
The conservation of volume percentage of extractant in the organic phase at the stage of
rank n is given by the mathematical expression (35).
(35)
=
-
The ratio of organic and aqueous flows at the stage of rank n is given by the
=
(36)
The conservation of mass flow of copper at the stage of rank n is given by the
+
The relation between the

and the concentrations of copper in the inlet and outlet
flows of stage of rank n is given the mathematical expression (38).
(38)
=
-
The value of free acid in outlet aqueous phase of stage of rank n is given the
=
(37)
+(
)x1.54
(39)
The extraction efficiency of copper of stage of rank n is given by the mathematical

expression (40).
=
x 100
(40)
cascade configuration
On the extraction step, the equations of mass balance in the cascade configuration
containing m stages in series are the following:
-
The conservation of volumetric flow of aqueous phase of cascade is given by the

=
(41)
The conservation of volumetric flow of organic phase of cascade is given by the

=
(42)
19
The conservation of volume percentage of extractant in the organic phase of cascade is

given by the mathematical expression (43).
=
(44)
(45)
(46)
The value of free acid in outlet aqueous phase of cascade is given by the mathematical
expression (47).
=
(43)

flows of cascade is given by the mathematical expression (46).
=
The conservation of mass flow of copper of cascade is given by the mathematical

expression (45).
+
The ratio of organic and aqueous flows of cascade is given by the mathematical
expression (44).
=
+ (PLS-Raf)x1.54
(47)
The extraction efficiency of copper of cascade is given by the mathematical expression

(48).
=
x 100
(48)
2.3.2. Stripping step

stage of rank n of stripping step
On the stripping step, the equations of mass balance for the stage of rank n are the
following:
-
The conservation of volumetric flow of aqueous phase of stage of rank n is given by

=
The conservation of volumetric flow of organic phase of stage of rank n is given by

=
(49)
(50)
The conservation of volume percentage of extractant in the organic phase of stage of

rank n is given by the mathematical expression (51).
20
(51)
=
-
The ratio of organic and aqueous flows of stage of rank n is given by the mathematical
expression (52).
=
(52)
The conservation of mass flow of copper of stage of rank n is given by the

+

flows of stage of rank n is given by the mathematical expression (54).
(54)
=
-
The value of free acid in outlet aqueous phase of stage of rank n is given by the
=
(53)
+(
)x1.54
(55)
The stripping efficiency of copper of stage of rank n is given by the mathematical

expression (56).
=
x 100
(56)
Cascade configuration
On the stripping step, the equations of mass balance of cascade configuration containing
p stages in series are the following:
-
The conservation of volumetric flow of aqueous phase of cascade is given by the

= =
= =
(57)
The conservation of volumetric flow of organic phase of cascade is given by the

= =
= =
(58)
The conservation of volume percentage of extractant in the organic phase of cascade is

given by the mathematical expression (59).
= =
= =
(59)
21
The ratio of organic flow and aqueous flow of cascade is given by the mathematical
expression (60).
= =
The conservation of mass flow of copper of cascade is given by the mathematical

expression (61).
+
(60)
= =
(61)

flows of cascade is given by the mathematical expression (62).
=
The value of free acid in outlet aqueous phase of cascade is given by the mathematical
expression (63).
=
+(
(63)
)x1.54
The stripping efficiency of copper of cascade is given by the mathematical expression

(64).
=
(62)
x 100
(64)
The copper transfer from organic phase to the aqueous phase is given by the
=
(65)
(g/l Cu/1%V%)
2.3.3. Equilibrium constraints between the extraction and the stripping steps
In solvent extraction installation having the extraction step containing one or more
cascades and the stripping step containing one or more cascades, the equilibrium constraints
between extraction and stripping steps are given by the mathematical expressions (66) and (67).
2.4.
(66)
(67)
Mixing efficiency
2.4.1. Description of mixing efficiency

In the industrial installation of copper solvent extraction, the copper concentrations out
of mixer on the extraction and the stripping stage in the aqueous and organic phases are not at
equilibrium. This phenomenon is due to the temperature, the residence time in the mixer, the
model of impeller, the impeller power, the percentage of extractant in the organic phase, the
22
presence of iron, the solution viscosity, the ratio O/A in the mixer, the quality of extractant and
the concentration of copper in the organic phase [5].
2.4.2. Flow parameters
Each aqueous phase leaving the extraction or the stripping stage of rank n is
-

= concentration of free acid (g/l).
= concentration of copper at equilibrium (g/l).
= concentration of free acid at equilibrium (g/).
= mixing efficiency (%).
Each organic phase leaving the extraction or the stripping stage of rank n is
-

= concentration of copper at equilibrium (g/l).
= mixing efficiency (%).
= volume percentage of extractant in the organic phase (%).
2.4.3. Correlations of concentrations of copper

Extraction step
On the extraction step, the concentrations of copper in the aqueous and organic phases
leaving the stage of rank n are given by the mathematical expressions (68) and (69).
=
x(1-
(68)
x(1-
(69)
Stripping step
On the stripping step at stage of rank n, the concentrations of copper in the aqueous
and organic phases leaving the stage of rank n are given by the mathematical expressions (70)
and (71).
=
x(1-
(70)
x(1-
(71)
23
2.4.4. Industrial data of mixing efficiency

Table 9 gives the industrial values of mixing efficiency of different stage on the extraction
and the stripping steps. This measurement has been done on the North America solvent
extraction plant [6].
Table 8: Industrial mixing efficiency at different stages
Stage
Mixing efficiency (%)
2.5.
922
94 2
972
98
98
MacCabe Thiele diagram
2.5.1. Extraction step

The MacCabe Thiele diagram of stage of rank n on the extraction step is shown in
Figure (8). The point A gives the feed coordinate, the point B gives the outlet coordinate,
and the point C gives the outlet equilibrium coordinate. The triangle EB BD DE gives
the MacCabe Thiele diagram of stage of rank n on the extraction step.
Cn
Cuor/e
(n)
Bn
Cuor
En
(n)
Cuor(n+1)
Dn
Cuaq/e(n)
An
Cuaq(n)
Cuaq(n-1)
Figure 8: MacCabe Thiele diagram of stage of rank n on extraction step

The slope of line ED is
=
and is given by the mathematical expression (72).
24
(72)
The slope of line AB is

=
=-
(73)
2.5.2. Stripping step

The MacCabe Thiele diagram of stage of rank n on the stripping step is shown in
Figure (9). The point A gives the feed coordinate, the point B gives the outlet coordinate,
and the point C gives the outlet equilibrium coordinate. The triangle DA AE DE gives
the MacCabe Thiele diagram of stage of rank n on the stripping step.
An
Dn
Cuor(n-1)
Bn
Cuor
(n)
En
Cuor/e(n)
Cn
Cuaq(n+1)
Cuaq(n)
Cuaq/e(n)
Aquous phase, Cu (g/l)
Figure 9: MacCabe diagram of stage of rank n on the stripping.

The slope of line ED is
=
The slope of line AB is

=
=-
(74)
(47)
25
3. Simulation of solvent extraction scheme

3.1.
Constraints of copper SX/EW configuration
The constraints of copper SX/EW come from the copper solvent extraction
configuration as well as the industrial practices.
3.1.1. Maximum value of V% in the organic phase
The organic phase is constituted with the extractant and the diluent. The extractant is Lix
984N which is the mixing of 50% of 2-hydroxy-5-nonylacetophenone oxime and 50% of 5nonylasalcylaldoxime. The diluents are the organic liquid in which the extractant is dissolved. The
diluents are the hydrocarbons.
The viscosity of organic phase increases with increasing of volume percentage of
extractant. In the industrial practices, the maximum value of volume percentage of extractant in
the organic phase is 30 33% [7].
3.1.2. PLS and spent electrolyte temperature
The PLS temperature is a function of leaching technique. The temperature of PLS
coming from in situ leaching, heap leaching and vat leaching is generally less than 40C. The
temperature of PLS coming from agitated leach of oxide ores can reach 50C because of the
chemical reaction and the dilution of sulphuric acid in water are exothermic. In all case, the
temperature of PLS is less than 40C after storage in the pond.
The temperature of spent electrolyte out of EW is around 50C. The heat-exchanger is
placed on the spent electrolyte to transfer the heat from the spent electrolyte to the advance
electrolyte before the stripping step.
The temperature has not any effect on the thermodynamic and the kinetic of copper
solvent extraction.
3.1.3. Free acid concentration in the PLS
The concentration of free acid in the PLS is a function of leaching technique [6]. Table 9
gives the level of free acid in the outlet of leaching circuit.
Table 9: Concentration of free acid in the outlet leaching circuit
Leaching techniques
In situ leaching
Heap leaching
Vat leaching
Oxide agitated leaching
Sulphide agitated leaching
Autoclave
Bacterial leaching
Free acid (g/l)

0,5 - 8
3-8
6 - 40
1 - 15
12 - 25
25 - 80
25 - 55
pH
1,3 2,2
1,5 2,2
1,5 2,0
1,5 2,0
<1 1,6
<1 2,0
<1 2,2
26
The value of maximum concentration of copper in the organic phase (MAC) decreases
with increasing of concentration of free acid in the PLS. Figure 10 gives the ratio (MAC/ML)
obtained with the first way method for the construction of isotherm curve on the extraction step
versus the free acid in the PLS for the PLS containing 7 g/l of copper and the organic phase
containing 20% of Lix984N.
100,0
Organic phase, MAC/ML (%)
95,0
90,0
85,0
80,0
75,0
70,0
0,00
5,00
10,00
15,00
20,00
Aqueous phase, PLS free acid (g/l)
Figure 10: Ratio MAC/ML versus the free acid in the PLS (PLS 7 g/l of copper and organic
phase 20% Lix984N)
3.1.4. Maximum concentration of free acid in the spent electrolyte
The value of maximum concentration of free acid in the spent electrolyte is 180 g/l
. This maximum value of concentration of free acid is fixed by the rate of anode corrosion in the
EW circuit. It has been observed that the increase of concentration of free acid in the electrolyte
increases the disconnection of PbO2 to the Pb metallic. Therefore, it increases the rate of anode
corrosion [8].
3.1.5. Minimum concentration of copper in the spent electrolyte
The value of minimum concentration of copper in the spent electrolyte is 30 g/l. In the
copper EW circuit, the current density limit is the current density beyond which the copper
powder is produced. The value of current density limit increases with the increase of
concentration of copper in the electrolyte. The critical current density is the current density
beyond which the structure of copper cathode starts to be granular. It has been observed that the
value of critical current density is 35% of current density limits [9].
27
The maximum value of current density in the copper EW circuit is fixed by the rate of
anode corrosion due to oxygen evolution on the anode. The evolution of oxygen on the anode
increases with increasing of current density. The increase of oxygen evolution on the anode
increases also the unhooking of PbO2 on the anode. The maximum value of current density is
320 A/m2. This value allows to the anodes to have a life of 5 years. The value of maximum
current density must be lower than the critical current density of the concentration of copper in
the spent electrolyte. It has been observed that the minimum value of copper concentration in
the spent electrolyte which respects this constraint is 30 g/l. In the industrial practice, the value
of copper in the spent electrolyte is 35 g/l.
3.1.6. Maximum concentration of copper in the advance electrolyte
In the past time, the
/
ratio was fixed. This ratio is the enrichment factor of
concentration of copper from the leach solution and to the electrolyte. Under these conditions,
the concentration of copper in advance electrolyte increases with increasing the amount of
copper transferred. The maximum concentration of copper in the advance electrolyte is reached
when the LO/MAC ratio is 100%. The amperage of current to the EW was adjusted depending
on the concentration of copper in advance electrolyte.
Currently, the copper tank house is designed to work at the maximum level of the current
amperage. For a conventional cell containing 75 cathodes, the flow rate of the electrolyte is
increased to reach 15 m3/h. The increase in the cell flow rate is for a better quality of surface of
cathodes. The copper tank house consists of two parts; the first part, called scavenger cell, is
treating the advance electrolyte to oxidize the soluble organic phase coming with advance
electrolyte. The second part, called commercial cell, is treating the mixture of the outlet solution
of cell scavenger and the recycled solution outlet of same part. Accordingly, the copper
concentration gradient across the cell is 3 g/l. The design of copper tank house is done such as
the flow rate of electrolyte to the commercial cells is 4 times greater than the advance flow rate of
the electrolyte to the scavenger cells. Under these conditions, the maximum gradient of the
copper concentration between the spent and advance electrolytes is 15 g/l and for a copper
concentration in the spent electrolyte of 35 g/l, the maximum concentration of copper in the
advance electrolyte is 50 g/l.
Also note that increasing the concentration of copper in the advance electrolyte increases the
concentration of copper in the stripped organic phase and decreases the copper extraction
efficiency.
3.1.7. Minimum value of
The minimum value of
is reached when the value of
is reached the value of
MAC. The extraction is stopped. Therefore, the values of concentration of copper in the PLS
and in the raffinate are the same. The value of
is zero.
At a given value of LO/MAC lower than 100%, the value of
increases with decreasing
the value of volume percentage of extractant in the organic phase for a given PLS. Figure 11
gives the MacCabe Thiele diagrams on the extraction step of Copper SX having 15 and 25 % of
volume percentage of extraction after the simulation of copper SX working with the
conventional configuration 2Ex2S. The PLS has 7g/l of copper and 4 g/l of free acid. The spent
electrolyte has 35 g/l of copper and 180 g/l of free acid. The advance electrolyte has 50 g/l of
copper. The values of mixing efficiency for all mixers are 100%. The extractant is Lix984N. The
value of LO/MAC is 98%.
28
16,00
14,00
Oranic phase, Cu (g/l)
12,00
10,00
8,00
6,00
4,00
V% = 25%
2,00
V% = 15%
0,00
0,00
2,00
4,00
6,00
8,00
Aquous phase, Cu (g/l)
Figure 11: MacCabe Thiele diagram (15 and 25 % V% Lix984N)

The ratio
and
are the externals ratios. The internal ratio is the ratio of volumetric
flows in side of mixer. When the value of internal ratio (O/A) is greater than 1.1, the aqueous
phase is dispersed in the organic phase. The mixer works in the organic continuity regime. In the
other side, when the ratio (A/O) is greater than 1.1, the organic phase is dispersed in the aqueous
phase. The mixer works in aqueous continuity regime.It has been observed that the crud
formation decreases when the mixer works in the organic continuity regime [10]. Therefore, all
mixers on the extraction and the stripping steps work in the organic continuity regime and the
minimum value of ratio
is now 1.1 which gives the smallest size of mixer and settler without
any organic or aqueous stage recycle.
3.1.8. Maximum value of
When the value of the loaded organic (
) is equal to the value of minimum
concentration of copper in the stripped organic (MIC), the stripping is stopped. The
concentrations of copper in the spent electrolyte and in the advance electrolyte are the same. The
value of ratio
is infinity.
When the value of loaded organic (
) is equal to the value of
which is at
equilibrium with the advance electrolyte, the ratio
is reached the maximum value which allows
to have the target value of AD on the stripping step.
When the ratio
increases, the extraction efficiency increases for a given PLS and the
volume percentage of extractant in the organic phase. There is a maximum value of ratio
above which the extraction efficiency
starts to decrease. The value of loaded organic (
)
corresponding to the maximum value of extraction efficiency stills greater than the
on the
stripping step. The new maximum value of ratio
increases with decreasing the volume
percentage of extractant in the organic phase for a given PLS. Table 10 gives the values of
29
extraction efficiency
and the ratio
as a function of ratio
after the simulation of
copper solvent extraction working with the conventional configuration 2Ex2S. The PLS has 7g/l
of copper and 4 g/l of free acid. The spent electrolyte has 35 g/l of copper and 180 g/l of free
acid. The advance electrolyte has 50 g/l of copper. The values of mixing efficiency for all mixers
are 100%. The volume percentage of extractant in the organic is 25% (Lix984N).
Table 10: Extraction efficiency versus the ratio of organic and aqueous flows on the extraction
step
0.882
1.085
1.370
2.000
2.500
3.000
4.000
3.2.
%
96.09
97.15
97.59
97.97
97.97
97.77
97.70
%
43.86
34.81
26.28
16.34
12.13
9.41
6.20
Optimum value of volume percentage of extractant in the organic
3.2.1. Constraints
All data for the copper solvent extraction simulation are fixed. It remains only the volume
percentage of extractant in the organic phase. The simply way to find the optimum value of
volume percentage of extractant is to change the volume percentage of extractant until the
maximum extraction efficiency is reached. Table 11 gives the values of extraction efficiency
,
stripping efficiency
, copper transfer
and ratio
as a function of the volume
percentage of extractant after the simulation of copper solvent extraction working with the
conventional configuration 2Ex2S. The PLS has 7g/l of copper and 4 g/l of free acid. The spent
electrolyte has 35 g/l of copper and 180 g/l of free acid. The advance electrolyte has 50 g/l of
the copper. The values of mixing efficiency for all mixers are 100%. The value of ratio
is 1.1.
The extractant is Lix984N.
Table 11: Results of copper solvent extraction at different values of V%
V%
12.5
15.0
17.5
20.0
22.5
25.0
27.5
30.0
32.5
%
71.74
84.77
92.51
95.52
96.67
97.19
97.44
97.57
97.62
%
72.63
72.32
70.89
68.65
66.22
63.84
61.58
59.46
57.46
g/l/1%V%
0.365
0.360
0.336
0.304
0.273
0.247
0.225
0.207
0.191
%
97.70
94.70
88.47
80.56
73.05
66.36
60.43
55.15
50.40
30
The results show that the extraction efficiency increases with increasing of volume
percentage of extraction in the organic phase. In the other side, the stripping efficiency, the
copper transfer, and the ratio LO/MAC decrease with increasing of volume percentage of
extractant in the organic.
In the old time, the choice of optimum was based on the high value of extraction
efficiency. Actually, the choice is based on the organic phase saturation with the copper.
3.2.2. Maximum extraction efficiency
For the choice based on the highest extraction efficiency, Figure 12 gives the extraction
efficiency as a function of stripping efficiency. The results show that the extraction efficiency
increases with decreasing of stripping efficiency. So the minimum value of stripping efficiency
which is given the highest extraction efficiency is 60% with two stages on the stripping step.
Below this minimum value of stripping efficiency, the gain on the extraction efficiency is
insignificant.
Other copper solvent extraction simulations having 60% of stripping efficiency are done.
Table 11 gives the values of volume percentage of extractant, the extraction efficiency
, the
copper transfer
, and the ratio LO/MAC as a function of ratio
after the simulation of
copper solvent extraction working with the conventional configuration 2Ex2S. The PLS has 7g/l
of copper and 4 g/l of free acid. The spent electrolyte has 35 g/l of copper and 180 g/l of free
acid. The advance electrolyte has 50 g/l of copper. The values of mixing efficiency for all mixers
are 100%. The extractant is Lix984N. The results show that, the volume percentage of extraction
decreases with increasing of ratio . In the other hand, the extraction efficiency and the copper
transfer remain constant with increasing of ratio .
Aqueous phase, extraction efficiency (%)
100
95
90
85
80
75
70
55
60
65
70
Organic phase, stripping efficiency (%)
31
Figure 12: Extraction efficiency versus stripping efficiency
Table 12: Results of copper solvent extraction simulation with 60% of stripping efficiency
1.1
1.3
1.5
1.7
1.9
%
29.34
24.74
21.37
18.79
16.76
%
97.55
97.51
97.42
97.30
97.16
g/l/1%V%
0.212
0.212
0.213
0.213
0.214
%
56.49
60.79
63.58
65.47
66.81
3.2.3. Saturation of organic phase with the copper

The ferric is the only impurity which can be transferred to the copper electrolyte by
chemical and physical entrainment. In the normal copper solvent plant working together with the
normal leaching technique of oxide ores, the chemical entrainment of iron is between 35 to 60%
of total entrainment [11]. The presence of iron in the copper electrolyte causes the reduction of
current efficiency. The maximum concentration of iron in the copper electrolyte is 2g/l. The
bleed of copper electrolyte is applied to maintain the iron concentration in the copper electrolyte
at less than 2 g/l. The increase of the flow rate of copper electrolyte bleed increases the cost of
cobalt reagent which is added to the copper EW circuit.
In all copper solvent extraction plants working in cascade configuration with two stages
on the extraction step, it has been observed that the concentration of iron in the partial loaded
organic out of stage 2 is greater than the concentration of iron in the loaded organic out of stage
1. This effect is called crowding [11].
The new copper solvent extraction design takes account the crowding effect. So the
copper loaded organic must be saturated with the copper. In the other hand, Figure 13 shows
that the extraction efficiency decreases with increasing of ratio LO/MAC. The data of Figure 13
come from Table 11. The minimum value of ratio LO/MAC above which the crowding effect
can work is 80%. The configuration of the copper solvent extraction is changed from 2Ex2S to
3Ex1S, series parallel, interlaced, double series parallel to improve the extraction efficiency.
Other copper solvent extraction simulation having 80% of ratio LO/MAC are done.
Table 13 gives the values of volume percentage of extractant
, the extraction efficiency
,
the stripping efficiency
, and the copper transfer
as a function of ratio
after the
simulation of copper solvent extraction working with the conventional configuration 2Ex2S. The
PLS has 7g/l of copper and 4 g/l of free acid. The spent electrolyte has 35 g/l of copper and 180
g/l of free acid. The advance electrolyte has 50 g/l of copper. The values of mixing efficiency for
all mixers are 100%. The ratio LO/MAC remains constant at 80%. The extractant is Lix984N.
The results show that the increase of the ratio
decreases the volume percentage of
extraction. In the other hand, the extraction efficiency remains constant with increasing of ratio
. The stripping efficiency and the copper transfer decrease with the increase of ratio .
32
Aqueous phase, extraction efficiency (%)
100
95
90
85
80
75
70
50
60
70
80
90
100
Organic phase, ratio LO/MAC (%)
Figure 13: Extraction efficiency versus the ratio LO/MAC

Table 13: Results of copper solvent extraction simulation
1.1
1.3
1.5
1.7
1.9
%
20.18
17.72
15.76
14.17
12.88
%
95.64
95.66
95.59
95.46
95.32
%
68.48
67.60
66.95
66.45
66.03
g/l/1%V%
0.302
0.291
0.283
0.277
0.273
33
3.3.
Procedure of copper solvent extraction simulation
3.3.1. Plant description

The explanation step by step of simulation procedure is done through an example. The
procedure is the combination of graphic and algebra methods. Table 14 gives the data of chosen
example of copper solvent extraction installation working with the conventional configuration
2Ex2S and Figure 14 gives the scheme.
Table 14: Parameters of copper solvent extraction simulation
Description
Symbol
Extraction step
Unity
Value
g/l
g/l
7
4
1.1
Constraint of optimum value of V%
80
Mixing efficiency extraction stage 1

Mixing efficiency extraction stage 2
Number of extraction stage
%
%
93
95
2
g/l
g/l
g/l
%
%
35
180
50
98
98
2
Copper concentration in the PLS

Acid concentration in the PLS
Ratio
Stripping step
Copper concentration in the SP
Acid concentration in the SP
Copper concentration in the AD
Mixing efficiency stripping stage 1
Mixing efficiency stripping stage 2
Number of stripping stage
AD
3.3.2. Simulation procedure

The simulation procedure of copper solvent extraction follows this step:
A. Copper solvent extraction simulation table

The simulation Table is given by Table 15 as it appears on the Excel Microsoft
spreadsheet. The simulation Table is made with tree small Tables which are Table of extraction
step, Table of stripping step, and Table of Goal seek. On the extraction and the stripping Tables,
there is, on the upper part, the extraction and stripping data coming from Table 14 and on the
lower part, the coordinates of points , ,
and
from Figures 8 and 9. For each stage on
the extraction step small Table; there is, on the right side, the parameters , A, B, C and
which allow calculating the value of copper concentration in the aqueous phase from the value of
concentration in the organic phase at equilibrium.
The simulation Table with all data from Table 14 is given by Table 16.
34
A
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
Table 15: simulation table of copper solvent extraction

Extraction step
Extraction step data
g/l
g/l
g/l
%
MAC
%
LO/MAC
Stage 1
%
%
Parameters
A
B
C
Stage 2
Parameters
A
B
C
Stripping step
Stripping step Data

g/l
g/l
%
AD
g/l
%
Stage 1
Stage 2
Goal seek
2
3
Set cell
By changing
Conditions
B value
35
A
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48

Extraction step
7
4
MAC
93
g/l
g/l
g/l
%
%
LO/MAC
Stage 1
1.1
80
95
%
%
Parameters
A
B
C
Stage 2
Parameters
A
B
C
Stripping step
Stripping step Data

35
180
98
g/l
g/l
%
AD
50
g/l
98
Stage 1
Stage 2
Goal seek
2
3
Set cell
By changing
Conditions
B value
36
PLS
Raf
E1
E2
LOe
SOe
LOs
SOs
S1
S2
AD
SP
Figure 14: Copper solvent extraction plant scheme
B. Simulation procedure of extraction step

1. The simulation is started by the calculation of MAC value for the PLS at different value
of volume percentage of extractant in the organic phase. If the extraction step is made by
more than one cascades (series parallel, interlaced, and others), the MAC value is
calculated with the first PLS which is the feed of stage of rank 1 on the extraction step.
The results of MAC value are in Table 17 and Figure 15. From Figure 15, the
extrapolation curve which gives the value of MAC versus the volume percentage of
extractant is found from Excel Microsoft application. The mathematical expression of
extrapolation curve is given on Figure 15.
Table 17: MAC value for different value of volume percentage of extractant
V%
%
10.0
12.5
15.0
17.5
20.0
22.5
25.0
27.5
30.0
g/l
7
7
7
7
7
7
7
7
7
g/l
4
4
4
4
4
4
4
4
4
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
2.286
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MAC
g/l
5.04
6.42
7.87
9.39
11.00
12.73
14.59
16.65
18.95
37
20,00
Organic phase, MAC (g/l)
16,00
12,00
8,00
4,00
y = 3,110E-04x3 - 8,741E-03x2 + 6,409E-01x - 8,195E-01

R = 1,000E+00
0,00
10,00
15,00
20,00
25,00
30,00
Organic phase, extractant volume percentage (%)
Figure 15: MAC versus the volume percentage of extractant V%

-
In the cell C8, type =3.11*10^-4*F6^3-8.741*10^-3*F6^2+0.6409*F6-0.8195
2. The starting value of volume percentage of extractant for the simulation is the random
value lower than 30%. The optimum value of volume percentage of extractant will be
known at the end of simulation by using the goal seek Excel Microsoft application. For
this case, the chosen starting value is 18%.
-
In the cell C45, type the value 18.

In the cell F6, type =C45.
3. The value of loaded organic

on the extraction step is calculated from the constraint
of optimum volume percentage on the extraction step (
= 80%). This value is the
of point
4.
. The
of point
is
In the cell D12, type =C8*F8/100.

In the cell C12, type =C6.
of point
is equal to
of point
In the cell D13, type =D12.
5.
of point
is greater than
of point
(Figure 8).
of the point is not
known from the extraction step data table. This value will be found by using goal seek
Excel Microsoft application. The starting value of
of point
is random value
greater than
of point
(the difference between
of point
and
is lower
than 1). This case the starting value is 8.
38
In the cell D45, type 8.

In the cell D46, type =if(D14>D13,yes,no).
6.
of point will be calculated from

of same point using the second way for the
construction of isotherm curve on the extraction step.
Type=((3.4657*LN(F6)-13.524)*(D14/F6)-1.553*LN(F6)+6.4051)*(3.303*F63.0842*D14)^2/D14in the cell G12.

In the cell G13, type 2.3716.
In the cell G14, type =-(3.08*C7+4.7432*C6+G12).
In the cell G15, type =(C7+1.54*C6)^2.
In the cell G16, type =G14^2-4*G13*G15.
In the cell C14, type =(-G14-G16^0.5)/(2*G13).
7.
8.
9.
-
of point
is calculated using the mathematical expression (68).
In the cell C13, type =C14*C9/100 + C12*(1-C9/100).

of point
is equal to
of point

of point
In the cell D15, type =D12-(C12-C13)/F7.
10. The goal seek condition of

expression (69).
-
of point
is calculated using the mathematical
In the cell D44, type =D14*C9/100+D15*(1-C9/100)-D13
11. The goal seek operation for

-
of point
can be applied.
In the Set cell field, type D44.
In the To value field, type 0.
In the By changing cell field, type D45.
dialog box.
Click Ok.
12. The coordinates of point
and the point
are the same.

39
13.

of point
is equal to
of point
.
14.
of point
is greater than
of point
(Figure 8).
of point
is not
known from the extraction step data table. This value will be found by using goal seek
of point
is random value
greater than
of point
of point
and
is lower
In the cell E45, type 4.

In the cell D21, type =E45.
In the cell E46, type =if(D21>D20,yes,no).
In the cell E47, type =D20.
15.
of point will be calculated from

of same point using the second way for the
construction of isotherm curve on the extraction step.
Type=((3.4657*LN(F6)-13.524)*(D21/F6)-1.553*LN(F6)+6.4051)*(3.303*F63.0842*D21)^2/D21in the cell G19.

In the cell G20, type 2.3716.
In the cell G21, type =-(3.08*C7+4.7432*C6+G19).
In the cell G22, type =(C7+1.54*C6)^2.
In the cell G23, type =G21^2-4*G20*G22.
In the cell C21, type =(-G21-G23^0.5)/(2*G20).
16.
17.
18.
-
of point
In the cell C20, type =C21*F9/100 + C19*(1-F9/100).

of point
is equal to
of point
In the cell D22, type =D19-(C19-C20)/F7.
of point
In the cell E44, type =D21*F9/100+D22*(1-F9/100)-D20

-

expression (69).
-
of point
of point
can be applied.
In the Set cell field, type E44.
In the By changing cell field, type E45.
40
dialog box.
Click Ok.
21. Table 18 is appeared
C. Simulation procedure of stripping step

1. The ratio
is calculated using the combination of mathematical expressions (62), (66)
and (67). If the
value is known, the concentration of copper of advance electrolyte
(AD) will be calculated using the combination of mathematical expressions (62), (66) and
(67).
-
In the cell F27, type =(F26-C26)/(D12-D22).
2. The
of point
at the stripping step is equal to the
extraction step (mathematical expression 66).
-
of point
is equal to the value of AD.
In the cell C31, type =F26.
4. The
-
at the
3. The
-
of point
of point
is equal to
of point
5. The
of point
is greater than
of point
(Figure 9).
of point
is not
known from the stripping step data Table. This value will be found by using goal seek
of point
is random value
greater than
of point
of point
and
is lower
-
In the cell F45, type 51.

In the cell C33, type =F45.
In the cell F46, type =if(C33>C32,yes,no).
In the cell F47, type =C32.
6. The
of point
will be calculated from the
of same point using the first way
for the construction of isotherm curve on the stripping step (mathematical expression
26).
-
Type=F6*((-6.295*10^-3*F6+0.6183)*(C33/(C27+(C26-C33)*1.54))+(1.39*10^3*F6+5.94*10^-3))in the cell D33.

7. The
-
of point
In the cell D32, type =D33*C28/100 + D31*(1-C28/100).
41
A
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48

Extraction step
7
4
MAC
9.698
93
g/l
g/l
g/l
%
LO/MAC
Stage 1
7
2.708
2.385
2.708
%
%
%
7.759
7.759
8.052
3.857
Parameters
51.728
A
2.3716
B
-97.250
C
218.45
7.385E+03
3.857
3.857
3.966
1.792
Parameters
643.21
A
2.3716
B
-688.73
C
218.45
4.723E+05
Stage 2
2.708
0.437
0.318
0.437
18
1.1
80
95
Stripping step
Stripping step Data
35
180
98
g/l
g/l
%
AD
50
g/l
98
Stage 1
Stage 2
1
Set cell
By changing
Conditions
B value
18
Goal seek
2
3
0.000
0.000
8.052
3.966
Yes
Yes
7.759
3.857
42
8. The
-
is equal to the
of point
In the cell C34, type =C31-F27*(D31-D34).

of point
can be applied.
and the point
are the same.

13. The
-
of point
In the Set cell field, type F44.
In the By changing cell field, type F45.
dialog box.
Click Ok.
12. The coordinates of point

-
In the cell F44, type =C33*C28/100+C34*(1-C28/100)-C32

-

expression (70).
-
of point
9. The
-
of point
of point
is equal to
of point
14. The
of point
is greater than
of point
(Figure 9).
of point
is
not known from the stripping step data Table. This value will be found by using goal
seek Excel Microsoft application. The starting value of
of point
is random value
greater than
of point
of point
and
is lower
-
In the cell G45, type 40.

In the cell C39, type =G45.
In the cell G46, type =if(C39>C38,yes,no).
In the cell G47, type =C38.
15. The
of point
will be calculated from the
of same point using the first way
for the construction of isotherm curve on the stripping step (mathematical expression
26).
-
Type=F6*((-6.295*10^-3*F6+0.6183)*(C39/(C27+(C26-C39)*1.54))+(1.39*10^3*F6+5.94*10^-3))in the cell D39.

43
16. The
-
of point
is equal to the
of point
In the cell C40, type =C37-F27*(D37-D40).
of point
In the cell G44, type =C39*F28/100+C40*(1-F28/100)-C38

-

expression (70).
-
of point
18. The
-
In the cell D38, type =D39*F28/100 + D37*(1-F28/100).
17. The
-
of point
of point
can be applied.
In the Set cell field, type G44.
In the By changing cell field, type G45.
dialog box.
Click Ok.
D. Goal seek operation of volume percentage of extractant

1. The goal seek condition of volume percentage of extractant is calculated using the
-
In the cell C44, type =D22-D40
2. It appears Table 19.

3. The goal seek operation for V% can be applied.
-
In the Set cell field, type C44.
In the By changing cell field, type C45.
dialog box.
Click Ok.
44
A
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48

Extraction step
7
4
MAC
9.698
93
g/l
g/l
g/l
%
LO/MAC
Stage 1
7
2.708
2.385
2.708
%
%
%
7.759
7.759
8.052
3.857
Parameters
51.728
A
2.3716
B
-97.250
C
218.45
7.385E+03
3.857
3.857
3.966
1.792
Parameters
643.21
A
2.3716
B
-688.73
C
218.45
4.723E+05
Stage 2
2.708
0.437
0.318
0.437
18
1.1
80
95
Stripping step
Stripping step Data
35
180
98
g/l
g/l
%
AD
50
2.514
98
g/l
4
0.000
50.22
Yes
50.00
5
0.000
39.49
Yes
39.44
Stage 1
50.00
50.00
50.22
39.44
7.759
3.558
3.473
3.558
39.44
39.44
39.49
37.15
3.558
2.649
2.631
2.649
Stage 2
1
Set cell
By changing
Conditions
B value
18
Goal seek
2
3
0.000
0.000
8.052
3.966
Yes
Yes
7.759
3.857
45
A
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48

Extraction step
7
4
MAC
10.869
93
g/l
g/l
g/l
%
LO/MAC
Stage 1
7
2.704
2.381
2.704
%
%
%
8.695
8.695
8.989
4.790
Parameters
51.867
A
2.3716
B
-97.389
C
218.45
7.412E+03
4.790
4.790
4.895
2.795
Parameters
509.33
A
2.3716
B
-554.85
C
218.45
3.058E+05
Stage 2
2.704
0.510
0.394
0.510
19.82
1.1
80
95
Stripping step
Stripping step Data
35
180
98
g/l
g/l
%
AD
50
2.542
98
g/l
4
0.000
50.25
Yes
50.00
5
0.000
37.87
Yes
37.81
Stage 1
50.00
50.00
50.25
37.81
8.695
3.901
3.804
3.901
37.81
37.81
37.87
35.00
3.901
2.796
2.773
2.796
Stage 2
Set cell
By changing
Conditions
B value
1
-0.001
19.82
Goal seek
2
3
0.000
0.000
8.989
4.895
Yes
Yes
8.695
4.790
46
4. The goal seek operation of all goal seek is repeated in the direction of clockwise until all
value of set-cell become zero. At each moment, the cell condition in the goal seek
table shows no, the value in the changing cell must be change to be greater than
the B value in the same column. It appears Table 20.
E. Results table
Table 21 gives the results of simulation of copper solvent extraction installation.
Table 21: Results Table of simulation of the copper solvent extraction
Extraction step
Description
Extractant volume percentage
Copper concentration of PLS
Acid concentration of PLS
Ratio of organic and aqueous flows
Extraction efficiency
Loaded organic
Maximum copper concentration in the organic phase
Copper concentration of Raffinate
Mixing efficiency stage 1
Stripping step
Ratio of organic and aqueous flows
Stripping efficiency
Copper transfer
Copper concentration of stripped organic
Copper concentration of advance electrolyte
Copper concentration of spent electrolyte
Acid concentration of spent electrolyte
Symbol
V%
LO
MAC
Raf
SO
AD
value
19.82
7
4
1.1
92.72
8.645
10.869
0.510
93
95
2.542
67.85
0.298
2.795
98
98
50
35
180
unity
%
g/l
g/l
%
g/l
g/l
g/l
%
%
%
g/l/V%
g/l
%
%
g/l
g/l
g/l
F. MacCabe Thiele diagram

The graphic representation of results of copper solvent extraction is in the form of the
Mac Cabe Thiele diagram. The coordinates of points , , , , , and
of stages 1 and 2
on the extraction step and the coordinates of points , , , , , and
of stages 1 and 2
on the stripping step are in Table 20. It remains only the construction of isotherm curves on the
extraction and the stripping step.
The construction of isotherm curve on the extraction step needs the values of volume
percentage of extractant in the organic phase and the concentrations of copper and free acid in
the PLS. The construction of isotherm curve on the stripping step needs the values of volume
percentage of extractant in the organic phase and the concentrations of copper and free acid in
the spent electrolyte. Table 21 gives the coordinates of isotherms curves on the extraction and
the stripping. Figures 16 and 17 give the MacCabe Thiele diagram of extraction and stripping
steps.
47
Table 21: Coordinates of isotherm curves on the extraction and the stripping
Extraction
g/l
0.26
0.33
0.41
0.52
0.64
0.80
0.99
1.23
1.53
2.39
3.89
Stripping
g/l
4.00
4.50
5.00
5.50
6.00
6.50
7.00
7.50
8.00
9.00
10.00
g/l
32.50
35.00
37.50
40.00
42.50
45.00
47.50
50.00
52.50
g/l
2.39
2.57
2.75
2.93
3.13
3.34
3.55
3.78
4.02
12,00
10,00
E1
8,00
B1
6,00
B2
4,00
D1
2,00
D2
0,00
0,00
2,00
4,00
6,00
8,00
Aqueous phase, Cu (g/)
Figure 16: MacCabe Thiele diagram of extraction step
48
10,00
D1
8,00
6,00
E1
B1
4,00
E2
B2
2,00
0,00
30,00
35,00
40,00
45,00
50,00
55,00
Figure 17: MacCabe Thiele diagram of stripping step
49
References
1. Hossen Aminian, Modlisation et simulation des oprations dextraction par solvant et
dlectrolyse du Cuivre, thse, universit de Laval, Canada, 1999.
2. 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.
3. AMEL A., Etude thermodynamique de lextraction des Mtaux de transition par la
Salicylidneaniline, thse, Universit Mohamed Khider, 2013.
4. BASF, Redbook mining solutions, 2014.
5. Sorderstrom M., Bednarki T., Villegas E., Stage efficiency in Copper solvent extraction
Plants, technical paper, 2010.
6. Cognis, Copper solvent extraction training, 2007.
7. Murdoch Mackenzie, The solvent extraction of some major metals: overviews, Henkel
Australia Pty ltd.
8. Jeffers T.H, Groves R.D, Minimizing lead contamination in copper produced by solvent
extraction electrowinning, Salt Lake City Research Center.
9. Cl. Feneau, R. Breckpot, Problmes relatifs llectrocristallisation du cuivre, Laboratoire
de chimie minrale, universit de Louvain.
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.
50

Design of Copper Solvent Extraction Configurations

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Design of Copper Solvent Extraction Configurations

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Joseph Kafumbila

Design of Copper solvent extraction

Copyright 2015 Joseph Kafumbila

Joseph Kafumbila | Process designer-2015

Joseph Kafumbila | Process designer-2015

1. Modeling and isotherm of copper solvent extraction

is the chemical or electrochemical potential of species i.

The chemical potential of species I is given by the mathematical expression (2).

where is the chemical activity coefficient of species I, I is the concentration of specie I in

Joseph Kafumbila | Process designer-2015

Joseph Kafumbila | Process designer-2015

Table 1: Extraction isotherm experimental data

Organic phase : Metal concentration (g/l)

Figure 1: valuesof K versus the concentrations of copper in the organic phase

On the Microsoft spreadsheet, type 0.09 of copper concentration in the aqueous

Joseph Kafumbila | Process designer-2015

Joseph Kafumbila | Process designer-2015

The second way

The concentration of copper in the aqueous phase is given by the mathematical

The value of is given by the mathematical expression (22).

Joseph Kafumbila | Process designer-2015

Table 5: Extraction isotherm established from copper concentration in organic phase

Organic phase, Copper (g/l)

Aqueous phase, copper (g/l)

Joseph Kafumbila | Process designer-2015

Maximum load, ML (g/l)

Organic phase, V% of Lix984N

1.2.1. Modeling of stripping

Joseph Kafumbila | Process designer-2015

Table 6: experimental data of isotherm curve of stripping step

Joseph Kafumbila | Process designer-2015

Organic phase : Cu (g/l)

Aqueous phase : Ratio Cu/acid

Joseph Kafumbila | Process designer-2015

Table 7: Concentration of copper in the organic phase on the stripping step

The second way

Joseph Kafumbila | Process designer-2015

Organic phase, Cu (g/l)

Aqueous phase, Cu (g/l)

Joseph Kafumbila | Process designer-2015

2. Mass balance of copper solvent extraction

Scheme of stage on the extraction and the stripping step

Figure 6: The scheme of the stage n on the extraction step

Figure 7: The scheme of stage of rank n on the stripping stage step

the aqueous phase

Flow parameters of copper solvent extraction

= volumetric flow rate (m3/h).

= volumetric flow rate (m3/h).

Equations of mass balance of copper solvent extraction

2.3.1. Extraction step

The relation between the

The extraction efficiency of copper of stage of rank n is given by the mathematical

The conservation of volumetric flow of aqueous phase of cascade is given by the

The conservation of volumetric flow of organic phase of cascade is given by the

The conservation of volume percentage of extractant in the organic phase of cascade is

The relation between the

The conservation of mass flow of copper of cascade is given by the mathematical

The extraction efficiency of copper of cascade is given by the mathematical expression

2.3.2. Stripping step

The conservation of volumetric flow of aqueous phase of stage of rank n is given by

The conservation of volumetric flow of organic phase of stage of rank n is given by

The conservation of volume percentage of extractant in the organic phase of stage of

The conservation of mass flow of copper of stage of rank n is given by the